JP2019059852A - Fiber reinforced polyamide resin substrate, manufacturing method therefor, and molded article and composite molded article containing the same - Google Patents

Abstract

To provide a fiber reinforced polyamide resin substrate excellent in impregnation property and heat stability, less in void and excellent in surface quality.SOLUTION: There is provided a fiber reinforced polyamide resin substrate by impregnating a polyamide resin into a continuous reinforced fiber or a reinforced fiber substrate in which discontinuous reinforced fiber is dispersed, in which the polyamide resin is a terminal modified polyamide resin in which at least a part of a polymer constituting the polyamide resin has a structure constituted by a structural unit different from a repeated structural unit constituting a main chain of the polymer at a terminal group of the polymer, the terminal modified polyamide resin contains a terminal structure represented by the following general formula (I) of 1 to 20 mass%. -X-(R-O)-H (I). In the general formula (I), m represents a range of 2 to 100, Rrepresents a bivalent hydrocarbon group having 2 to 10 carbon atoms, -X- represents -NH-, -N(CH)- or -(C=O)-. m Rcontained in the general formula (I) may be same or different.SELECTED DRAWING: None

Description

  The present invention relates to a fiber-reinforced polyamide resin substrate, a method for producing the same, a molded article and a composite molded article containing the same.

  A fiber-reinforced polyamide resin substrate obtained by impregnating a polyamide resin with a continuous reinforcing fiber or a reinforcing fiber base in which discontinuous reinforcing fibers are dispersed is excellent in specific strength and specific rigidity, and has a high weight saving effect. Because of their high heat resistance and chemical resistance, they are preferably used in transportation equipment such as aircraft and automobiles, and in various applications such as sports and electric and electronic parts. In recent years, with the increasing demand for weight reduction, the substitution of metal parts to resin parts and the miniaturization and modularization of parts are progressing mainly in aircraft and automobile applications, and therefore, it has excellent formability and processability. Material development with excellent mechanical properties is required.

As a composite material for a structural material excellent in moldability and mechanical properties, for example, a carbon fiber reinforced polyamide resin prepreg (see, for example, Patent Document 1) formed by containing carbon fiber in a polyamide resin is known.
JP, 2013-159675, A

  However, in the technique disclosed in Patent Document 1, although it is expected as a weight reduction material because of high mechanical properties, it takes time to impregnate a carbon fiber bundle with a polyamide resin, so the productivity is low and the impregnatability is low. Further improvements were required. The melt flowability of the polyamide resin decreases as the molecular weight increases. Therefore, when it is used as a fiber-reinforced polyamide resin base material, the impregnating ability to the reinforcing fiber bundle decreases, and the problem of increasing voids, fluff generation and resin rich There has been a problem that the surface quality is lowered due to the increase in the number of parts. Although it is possible to improve the melt flowability by raising the processing temperature, the thermal stability is lowered, and thermal decomposition accompanied by gas generation occurs during processing, so surface grade due to increase of voids and deterioration of matrix resin There was a problem that caused a decline. Then, this invention makes it a subject to provide the fiber reinforced polyamide resin base material which was excellent in impregnatability and thermal stability, and which has few voids and excellent surface quality.

In order to solve the said subject, the fiber reinforced polyamide resin base material of this invention has the following structures. That is,
A fiber-reinforced polyamide resin base material comprising a continuous reinforcing fiber or a reinforcing fiber base in which discontinuous reinforcing fibers are dispersed is impregnated with a polyamide resin, wherein the polyamide resin is at least a polymer constituting the polyamide resin A terminal-modified polyamide resin having a structure composed of a structural unit different from the repeating structural unit constituting the main chain of the polymer at the terminal group of the polymer, wherein the terminal-modified polyamide resin has the following general formula (I The fiber reinforced polyamide resin base material which contains the terminal structure represented by 1.) in 1-20 mass%.
_{^{-X- (R 1 -O) m -H}} (I)

In the above general formula (I), m represents a range of 2 to 100. R ¹ represents a divalent hydrocarbon group having 2 to 10 carbon atoms. -X- is _{-NH -, - N (CH 3} ) - or - (C = O) - represents a. The m R ^{1 s} contained in the general formula (I) may be the same or different.

The method for producing a fiber-reinforced polyamide resin substrate of the present invention has the following constitution. That is,
When polymerizing an amino acid, a lactam, and / or a diamine and a dicarboxylic acid, the terminal modifying compound represented by the following general formula (III) is 1 to 20 mass based on the total of the amino acid, lactam, diamine and dicarboxylic acid %, And a terminal-modified polyamide resin containing 1 to 20% by mass of a terminal structure represented by the following general formula (I) is obtained by bonding a terminal-modifying compound to the terminal of the polyamide resin, and continuously The method for producing a fiber-reinforced polyamide resin substrate according to any one of the above, further comprising the step of impregnating the end-modified polyamide resin with the reinforcing fiber in which the reinforcing fiber is dispersed or in the reinforcing fiber base in which the reinforcing fiber of discontinuous fiber is dispersed.
H-X- (R ¹ -O) _m -H (III)
_{^{-X- (R 1 -O) m -H}} (I)

In the above general formulas (III) and (I), m represents a range of 2 to 100. R ¹ represents a divalent hydrocarbon group having 2 to 10 carbon atoms. The general case expression is (III), -X- is _{-NH -, - N (CH 3} ) - or -O (C = O) - represents a. The general case expression is (I), -X- is _{-NH -, - N (CH 3} ) - or - (C = O) - represents a. The m R ^{1 s} contained in the general formula (III) may be the same or different.

The molded article containing the fiber reinforced polyamide resin base material of this invention has the following structure. That is,
It is a molded article containing the said fiber reinforced polyamide resin base material.

The composite molded article of the present invention has the following constitution. That is,
It is a composite molded article in which the fiber reinforced polyamide resin substrate and a molded article containing a thermoplastic resin are joined at least in part.

  In the fiber-reinforced polyamide resin substrate of the present invention, the terminal-modified polyamide resin preferably contains 1 to 20% by mass of the terminal structure represented by the general formula (I).

In the fiber-reinforced polyamide resin base material of the present invention, the terminal-modified polyamide resin preferably further contains 0.1 to 5% by mass of a terminal structure represented by the following general formula (II).
-Y-R ³ (II)

In the general formula (II), ^{R 3} represents a monovalent hydrocarbon group having 1 to 30 carbon atoms. When X in the general formula (I) is -NH- or -N (CH ₃ )-, -Y- in the general formula (II) represents-(C = O)-and the general formula (I) for, the Y in the general formula (II) -NH- or -N (CH ₃₎ - - X is the - (C = O) represents the.

  The fiber-reinforced polyamide resin substrate of the present invention is preferably a discontinuous fiber in which the reinforcing fibers are continuously arranged in one direction or a number average fiber length of 3 to 100 mm.

  In the fiber-reinforced polyamide resin base material of the present invention, it is preferable that the reinforcing fibers contain carbon fibers and contain 20 to 70% by volume of reinforcing fibers.

  In the fiber-reinforced polyamide resin substrate of the present invention, the terminal-modified polyamide resin has a total of 60 to 250 mol / l of the terminal structure represented by the general formula (I) and the terminal structure represented by the general formula (II). t] The ratio of the content [mol / t] of the terminal structure contained and represented by the general formula (I) to the content [mol / t] of the terminal structure represented by the general formula (II) It is preferable that (I) / (II)) is 0.3-2.5.

  In the fiber-reinforced polyamide resin substrate of the present invention, the terminal-modified polyamide resin contains an amino terminal group and a carboxyl terminal group in total of 50 to 150 [mol / t], and the amino terminal group content [mol / t] It is preferable that ratio (amino terminal group / carboxyl terminal group) of content [mol / t] of a carboxyl terminal group is 0.5-2.5.

The fiber-reinforced polyamide resin substrate of the present invention has a relative viscosity (( _r ) at 25 ° C. of a 98% sulfuric acid solution having a resin concentration of 0.01 g / mL of the terminal-modified polyamide resin of 1.3 to 3.0. Is preferred.

  The fiber-reinforced polyamide resin substrate of the present invention preferably has a weight average molecular weight Mw of 15,000 to 50,000 as measured by gel permeation chromatography of the terminal-modified polyamide resin.

The fiber-reinforced polyamide resin substrate of the present invention preferably has a melt viscosity of 30 Pa · s or less under the conditions of the melting point + 60 ° C. and the shear rate of 9,728 sec ⁻¹ of the terminal-modified polyamide resin.

  In the fiber-reinforced polyamide resin base material of the present invention, the content retention ratio of the terminal structure of the terminal modified polyamide resin represented by the general formula (I) before and after 60 minutes of melting point + 60 ° C. The amount / content before residence) × 100) is preferably 80% or more.

  The fiber-reinforced polyamide resin base material of the present invention has a weight-average molecular weight retention ratio before and after retention for 60 minutes under the condition of melting point + 60 ° C. of the terminal-modified polyamide resin ((weight-average molecular weight after retention / weight-average molecular weight before retention) × 100) Is preferably 80% to 120%.

  The fiber-reinforced polyamide resin base material of the present invention is 80% of melt viscosity retention ((post melt viscosity / pre melt viscosity) × 100) of the terminal-modified polyamide resin before and after 60 minutes of melting point + 60 ° C. It is preferable that it is -120%.

  The fiber-reinforced polyamide resin base material of the present invention preferably has a weight reduction rate of 4% or less before and after retention for 40 minutes under a nitrogen atmosphere at a melting point + 60 ° C. of the terminal-modified polyamide resin.

  According to the present invention, it is possible to obtain a fiber-reinforced polyamide resin base material which is excellent in the impregnation property and the thermal stability and which has a small number of voids and an excellent surface quality. The fiber-reinforced polyamide resin substrate of the embodiment of the present invention can be formed into a desired shape by any forming method such as autoclave forming, press forming, film forming and the like. Molded articles obtained by molding a fiber reinforced polyamide resin base material include, for example, aircraft engine peripheral parts, aircraft interior parts, aircraft exterior parts, vehicle skeletons, automobile engine peripheral parts, automobile underhood parts, automobile gear parts, automobile interiors Processing for automotive applications such as parts, automobile exterior parts, intake / exhaust parts, engine cooling water system parts, automobile electrical parts, etc., and electrical / electronic parts applications such as LED reflectors and SMT connectors are effective.

  Hereinafter, embodiments of the present invention will be described in detail. The fiber-reinforced polyamide resin substrate of the embodiment of the present invention has one of the following two aspects. The first embodiment is a fiber-reinforced polyamide resin substrate obtained by impregnating continuous reinforcing fibers with the terminal modified polyamide resin described later, and the second embodiment is a reinforcing fiber substrate in which reinforcing fibers of discontinuous fibers are dispersed. It is a fiber reinforced polyamide resin base material which is made to impregnate below-mentioned terminal modification polyamide resin.

  In the embodiment of the present invention, the continuous reinforcing fiber in the first aspect refers to a fiber-reinforced polyamide resin substrate in which the reinforcing fiber has no break. The form and arrangement of reinforcing fibers in the embodiment of the present invention include, for example, those aligned in one direction, cloth (cross), knitting, braid, tow and the like. Among them, it is preferable that reinforcing fibers be arranged in one direction, since mechanical characteristics in a specific direction can be efficiently enhanced.

  The reinforcing fiber base in which discontinuous fibers are dispersed in the second embodiment refers to a mat-like one in which the reinforcing fibers are cut and dispersed in a fiber-reinforced polyamide resin base. The reinforcing fiber base in the embodiment of the present invention may be obtained by any method such as a wet method of producing fibers in a solution after dispersion in a solution, or a dry method using a carding apparatus or an air laid apparatus. it can. From the viewpoint of productivity, a dry method using a carding apparatus or an air laid apparatus is preferable.

  The number average fiber length of discontinuous fibers in the reinforcing fiber base according to the embodiment of the present invention is preferably 3 to 100 mm. When the number average fiber length of the discontinuous fibers is 3 mm or more, the reinforcing effect by the discontinuous fibers is sufficiently exhibited, and the mechanical strength of the obtained fiber-reinforced polyamide resin substrate can be further improved. 5 mm or more is preferable. On the other hand, if the number average fiber length of the discontinuous fibers is 100 mm or less, the flowability at the time of molding can be further improved. As for the number average fiber length of a discontinuous fiber, 50 mm or less is more preferable, and 30 mm or less is further more preferable.

The number average fiber length of discontinuous fibers in the fiber-reinforced polyamide resin substrate of the embodiment of the present invention can be determined by the following method. First, a sample of 100 mm × 100 mm is cut out of a fiber-reinforced polyamide resin substrate, and the cut out sample is heated in an electric furnace at 600 ° C. for 1.5 hours to burn off the matrix resin. From the fiber-reinforced polyamide resin substrate thus obtained, 400 discontinuous reinforcing fiber bundles are randomly collected. With respect to the discontinuous reinforcing fiber bundle taken out, the fiber length is measured in 1 mm units using a caliper, and the number average fiber length (Ln) can be calculated by the following equation.
Ln = ΣLi / 400
(Li: Measured fiber length (i = 1, 2, 3,... 400) (unit: mm)).

  The number average fiber length of the discontinuous fibers can be adjusted to the above range by cutting the fibers into a desired length at the time of production of the reinforcing fiber base. The orientation of the discontinuous fiber mat is not particularly limited, but is preferably isotropically dispersed from the viewpoint of formability.

  The type of reinforcing fiber in the first and second embodiments is not particularly limited, and carbon fiber, metal fiber, organic fiber and inorganic fiber are exemplified. Two or more of these may be used.

  Examples of carbon fibers include PAN-based carbon fibers made of polyacrylonitrile (PAN) fibers, pitch-based carbon fibers made of petroleum tar and petroleum pitch, and cellulose-based carbon made of viscose rayon and cellulose acetate. Fibers, vapor grown carbon fibers made from hydrocarbons and the like as raw materials, graphitized fibers thereof and the like can be mentioned. Among these carbon fibers, PAN-based carbon fiber is preferably used in that it is excellent in the balance between strength and elastic modulus.

  As a metal fiber, the fiber which consists of metals, such as iron, gold | metal | money, silver, copper, aluminum, brass, stainless steel, is mentioned, for example.

  Examples of the organic fiber include fibers made of an organic material such as aramid, polybenzoxazole (PBO), polyphenylene sulfide, polyester, polyamide, polyethylene and the like. Examples of aramid fibers include para-aramid fibers excellent in strength and elastic modulus, and meta-aramid fibers excellent in flame retardancy and long-term heat resistance. Examples of para-aramid fibers include poly-p-phenylene terephthalamide fibers, copoly-para-phenylene-3,4'-oxydiphenylene terephthalamide fibers, etc. As meta-aramid fibers, poly-meta-phenylene isophthalamide fibers and the like Can be mentioned. As aramid fibers, para-aramid fibers having a higher elastic modulus than meta-aramid fibers are preferably used.

As an inorganic fiber, the fiber which consists of inorganic materials, such as glass, a basalt, silicon carbide, silicon nitride, etc. is mentioned, for example. As glass fiber, E glass fiber (for electricity), C glass fiber (food-resistant), S glass fiber, T glass fiber (high strength, high elastic modulus) etc. are mentioned, for example. Basalt fiber is a fiber of mineralized basalt and is a highly heat-resistant fiber. Basalt generally contains 9 to 25% by weight of FeO or FeO ₂ which is a compound of iron and 1 to 6% by weight of TiO or TiO ₂ which is a compound of titanium, but these components are increased in the molten state It is also possible to fiberize.

  Since the fiber-reinforced polyamide resin base material in the first and second embodiments of the present invention is expected to serve as a reinforcing material in many cases, it is desirable to express high mechanical properties and to express high mechanical properties. Preferably, the reinforcing fiber comprises carbon fiber.

  In the fiber-reinforced polyamide resin base material according to the first and second embodiments of the present invention, the reinforcing fibers are usually formed by arranging one or more reinforcing fiber bundles in which a large number of single fibers are bundled. The total number of filaments of the reinforcing fibers (the number of single fibers) when one or more reinforcing fiber bundles are arranged is preferably 1,000 to 2,000,000. From the viewpoint of productivity, the total number of filaments of reinforcing fibers is preferably 1,000 to 1,000,000, more preferably 1,000 to 600,000, and 1,000 to 300,000. Particularly preferred. The upper limit of the total number of filaments of the reinforcing fiber may be such as to maintain good productivity, dispersibility, and handleability in consideration of balance with dispersibility and handleability.

  One reinforcing fiber bundle in the first and second embodiments of the present invention is constituted by bundling 1,000 to 50,000 single fibers of reinforcing fibers preferably having an average diameter of 5 to 10 μm.

  The fiber-reinforced polyamide resin base material in the first embodiment of the present invention is characterized in that the polyamide resin to be impregnated into continuous reinforcing fibers is a terminal-modified polyamide resin. The fiber-reinforced polyamide resin base material in the second embodiment of the present invention is characterized in that the polyamide resin to be impregnated into the reinforcing fiber base material in which the reinforcing fibers of the discontinuous fiber are dispersed is a terminal-modified polyamide resin. Here, in the “terminal-modified polyamide resin” in the present invention, at least a part of the polymer constituting the polyamide resin is a structure composed of structural units different from the repeating structural units constituting the main chain of the polymer (hereinafter referred to as It refers to a polyamide resin having a modified structure) at the end group of the polymer. Reducing the melt viscosity of the polyamide resin while maintaining mechanical properties such as tensile strength and impact resistance by at least a part of the polymer constituting the polyamide resin having a modified structure at the terminal group of the polymer Can. Therefore, even when the processing temperature is appropriately low, the impregnation can be improved, and the generation of voids in the fiber-reinforced polyamide resin substrate can be significantly suppressed. The reason for this is that by having a structure in which at least a part of the polymer constituting the polyamide resin is modified at the terminal group of the polymer, the polymer is effective due to the effects such as reduction of intermolecular interaction of polymer chains and increase of free volume. It is believed that the molecular mobility of the chain is greatly increased.

  The terminal-modified polyamide resin in the embodiment of the present invention is a polyamide resin which can be obtained as a main raw material of one or more selected from an amino acid, a lactam and a “mixture of diamine and dicarboxylic acid”. It has a terminal structure represented by the terminal structure represented by). In other words, the terminal-modified polyamide resin in the present invention is a polymer comprising at least one member selected from the group consisting of diamine and dicarboxylic acid, amino acid, and lactam as a main raw material, It has a terminal structure represented by

  As an chemical structure which comprises the main structural unit of a polyamide resin, when using an amino acid or a lactam as a raw material, the thing of a C4-C20 range is preferable. Moreover, when using diamine and dicarboxylic acid as a raw material, the carbon number of the diamine has the preferable range of 2-20, and the carbon number of dicarboxylic acid has the preferable range of 2-20. The following are mentioned as a representative example of a raw material.

  Specifically, amino acids such as 6-aminocaproic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, para-aminomethylbenzoic acid and the like. Lactams such as ε-caprolactam, ω-undecane lactam, ω-laurolactam and the like. Ethylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decanediamine, undecanediamine, dodecanediamine, tridecanediamine, tetradecanediamine, pentadecanediamine, hexadecane Aliphatic diamines such as diamine, heptadecane diamine, octadecane diamine, nonadecane diamine, eicosane diamine, 2-methyl-1,5-diaminopentane, 2-methyl-1,8-diaminooctane; cyclohexane diamine, bis- ( Alicyclic diamines such as 4-aminocyclohexyl) methane and bis (3-methyl-4-aminocyclohexyl) methane; Diamine such as family diamine. Aliphatic dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid; terephthalic acid, isophthalic acid, 2-chloroterephthalic acid, Aromatic dicarboxylic acids such as 2-methylterephthalic acid, 5-methylisophthalic acid, 5-sodiumsulfoisophthalic acid, hexahydroterephthalic acid and hexahydroisophthalic acid; alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid; Examples include dialkyl esters, and dichlorides.

In the embodiment of the present invention, polyamide homopolymers or copolymers derived from these raw materials can be used as the polyamide resin for introducing the terminal structure. Two or more such polyamides may be mixed to form a polyamide resin. In the embodiment of the present invention, the structural units derived from the above-exemplified materials are modified from the viewpoint of further improving the mechanical properties and the thermal stability at the time of melting retention and further reducing the voids caused by the generated gas. It is preferable to have 80 mol% or more, 100 mol% or more is more preferable, and it is more preferable to have 100 mol% in 100 mol% of the total structural units constituting the polyamide resin excluding the above structure. Moreover, it is preferable that the polymerization structure derived from the raw material illustrated above is linear.
The terminal-modified polyamide resin of the embodiment of the present invention has a terminal structure represented by the following general formula (I). The terminal structure represented by the following general formula (I) has an alkylene oxide structure, so the molecular mobility of the obtained polymer is high, and the affinity to an amide group is excellent. The structure represented by the following general formula (I) at the end of the polyamide resin intervenes between polyamide molecular chains to further increase the free volume of the polymer and to reduce the entanglement. As a result, the molecular mobility of the polymer can be further increased to reduce the melt viscosity, and the impregnatability and the surface quality can be further improved. Such an effect is extremely high as compared with the case of mainly having a polyalkylene oxide structure in the main chain of the polyamide resin.
^{-X- (R 1 -O) m-} H (I)

  In said general formula (I), m represents the range of 2-100 (2 or more and 100 or less). The larger the value of m, the more effectively the melt viscosity is reduced. m is preferably 5 or more, more preferably 8 or more, and still more preferably 16 or more. On the other hand, the smaller the value of m, the higher the heat resistance can be maintained. 70 or less are preferable and 50 or less are more preferable. From the viewpoint of maintaining the properties derived from the main structural unit of the polyamide resin, the terminal-modified polyamide resin in the present invention preferably has the structure represented by the above general formula (I) only at the terminal of the polymer.

In said general formula (I), R < ¹ > represents a C2-C10 (2 or more and 10 or less) bivalent hydrocarbon group. From the viewpoint of the affinity to the main structural unit of the polyamide resin, a hydrocarbon group having 2 to 6 carbon atoms is more preferable, and a hydrocarbon group having 2 to 4 carbon atoms is more preferable.

From the viewpoint of the thermal stability of the terminally modified polyamide resin and the prevention of coloration, a saturated hydrocarbon group is more preferable. Examples of R ¹ include ethylene, 1,3-trimethylene, isopropylene, 1,4-tetramethylene, 1,5-pentamethylene, 1,6-hexamethylene, etc. m Each R ¹ may be a combination of hydrocarbon groups of different carbon numbers. R ¹ is preferably at least composed of a bivalent saturated hydrocarbon group having 2 carbon atoms and a bivalent saturated hydrocarbon group having 3 carbon atoms. It is more preferable to be composed of an ethylene group excellent in affinity with the main structural unit of the polyamide resin and an isopropylene group having a large free volume, and the melt viscosity reduction effect can be more effectively exhibited. In this case, it is preferable that the terminal structure represented by the general formula (I) contains 10 or more ethylene groups and 6 or less isopropylene groups, and introduce a desired amount of terminal structures into the polyamide resin. The melt viscosity reduction effect can be further enhanced. In addition, when the terminal of the polyamide resin is -H, the affinity with the main structural unit of the polyamide resin is excellent.

In the general formula (I), -X- is _{-NH -, - N (CH 3} ) - or - (C = O) - represents a. Among these, -NH- which is excellent in affinity with the main structural unit of the polyamide resin is more preferable.

  The terminal-modified polyamide resin of the embodiment of the present invention preferably has the terminal structure represented by the general formula (I) in at least a part of the terminal groups of the polymer constituting the terminal-modified polyamide resin. In other words, the terminal-modified polyamide resin of the present invention preferably has the terminal structure represented by the general formula (I) at at least one terminal of the polymer constituting the terminal-modified polyamide resin.

  The terminal-modified polyamide resin of the embodiment of the present invention contains the terminal structure represented by the general formula (I) in an amount of 1 to 20% by mass (1 to 20% by mass) in 100% by mass of the terminal-modified polyamide resin. is necessary. When the content of the terminal structure represented by the general formula (I) is 1% by mass or more, the melt viscosity of the terminal modified polyamide resin is further reduced, the impregnatability and the surface quality are further improved, and the voids are further reduced. be able to. 3 mass% or more is more preferable, and, as for content of the terminal structure represented by General formula (I), 5 mass% or more is further more preferable. On the other hand, when the content of the terminal structure represented by the general formula (I) is 20% by mass or less, the increase in the gas component due to the thermal decomposition of the structure represented by the general formula (I) during melting retention is suppressed While the thermal stability at the time of melting retention can be further improved, the voids resulting from the generated gas can be further reduced, and the surface quality can be improved. In addition, since the molecular weight of the terminal-modified polyamide resin can be further increased, mechanical properties can be further improved. 15 mass% or less is more preferable, and, as for content of the terminal structure represented by the said General formula (I), 10 mass% or less is more preferable.

  In the embodiment of the present invention, the content of the terminal structure represented by the general formula (I) in the terminal-modified polyamide resin is, for example, the general formula (III) described later used when producing the terminal-modified polyamide resin A desired range can be adjusted by adjusting the compounding amount of the terminal modifying compound to be represented.

  The terminal-modified polyamide resin of the embodiment of the present invention preferably further has a terminal structure represented by the following general formula (II). As described above, by introducing the terminal structure represented by the general formula (I), the melt viscosity of the terminal-modified polyamide resin can be reduced, and the impregnatability and the surface quality can be improved. During the period of melt retention, the thermal decomposition of the terminal structure represented by the general formula (I) tends to proceed. In particular, since the amino end group and the carboxyl end group of the polyamide resin act as a thermal decomposition catalyst for the terminal structure represented by the general formula (I), the amount of the amino end group and the amount of the carboxyl end group in the polyamide resin are reduced. By suppressing the thermal decomposition of the terminal structure represented by the general formula (I) and maintaining the melt viscosity reduction effect by the terminal structure represented by the general formula (I) It can be improved. For this reason, the impregnatability and the surface quality can be further improved, and the voids can be further reduced. For example, as compared with the case where only the terminal structure represented by General Formula (I) is introduced by reacting the compound for terminal modification represented by General Formula (III) described later with the carboxyl terminal group of the polyamide resin, Furthermore, by introducing the terminal structure represented by the following general formula (II) into the amino terminal group, the thermal decomposition of the structure represented by the general formula (I) is suppressed, and the melt viscosity reduction effect is maintained while the melting is performed. The thermal stability at the time of retention can be further improved, and the surface quality can be improved along with the reduction of voids.

  It will be described more specifically. For example, a compound for terminal modification represented by General Formula (III) described later is reacted with a carboxyl terminal group of the polyamide resin to obtain a polyamide resin having only the terminal structure represented by General Formula (I). Can. However, one end of the polyamide resin is modified with the end structure represented by the general formula (I), but the other end is not modified and remains as an amino end group or a carboxyl group. Therefore, the amino terminal group or the carboxyl terminal group acts as a thermal decomposition catalyst of the terminal structure represented by the general formula (I), and the thermal decomposition of the structure represented by the general formula (I) is facilitated. Thus, for example, a terminal-modifying compound represented by the general formula (IV) described later in the polyamide resin (that is, a polyamide resin in which only one end is modified by the structure represented by the general formula (I)) The other terminal can be modified by further reacting, etc., to obtain a polyamide resin further having a terminal structure represented by the following general formula (II). The effect described above can be exhibited by further introducing the terminal structure represented by the general formula (II) into the polyamide resin modified with the structure represented by the general formula (I).

-Y-R ³ (II)
In the general formula (II), ^{R 3} represents a monovalent hydrocarbon group having 1 to 30 carbon atoms (1 to 30). The lower the carbon number of R ³ is, the better the affinity with the main structural unit of the polyamide resin is, and therefore the hydrocarbon group having 1 to 30 carbon atoms is preferable. Specifically, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, Straight chain such as heptadecyl group, octadecyl group, nonadecyl group, icosyl group, eicosyl group, helicosyl group, heneicosyl group, helicosyl group, docosyl group, tricosyl group, tetracosyl group, pentacosyl group, hexacosyl group, heptacosyl group, octacosyl group, nonacosyl group, triacontyl, etc. Branched alkyl groups such as alkyl, isopropyl, isobutyl, tert-butyl, isopentyl and neopentyl, cycloalkyls such as cyclopentyl, cyclohexyl and cycloheptyl, and aryls such as phenyl and tolyl Benzyl group, and aralkyl groups such as 2-phenylethyl groups. From the viewpoint of the thermal stability of the terminal-modified polyamide resin and the prevention of coloration, it is a further preferred embodiment that R ³ is a monovalent hydrocarbon group having a carbon number of 1 to 20 and a saturated hydrocarbon group or an aryl group.

When X in the general formula (I) is -NH- or -N (CH ₃ )-, -Y- in the general formula (II) represents-(C = O)-and the general formula (I) for, the Y in the general formula (II) -NH- or -N (CH ₃₎ - - X is the - (C = O) represents the.

Usually, the end groups of the polyamide resin which are not modified at both ends have one end group being an amino end group and the other end group being a carboxyl end group. Here, when the terminal modifying compound represented by the general formula (III) has an amino terminal group, the terminal modifying compound reacts with the carboxyl terminal group of the polyamide resin, and X in the general formula (I) is -NH. - or -N (CH ₃₎ - and it becomes. In this case, the other end of the polyamide resin is converted to the above general formula (II) by reacting the amino end group, which is the other end of the polyamide resin, with the terminal modifying compound represented by the general formula (IV). It can be sealed by the terminal structure of In this case, Y in the above general formula (II) is-(C = O)-. On the other hand, when the terminal modifying compound represented by the general formula (III) has a carboxyl terminal group, the terminal modifying compound reacts with the amino terminal group of the polyamide resin, and X in the general formula (I) is-(C = O)-. In this case, the other end of the polyamide resin is converted to the above general formula (II) by reacting the carboxyl end group which is the other end of the polyamide resin with the terminal modifying compound represented by the general formula (IV). blocked by the terminal structure, the Y in the general formula (II) -NH- or -N (CH ₃₎ - and becomes.

  The terminal-modified polyamide resin of the present invention contains the terminal structure represented by the general formula (II) in an amount of 0.1 to 5% by mass (0.1 to 5% by mass) in 100% by mass of the terminal-modified polyamide resin Is preferred. When the content of the terminal structure represented by the general formula (II) is 0.1% by mass or more, the thermal decomposition of the structure represented by the general formula (I) in the terminal-modified polyamide resin is suppressed during melt retention The thermal stability at the time of retention of melting can be further improved, and the voids can be further reduced and the surface quality can be improved. 0.2 mass% or more is more preferable, and, as for content of the terminal structure represented by General formula (II), 0.4 mass% or more is further more preferable. On the other hand, when the content of the terminal structure represented by the general formula (II) is 5% by mass or less, the mechanical properties and the thermal stability at the time of melting retention can be further improved, and the voids can be further reduced. While being able to do, it can improve surface quality. 3 mass% or less is more preferable, and, as for content of the terminal structure represented by General formula (II), 1 mass% or less is further more preferable.

  In the present invention, the content of the terminal structure represented by the general formula (II) in the terminal modified polyamide resin is, for example, represented by the following general formula (IV) used when producing the terminal modified polyamide resin A desired range can be adjusted by adjusting the compounding amount of the terminal modifying compound.

  The terminal-modified polyamide resin in the present invention is a polyamide resin having a terminal structure represented by the general formula (I) and a terminal structure represented by the general formula (II) (ie, one end is a compound represented by the general formula (I) Preferably, the other end is modified with the end structure shown, and the other end contains a polyamide resin modified with the end structure represented by the general formula (II). A polyamide resin having only the terminal structure represented by the general formula (I) (for example, a polyamide having one terminal modified by the terminal structure represented by the general formula (I) but not having the other terminal modified Resin) and a polyamide resin having only the terminal structure represented by the general formula (II) (for example, one end is modified with the terminal structure represented by the general formula (II), the other end is The aspect which contains the polyamide resin which is not modified | denatured may be sufficient.

  In addition, the terminal-modified polyamide resin of the present invention has a content [mol / t] of the terminal structure represented by the general formula (I) and a content [mol / t] of the terminal structure represented by the general formula (II) It is preferable that the total of these is 60-250 mol / t (60 mol / t or more and 250 mol / t or less). By containing the terminal structure represented by the general formula (I) and the terminal structure represented by the general formula (II) in total 60 mol or more in the terminal modified polyamide resin 1t, the melt viscosity of the terminal modified polyamide resin is further reduced Impregnability can be further improved, thermal stability at the time of melt retention can be further improved, voids can be further reduced, and surface quality can be improved. The total content of these terminal structures is more preferably 70 mol / t or more, and still more preferably 80 mol / t or more. On the other hand, mechanical properties and thermal stability at the time of melt retention can be obtained by containing in total 250 mol or less of the terminal structure represented by the general formula (I) and the terminal structure represented by the general formula (II) in the terminal modified polyamide resin 1t. The properties can be further improved, the voids can be further reduced, and the surface quality can be improved. The total content of these terminal structures is more preferably 225 mol / t and even more preferably 200 mol / t or less.

  In the present invention, the total amount of the terminal structure represented by the general formula (I) and the terminal structure represented by the general formula (II) in the terminal modified polyamide resin is, for example, used when producing the terminal modified polyamide resin The desired range can be adjusted by adjusting the blending amounts of the terminal modifying compound represented by the general formula (III) described later and the terminal modifying compound represented by the general formula (IV).

  Furthermore, in the terminal-modified polyamide resin of the present invention, the content [mol / t] of the terminal structure represented by the general formula (I) relative to the content [mol / t] of the terminal structure represented by the general formula (II) The ratio of (I) / (II) is preferably 0.3 to 2.5. In the polyamide resin, the molecular weight increase due to the polymerization reaction of the amino end group and the carboxyl end group proceeds simultaneously with the molecular weight decrease due to thermal decomposition at the time of melt retention. It is shown that the difference between the amount of amino end groups to be modified (blocked) and the amount of carboxyl end groups increases as the molar ratio ((I) / (II)) deviates from 1, and the difference increases. The polymerization reaction at the time of melt retention is difficult to progress, and the molecular weight decrease due to thermal decomposition is larger, so the melt viscosity at molecular weight retention and the decrease in molecular weight tend to be large. Also, as the difference becomes larger, the polymerization reaction is less likely to proceed during melt retention, and terminal groups (amino terminal group and carboxyl terminal group) are not consumed in the polymerization reaction, so as described above, these terminal groups are represented by general formula (I) Since it becomes a thermal decomposition catalyst of the terminal structure represented and promotes the thermal decomposition of the alkylene oxide structure in the terminal structure represented by the general formula (I), the melt viscosity tends to increase. By setting the molar ratio ((I) / (II)) to 0.3 or more, the melt viscosity of the terminal modified polyamide resin is further reduced to further improve the impregnating property, and the terminal modified polyamide resin at the time of melt retention The thermal decomposition of the structure represented by the above general formula (I) can be further suppressed, the thermal stability can be further improved, the voids can be further reduced, and the surface quality can be improved. The molar ratio ((I) / (II)) is more preferably 0.5 or more, preferably 0.6 or more, and most preferably 0.8 or more. On the other hand, by setting the molar ratio ((I) / (II)) to 2.5 or less, the thermal decomposition of the terminal structure represented by the general formula (I) in the terminal-modified polyamide resin during melt retention is further suppressed As a result, the thermal stability can be further improved, the voids resulting from the generated gas can be further reduced, and the surface quality can be improved. The molar ratio ((I) / (II)) is more preferably 2.2 or less, still more preferably 2.0 or less.

Here, the content of the terminal structure represented by the general formula (I) and the terminal structure represented by the general formula (II) in the terminal-modified polyamide resin can be determined by ¹ H-NMR measurement. The measurement method and calculation method are as follows.

First, a deuterated sulfuric acid solution in which the concentration of the polyamide resin is 50 mg / mL is prepared, and ¹ H-NMR measurement is performed by 256 times of integration. From the spectral integration value of R ^1, the spectral integration value of R ³ , and the spectral integration value of repeating structural units of the polyamide resin skeleton (repeating structural units constituting the main chain of the polymer), the content (mass%) of each terminal structure Alternatively, it may also be referred to as a ratio (hereinafter referred to as "molar ratio") of the content (mol / t) of terminal structure (I) to the content (mol / t) of mol / t) and terminal structure (II) Yes) can be calculated.

  In the present invention, the molar ratio ((I) / (II)) in the terminal-modified polyamide resin is, for example, the terminal represented by the following general formula (III) used when producing the terminal-modified polyamide resin The compounding ratio of the modifying compound and the terminal modifying compound represented by the general formula (IV) can be adjusted to a desired range.

  The terminal-modified polyamide resin of the present invention preferably contains a total of 50 to 150 mol / t (50 mol / t or more and 150 mol / t or less) of an amino terminal group and a carboxyl terminal group. By including these terminal groups in total of 50 mol or more in the terminal-modified polyamide resin 1t, it is possible to further suppress the decrease in molecular weight retention at the time of melt retention, to further improve the thermal stability, and voids caused by generated gas And the surface quality can be improved. 60 mol / t or more is more preferable, and, as for the total content of these terminal groups, 80 mol / t or more is further more preferable. On the other hand, by containing an amino end group and a carboxyl end group in total of 150 mol / t or less in the terminal-modified polyamide resin, thermal decomposition of the structure represented by the above general formula (I) in the terminal-modified polyamide resin at the melt retention time In addition, the increase in molecular weight can be further suppressed, the thermal stability can be further improved, the voids can be further suppressed, and the surface quality can be improved. The total content of these end groups is more preferably 135 mol / t or less, still more preferably 120 mol / t or less.

  Furthermore, in the terminal-modified polyamide resin of the present invention, the ratio of the content [mol / t] of the amino terminal group to the content [mol / t] of the carboxyl terminal group (content of amino terminal group / content of carboxyl terminal group It is preferable that it is 0.5-2.5 (0.5 or more and 2.5 or less). As described above, the larger the difference between the amount of amino end groups and the amount of carboxyl end groups, the more difficult the polymerization at the time of melting retention proceeds, and the molecular weight reduction due to thermal decomposition becomes larger, so the melt viscosity and molecular weight reduction at melting retention become large. There is a tendency. In addition, since polymerization does not easily proceed during melt retention and terminal groups (amino terminal groups and carboxyl terminal groups) are not consumed in the polymerization reaction, as described above, these terminal groups become thermal decomposition catalysts of general formula (I), In order to promote the thermal decomposition of the alkylene oxide structure in the terminal structure represented by the formula (I), the melt viscosity tends to increase. By setting the molar ratio (content of amino end group / content of carboxyl end group) to 0.5 or more, the heat of the structure represented by the general formula (I) in the terminal-modified polyamide resin at the time of melt retention It is possible to further suppress the decomposition and the molecular weight increase, to further improve the thermal stability and the impregnatability, to further reduce the void and to improve the surface quality. The molar ratio (amino end group / carboxyl end group) is more preferably 0.6 or more, and still more preferably 0.8 or more. On the other hand, by setting the molar ratio (amino end group / carboxyl end group) to 2.5 or less, the thermal decomposition of the structure represented by the general formula (I) in the terminal-modified polyamide resin during melt retention is further suppressed. The thermal stability can be further improved, and the voids in the base material resulting from the generated gas can be further reduced and the surface quality can be improved. The molar ratio (content of amino end group / content of carboxyl end group) is more preferably 2.4 or less, still more preferably 2.3 or less.

  Here, the content of the amino terminal group in the terminal modified polyamide resin is obtained by dissolving the terminal modified polyamide resin in a phenol / ethanol mixed solution (ratio: 83.5 / 16.5 weight ratio) and using thymol blue as an indicator And by titration with aqueous hydrochloric acid. The carboxyl terminal group content in the terminal-modified polyamide resin can be determined by dissolving the terminal-modified polyamide resin in benzyl alcohol at 195 ° C., using phenolphthalein as an indicator, and titrating with an ethanol solution of potassium hydroxide. It can measure.

  In the present invention, the ratio of the content of the amino terminal group to the content of the carboxyl terminal group of the terminal modified polyamide resin is, for example, represented by the following general formula (III) used when producing the terminal modified polyamide resin. The compounding ratio of the terminal modifying compound and the terminal modifying compound represented by the general formula (IV) can be adjusted to a desired range by adjusting the reaction time.

  The melting point (Tm) of the terminal-modified polyamide resin according to the embodiment of the present invention is preferably 200 ° C. or more. Here, the melting point of the terminally modified polyamide resin can be determined by differential scanning calorimetry (DSC). The measurement method is as follows. Weigh 5 to 7 mg of terminally modified polyamide resin. In a nitrogen atmosphere, the temperature is raised from 20 ° C. to Tm + 30 ° C. at a temperature rising rate of 20 ° C./min. Subsequently, the temperature is lowered to 20 ° C. at a temperature lowering rate of 20 ° C./min. The temperature at the top of the endothermic peak that appears when the temperature is raised again to 20 ° C. to Tm + 30 ° C. at a heating rate of 20 ° C./min is defined as the melting point (Tm).

  Examples of terminal-modified polyamide resins having a melting point of 200 ° C. or higher include those having a modified structure at the terminals of the following polyamides and their copolymers. Two or more of these may be used depending on the required properties such as heat resistance, toughness, and surface properties. Examples of polyamides include polycaproamide (polyamide 6), porundecane amide (polyamide 11), polydodecane amide (polyamide 12), polyhexamethylene adipamide (polyamide 66), polytetramethylene adipamide (polyamide 46), Polypentamethylene adipamide (polyamide 56), polytetramethylene sebacamide (polyamide 410), polypentamethylene sebacamide (polyamide 510), polyhexamethylene sebacamide (polyamide 610), polyhexamethylene dodecamide Polyamide 612), polydecamethylene sebacamide (nylon 1010), polydecamethylene dodecamide (nylon 1012), polymethaxylylene adipamide (MXD6), polymethaxylylene sebacamide (MXD10), polyparadex Silylene sebacamide (PXD10), polynonamethylene terephthalamide (nylon 9T), polydecamethylene terephthalamide (polyamide 10T), polyundecamethylene terephthalamide (polyamide 11T), polydodecamethylene terephthalamide (polyamide 12T), poly Pentamethylene terephthalamide / polyhexamethylene terephthalamide copolymer (polyamide 5T / 6T), poly-2-methylpentamethylene terephthalamide / polyhexamethylene terephthalamide (polyamide M5T / 6T), polyhexamethylene adipamide / polyhexamethylene Terephthalamide copolymer (polyamide 66 / 6T), polyhexamethylene adipamide / polyhexamethylene isophthalamide copolymer (polyamide 66 / 6I) , Polyhexamethylene adipamide / polyhexamethylene terephthalamide / polyhexamethylene isophthalamide (polyamide 66 / 6T / 6I), polybis (3-methyl-4-aminocyclohexyl) methane terephthalamide (polyamide MACMT), polybis (3) -Methyl-4-aminocyclohexyl) methaneisophthalamide (polyamide MACMI), polybis (3-methyl-4-aminocyclohexyl) methandodecamide (polyamide MACM 12), polybis (4-aminocyclohexyl) methane terephthalamide (polyamide PACMT), Polybis (4-aminocyclohexyl) methane isophthalamide (polyamide PACMI), polybis (4-aminocyclohexyl) methan dodecamide (polyamide PACM 12) Can be mentioned.

  Particularly preferred are those having a modified structure at the end of polyamide 6, polyamide 66, polyamide 56, polyamide 410, polyamide 510, polyamide 610, polyamide 6/66, polyamide 6/12, polyamide 9T, polyamide 10T, etc. The thing can be mentioned.

The terminal-modified polyamide resin of the present invention has a relative viscosity (η _r ) of 1.3 to 3.0 (1.3 or more and 3.0 or less) at 25 ° C. of a 98% sulfuric acid solution having a resin concentration of 0.01 g / mL. It is preferable that it is a range. By setting η _r to 1.3 or more, the toughness can be improved, and the mechanical properties of the substrate can be improved. 1.4 or more are preferable and 1.5 or more are more preferable. On the other hand, the impregnation can be further improved by setting 以下_r to 3.0 or less. 2.5 or less is preferable and 2.1 or less is more preferable. 2.05 or less is further preferable, and 2.0 or less is the most preferable.

  In the present invention, the relative viscosity of the terminal-modified polyamide resin is represented, for example, by a terminal-modifying compound represented by the following general formula (III) used when producing the terminal-modified polyamide resin and the general formula (IV) The desired range can be adjusted by adjusting the compounding amount of the terminal modifying compound and the reaction time.

  The weight average molecular weight (Mw) of the terminally modified polyamide resin of the present invention measured by gel permeation chromatography (GPC) is preferably 15,000 or more. By setting Mw to 15,000 or more, mechanical properties can be further improved. The Mw is more preferably 18,000 or more, and further preferably 20,000 or more. In addition, Mw is preferably 50,000 or less. By setting the Mw to 50,000 or less, the melt viscosity can be further reduced, and the impregnatability can be further improved. Mw is more preferably 45,000 or less, and further preferably 40,000 or less. In the present invention, the weight average molecular weight (Mw) used is hexafluoroisopropanol (0.005N-trifluoroacetic acid sodium added) as a solvent, and "Shodex" (registered trademark) HFIP-806M (two) and HFIP as a column It is obtained by GPC measurement at 30 ° C. using LG. Use polymethyl methacrylate as molecular weight reference material.

  In the present invention, the weight-average molecular weight of the terminal-modified polyamide resin is, for example, a terminal-modifying compound represented by the following general formula (III) used when manufacturing the terminal-modified polyamide resin and a table of the general formula (IV) The desired range can be adjusted by adjusting the compounding amount of the terminal modifying compound to be treated and the reaction time.

The terminal-modified polyamide resin of the present invention preferably has a melt viscosity of 30 Pa · s or less under the conditions of a melting point of + 60 ° C. and a shear rate of 9,728 sec ⁻¹ . By setting the melt viscosity under the conditions of the melting point + 60 ° C. and the shear rate of 9,728 sec ⁻¹ to 30 Pa · s or less, the impregnatability can be further improved. The melt viscosity is more preferably 20 Pa · s or less, still more preferably 15 Pa · s or less, and still more preferably 10 Pa · s or less. On the other hand, from the viewpoint of handleability, the melt viscosity is preferably 0.1 Pa · s or more, more preferably 0.5 or more, and most preferably 1.0 or more.

This melt viscosity is retained at a temperature of the melting point of the terminal-modified polyamide resin + 60 ° C. for 5 minutes to melt the terminal-modified polyamide resin, and then, by a capillary flow meter under a shear rate of 9,728 sec ⁻¹ . It can be measured. In the present invention, the melting point + 60 ° C. is selected as the temperature condition in which the effect of melt good fluidity tends to appear and the thermal decomposition does not easily progress in the residence for a short time as an index for evaluating the melt viscosity. 9,728 sec- ¹ was selected as a shear rate which is a high shear condition assuming time.

  In the present invention, the melt viscosity of the terminal-modified polyamide resin is, for example, a terminal-modifying compound represented by the following general formula (III) and a general formula (IV) which are used when producing the terminal-modified polyamide resin. The desired range can be adjusted by adjusting the compounding amount of the terminal modifying compound and the reaction time.

  In the terminal-modified polyamide resin of the present invention, the content retention ratio of the terminal structure represented by the general formula (I) ((content after residence / content before residence)) x 60 minutes of residence under conditions of melting point + 60 ° C. Preferably, 100) is 80% or more. By setting the content retention of the terminal structure represented by the general formula (I) to 80% or more, the thermal decomposition of the terminal structure represented by the general formula (I) in the terminal-modified polyamide resin at the time of melt retention The amount of generated gas can be further reduced to further improve the thermal stability at the time of melting and retention, and the voids resulting from the generated gas can be further reduced and the surface quality can be improved. The content retention rate of the terminal structure represented by the general formula (I) is more preferably 85% or more, further preferably 90% or more. Further, from the viewpoint of mechanical properties, the content retention of the terminal structure represented by the general formula (I) is preferably 100% or less.

In addition, this content retention rate calculates | requires content of the terminal structure represented by General formula (I) by ¹ H-NMR measurement mentioned above about terminal modified polyamide resin, Then, in a capillary flow meter, terminal modification is carried out After staying for 60 minutes at a temperature of the melting point + 60 ° C. of the polyamide resin, the content of the end structure represented by the general formula (I) is similarly determined, and the end structure represented by the general formula (I) before melt retention It can be calculated by dividing by the content of and multiplying by 100. In the present invention, as an index for evaluating the melt viscosity, the melting point + 60 ° C. is selected as a temperature condition in which the effect of good melt fluidity tends to appear and thermal decomposition does not easily progress in a short period of residence.

  In the present invention, the content retention rate of the terminal structure represented by the general formula (I) in the terminal modified polyamide resin is, for example, represented by the following general formula (III) used when producing the terminal modified polyamide resin The desired range can be adjusted by adjusting the compounding amounts of the terminal modifying compound and the terminal modifying compound represented by the general formula (IV), and the reaction time.

  The terminal-modified polyamide resin of the present invention has a weight-average molecular weight retention rate ((post-retention weight average molecular weight / pre-retention weight average molecular weight) x 100) of 80 to 120% (80%) It is preferable that it is more than 120%). By setting the weight average molecular weight retention to 80% or more, mechanical properties can be further improved. The weight average molecular weight retention is more preferably 85% or more, and still more preferably 90% or more. On the other hand, by setting the weight molecular weight retention to 120% or less, the melt viscosity can be further reduced, and the impregnatability can be further improved. As for a weight average molecular weight retention, 115% or less is more preferable, and 110% or less is more preferable.

  The weight-average molecular weight retention of the terminal-modified polyamide resin is measured by gel permeation chromatography (GPC) as described above, and then, in a capillary flow meter, the melting point + 60 ° C. of the terminal-modified polyamide resin After staying at temperature for 60 minutes, the weight average molecular weight can be measured in the same manner and divided by the weight average molecular weight before melt retention to multiply by 100. In the present invention, as an index for evaluating the melt viscosity, the melting point + 60 ° C. is selected as a temperature condition in which the effect of good melt fluidity tends to appear and thermal decomposition does not easily progress in a short period of residence.

  In the present invention, the weight-average molecular weight retention of the terminal-modified polyamide resin is, for example, a terminal-modifying compound represented by the following general formula (III) used when producing the terminal-modified polyamide resin and the general formula (IV) The compound can be adjusted to a desired range by adjusting the compounding amount of the terminal modifying compound represented by and the reaction time.

  The terminal-modified polyamide resin of the present invention has a melt viscosity retention rate ((post-retention melt viscosity / pre-retention melt viscosity) x 100) of 80 to 120% (80% to 120%) before and after retention for 60 minutes under the condition of melting point + 60 ° C. Or less). By making the melt viscosity retention rate 80% or more, the impregnatability and mechanical properties can be further improved. The melt viscosity retention is more preferably 85% or more, further preferably 90% or more, and still more preferably 95% or more. On the other hand, by setting the melt viscosity retention rate to 120% or less, the impregnatability can be further improved. As for melt viscosity retention, 115% or less is more preferable, and 110% or less is more preferable.

The melt viscosity retention rate is a temperature of the melting point of the terminal-modified polyamide resin + 60 ° C., and after holding for 5 minutes in order to melt the terminal-modified polyamide resin, capillary flow under a condition of a shear rate of 9,728 sec ⁻¹ After the terminally modified polyamide resin is allowed to stay for 60 minutes at a melt viscosity (melt viscosity before staying) and a temperature of the melting point of the terminally modified polyamide resin + 60 ° C, under the conditions of a shear rate of 9,728 sec ^-1 From the melt viscosity (melt viscosity after residence) measured by a capillary flow meter, it can be calculated by (melt viscosity after residence / melt viscosity before residence) × 100. In the present invention, as the index for evaluating the melt viscosity retention rate, the melting point + 60 ° C. is selected as the temperature condition in which the effect of the melt good fluidity tends to appear and the thermal decomposition hardly progresses in the short-term retention, As a shear rate under high shear conditions assuming resin impregnation, 9,728 sec ⁻¹ was selected.

  In the present invention, the melt viscosity retention rate of the terminal-modified polyamide resin is, for example, a terminal-modifying compound represented by the following general formula (III) and a general formula (IV) which are used when producing the terminal-modified polyamide resin. A desired range can be adjusted by adjusting the compounding amount of the terminal modifying compound to be represented and the reaction time.

  The terminal-modified polyamide resin of the present invention preferably has a weight reduction rate of 4% or less before and after retention for 40 minutes under a nitrogen atmosphere at a melting point of + 60 ° C. By setting the weight reduction rate to 4% or less, it is possible to suppress voids and the like in the fiber reinforced terminal-modified polyamide resin due to a gas caused by thermal decomposition at the time of processing, and mechanical properties can be further improved. In addition, it is possible to suppress the deterioration of the surface quality due to the deterioration of the resin and the like. The weight reduction rate is more preferably 3% or less, further preferably 2% or less.

  The weight loss rate can be measured using a thermogravimetric analyzer (TGA). In the present invention, the melting point + 60 ° C. is selected as a temperature condition in which the effect of melting and fluidization tends to appear and the thermal decomposition does not easily progress in a short period of residence as an index for evaluating the weight loss rate.

  In the present invention, the weight loss rate of the terminal-modified polyamide resin can be determined, for example, by using a terminal-modifying compound represented by the following general formula (III) and a general formula (IV), which are used when producing the terminal-modified polyamide resin. The desired range can be adjusted by adjusting the compounding amount of the terminal modifying compound to be treated and the reaction time.

  Next, a method of producing the terminal-modified polyamide resin used in the embodiment of the present invention will be described.

As a manufacturing method of the polyamide resin used for the embodiment of the present invention,
(1) A method of melt-kneading a polyamide resin, a compound for terminal modification, and other components, if necessary, above the melting point of the polyamide resin and reacting them, or mixing and reacting them in a solution and then a solvent Method to remove, and (2) Raw material constituting the main structural unit of polyamide resin (main raw material of polyamide resin), compound for terminal modification, and method for adding and reacting other components as necessary (reaction method And the like.

  Hereinafter, the case where the terminal modified polyamide resin of the embodiment of the present invention has the terminal structure represented by the general formula (I) and the terminal structure represented by the above (II) will be described as an example. As a method for producing such a terminal-modified polyamide resin, for example, a raw material of a polyamide resin, a terminal-modifying compound represented by the following general formula (III), and a terminal-modifying compound represented by the following general formula (IV) The method of making it react at the time of superposition | polymerization, the method of melt-kneading a polyamide resin and the compound for terminal modification, etc. are mentioned. As a method of reacting at the time of polymerization, for example, after mixing the raw material of the polyamide resin and the compound for terminal modification in advance, heating is carried out to promote condensation, or the terminal modifying compound is added during the polymerization of the raw material as the main component. And the like.

The terminal-modified polyamide resin having a terminal structure represented by the general formula (I) can be polymerized using a terminal modifying compound represented by the following general formula (III). For example, when polymerizing an amino acid, a lactam, and / or a diamine and a dicarboxylic acid (in other words, using at least one selected from the group consisting of a combination consisting of a diamine and a dicarboxylic acid, an amino acid, and a lactam as a main raw material) 1 to 20% by mass (1% by mass or more and 20% by mass) of a terminal modifying compound represented by the following general formula (III) with respect to the total of amino acids, lactams, diamines and dicarboxylic acids (main raw materials)) % Or less) to obtain a terminal-modified polyamide resin containing 1 to 20% by mass of the terminal structure represented by the general formula (I) by combining the terminal modifying compound with the terminal of the polyamide resin it can.
H-X- (R ¹ -O) _n -H (III)

In the above general formula (III), n represents a range of 2 to 100. Like m in the general formula (I), 5 or more is preferable, 8 or more is more preferable, and 16 or more is more preferable. On the other hand, n is preferably 70 or less, more preferably 50 or less. R ¹ represents a divalent hydrocarbon group having 2 to 10 carbon atoms. What was illustrated as R ¹ in General formula (I) is mentioned, respectively. X- is _{-NH -, - N (CH 3} ) - or -O (C = O) - shows the. More preferred is -NH-, which is excellent in reactivity with the end of the polyamide.

  The terminal-modified polyamide resin having a terminal structure represented by the general formula (II) can be polymerized using a terminal modifying compound represented by the following general formula (IV). For example, when polymerizing an amino acid, a lactam, and / or a diamine and a dicarboxylic acid (in other words, using at least one selected from the group consisting of a combination consisting of a diamine and a dicarboxylic acid, an amino acid, and a lactam as a main raw material) 0.1 to 5% by mass (0.1% by mass) of a terminal modifying compound represented by the following general formula (IV) with respect to the total of amino acid, lactam, diamine and dicarboxylic acid (main raw material)) % Or more and 5% by mass or less) and by adding a terminal modifying compound to the end of the polyamide resin, the terminal modification containing 0.1 to 5% by mass of the terminal structure represented by the general formula (II) A polyamide resin can be obtained.

H-Y-R ³ (IV)
In the general formula (IV), ^{R 3} represents a monovalent hydrocarbon group having 1 to 30 carbon atoms. As in the case of the general formula (II), R ³ is more preferably a monovalent saturated hydrocarbon group from the viewpoint of the thermal stability of the terminally modified polyamide resin and the prevention of coloration. When X in the general formula (III) is -NH- or -N (CH ₃ )-, -Y- in the general formula (IV) represents -O (C = O)-, and the general formula (III) ) in X is -O (C = O) - for, the Y in the general formula (IV) -NH- or -N (CH ₃₎ - represents a.

  The number average molecular weight of the terminal modifying compound represented by the general formula (III) is preferably 500 to 10,000. By setting the number average molecular weight to 500 or more, the melt viscosity can be further reduced, and the impregnatability can be further improved. More preferably, it is 800 or more, more preferably 900 or more. On the other hand, by setting the number average molecular weight to 10,000 or less, the affinity to the main structural unit of the polyamide resin can be further improved, and the mechanical properties of the substrate can be further improved. More preferably, it is 5,000 or less, more preferably 2,500 or less, and still more preferably 1,500 or less.

  Specific examples of the terminal modifying compound represented by the general formula (III) include poly (ethylene glycol) amine, poly (trimethylene glycol) amine, poly (propylene glycol) amine, poly (tetramethylene glycol) amine , Poly (ethylene glycol) poly (propylene glycol) amine, poly (ethylene glycol) carboxylic acid, poly (trimethylene glycol) carboxylic acid, poly (propylene glycol) carboxylic acid, poly (tetramethylene glycol) carboxylic acid, poly (ethylene) Glycol) poly (propylene glycol) carboxylic acid etc. are mentioned. When two types of polyalkylene glycols are included, they may have a block polymerization structure or a random copolymerization structure. Two or more kinds of the terminal modifying compounds described above may be used.

  Specific examples of the terminal modifying compound represented by the general formula (IV) include acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthate, caprylic acid, pelargonic acid, undecanoic acid, lauric acid, tridecane Aliphatic monocarboxylic acids such as acid, myristic acid, myristoleic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, arachic acid, and celtic acid, and alicyclic monocarboxylic acids such as cyclohexanecarboxylic acid and methylcyclohexanecarboxylic acid , Aromatic monocarboxylic acids such as benzoic acid, toluic acid, ethylbenzoic acid and phenylacetic acid, methylamine, ethylamine, propylamine, butylamine, pentylamine, hexylamine, heptylamine, octylamine, 2-ethylhexylamine, nonylamine, Decylamine, undesi Aliphatic monoamines such as amine, dodecylamine, tridecylamine, tetradecylamine, pentadecylamine, hexadecylamine, octadecylamine, nonadecylamine, icosylamine, cycloaliphatic monoamines such as cyclohexylamine and methylcyclohexylamine, benzylamine, and Aromatic monoamines such as β-phenylethylamine and the like can be mentioned. Two or more kinds of the terminal modifying compounds described above can also be used.

Next, for obtaining an end-modified polyamide resin, the end-modified polyamide resin of the present invention has an end structure represented by the above general formula (I) and an end structure represented by the above general formula (II) An example of the method will be described. Although the methods (1) and (2) have been described above, they will be described in more detail below.
(1) In the case of producing a terminal-modified polyamide resin by melt-kneading a polyamide resin and a terminal-modifying compound, the melt-kneading temperature is 10 ° C. to 40 ° C. higher than the melting point (Tm) of the polyamide resin. It is preferable to make it react. For example, when melt-kneading using an extruder, it is preferable to make cylinder temperature of an extruder into the said range. By setting the melt-kneading temperature in this range, the terminal of the polyamide resin and the terminal modifying compound can be efficiently bonded while suppressing volatilization of the terminal modifying compound and decomposition of the polyamide resin. The above-mentioned polyamide resin is illustrated as a polyamide resin.
(2) In the case of producing a terminal-modified polyamide resin by reacting the raw material of the polyamide resin and the compound for terminal modification at the time of polymerization, a melt polymerization method in which the reaction is carried out at the melting point or more of the polyamide resin; Any solid phase polymerization method may be used. Examples of the raw material for giving a polyamide resin include the above-mentioned amino acids, lactams and "mixtures of diamines and dicarboxylic acids".

  Specifically, it is preferable to charge the raw material of the terminally modified polyamide resin in a reaction vessel, carry out nitrogen substitution, and react by heating. If the reaction time at this time is too short, not only the molecular weight does not increase, but also the mechanical properties may decrease because the oligomer component increases. Therefore, it is preferable that the time of the nitrogen flow which occupies for reaction time is 15 minutes or more. On the other hand, if the reaction time is too long, thermal decomposition proceeds and coloring occurs, so the nitrogen flow time in the reaction time is preferably 8 hours or less.

  When producing a terminal-modified polyamide resin by a method of reacting a raw material of a polyamide resin and a terminal-modifying compound at the time of polymerization, a polymerization accelerator can be added as needed. As the polymerization accelerator, for example, inorganic phosphorus compounds such as phosphoric acid, phosphorous acid, hypophosphorous acid, pyrophosphoric acid, polyphosphoric acid and alkali metal salts thereof, alkaline earth metal salts and the like are preferable, and phosphorus is particularly preferable. Sodium acid and sodium hypophosphite are preferably used. The polymerization accelerator is preferably used in an amount of 0.001 to 1 part by mass with respect to 100 parts by mass of the raw material of the polyamide resin (excluding the terminal modifying compound). By setting the addition amount of the polymerization accelerator to 0.001 to 1 part by mass, it is possible to obtain a terminal-modified polyamide resin which is more excellent in the balance between the mechanical properties and the impregnation property.

  The fiber-reinforced polyamide resin substrate of the embodiment of the present invention is obtained by impregnating the above-described terminal-modified polyamide resin into continuous reinforcing fibers or reinforcing fiber substrates in which reinforcing fibers of discontinuous fibers are dispersed, Depending on the content, fillers, other polymers, various additives and the like may be further contained.

  As the filler, any one generally used as a filler for resin can be used, and the strength, rigidity, heat resistance and dimensional stability of the fiber-reinforced polyamide resin base material and the molded product can be further improved. As the filler, for example, glass fiber, carbon fiber, potassium titanate whisker, zinc oxide whisker, aluminum borate whisker, aramid fiber, alumina fiber, silicon carbide fiber, ceramic fiber, asbestos fiber, gypsum fiber, metal fiber, etc. Fibrous inorganic filler, warastenite, zeolite, sericite, kaolin, mica, talc, clay, pyrophyllite, bentonite, montmorillonite, asbestos, aluminosilicate, alumina, silicon oxide, magnesium oxide, zirconium oxide, titanium oxide, oxidized Iron, calcium carbonate, magnesium carbonate, dolomite, calcium sulfate, barium sulfate, magnesium hydroxide, calcium hydroxide, aluminum hydroxide, glass beads, ceramic beads, boron nitride, silicon carbide, silica, etc. Such as fibrous inorganic filler and the like. Two or more of these may be contained. These fillers may be hollow. Moreover, you may be processed by coupling agents, such as an isocyanate type compound, an organic silane type compound, an organic titanate type compound, an organic borane type compound, and an epoxy compound. Alternatively, organic montmorillonite in which interlayer ions are cation-exchanged with an organic ammonium salt may be used as montmorillonite. In the fiber-reinforced polyamide resin base material in the first embodiment, as long as the fibrous filler is composed of discontinuous fibers, it functions without impairing the reinforcing effect of the reinforcing fibers in the fiber-reinforced polyamide resin base material. Can be granted. On the other hand, in the fiber-reinforced polyamide resin base material in the second embodiment, the fibrous filler can be used within the range that does not impair the reinforcing effect of the discontinuous fiber base material.

  Other types of polymers include, for example, polyolefins such as polyethylene and polypropylene, elastomers such as polyamide-based elastomers and polyester-based elastomers, polyesters, polycarbonates, polyphenylene ethers, polyphenylene sulfides, liquid crystal polymers, polysulfones, polyether sulfones, ABS resins, SAN Resin, polystyrene, etc. can be mentioned. Two or more of these may be contained. In order to improve the impact resistance of a fiber-reinforced polyamide resin substrate, the impact resistance of a modified polyolefin such as an olefin compound and / or a (co) polymer of a conjugated diene compound, a polyamide elastomer, a polyester elastomer, etc. Modifiers are preferably used.

  Examples of (co) polymers of olefin compounds and / or conjugated diene compounds include ethylene copolymers, conjugated diene polymers, conjugated diene-aromatic vinyl hydrocarbon copolymers, and the like.

  Examples of ethylene-based copolymers include copolymers of ethylene with α-olefins of 3 or more carbon atoms, nonconjugated dienes, vinyl acetate, vinyl alcohol, α, β-unsaturated carboxylic acids and their derivatives, etc. It can be mentioned. Examples of the α-olefin having 3 or more carbon atoms include propylene and butene-1. Examples of non-conjugated dienes include 5-methylidene-2-norbornene, 5-ethylidene-2-norbornene, dicyclopentadiene, 1,4-hexadiene and the like. Examples of the α, β-unsaturated carboxylic acid include acrylic acid, methacrylic acid, ethacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid and butenedicarboxylic acid. Examples of the derivative of the α, β-unsaturated carboxylic acid include alkyl esters, aryl esters, glycidyl esters, acid anhydrides, imides and the like of the α, β-unsaturated carboxylic acids.

  The conjugated diene polymer refers to a polymer of at least one conjugated diene. Examples of conjugated dienes include 1,3-butadiene, isoprene (2-methyl-1,3-butadiene), 2,3-dimethyl-1,3-butadiene, and 1,3-pentadiene. In addition, some or all of the unsaturated bonds of these polymers may be reduced by hydrogenation.

  The conjugated diene-aromatic vinyl hydrocarbon copolymer refers to a copolymer of a conjugated diene and an aromatic vinyl hydrocarbon, and may be a block copolymer or a random copolymer. Examples of conjugated dienes include 1,3-butadiene and isoprene. As an aromatic vinyl hydrocarbon, styrene etc. are mentioned, for example. In addition, part or all of unsaturated bonds other than the double bonds other than the aromatic ring of the conjugated diene-aromatic vinyl hydrocarbon copolymer may be reduced by hydrogenation.

  Specific examples of impact modifiers include ethylene / methacrylic acid copolymers and some or all of carboxylic acid moieties in these copolymers as salts with sodium, lithium, potassium, zinc, calcium, Ethylene / propylene-g-maleic anhydride copolymer, ethylene / butene-1-g-maleic anhydride copolymer and the like can be mentioned.

As various additives, for example, antioxidants and heat stabilizers (hindered phenols, hydroquinones, phosphites and their substituted products, copper halides, iodine compounds, etc.), weathering agents (resorcinol, salicylates) , Benzotriazoles, benzophenones, hindered amines, etc., mold release agents and lubricants (aliphatic alcohols, aliphatic amides, aliphatic bisamides, bisureas, polyethylene waxes, etc.), pigments (cadmium sulfide, phthalocyanines, carbon black, etc.) Dyes (nigrosine, aniline black, etc.), plasticizers (octyl p-hydroxybenzoate, N-butylbenzenesulfonamide, etc.), antistatic agents (alkyl sulfate type antistatic agents, quaternary ammonium salt type cationic charges) Inhibitor, polyoxyethylene so Nonionic antistatic agents such as bitan monostearate, betaine amphoteric antistatic agents, etc., flame retardants (hydroxides such as melamine cyanurate, magnesium hydroxide, aluminum hydroxide etc.) ammonium polyphosphate, brominated polystyrene, Brominated polyphenylene oxide, brominated polycarbonate, brominated epoxy resin, combinations of these brominated flame retardants and antimony trioxide, etc. may be mentioned. Two or more of these may be blended.

  The fiber-reinforced polyamide resin substrate of the embodiment of the present invention can be obtained by impregnating a continuous reinforcing fiber with a terminal-modified polyamide resin (first aspect). Alternatively, it can be obtained by impregnating a terminally modified polyamide resin with a reinforcing fiber base in which reinforcing fibers of discontinuous fibers are dispersed (second embodiment).

  In the first embodiment, as a method for impregnating a continuous reinforcing fiber with a terminal-modified polyamide resin, for example, a film-like terminal-modified polyamide resin is melted and pressurized to impregnate the terminal-modified polyamide resin with a reinforcing fiber bundle. Film method, Comingle method in which fiber end-modified polyamide resin is melted and pressed after impregnating fiber end-modified polyamide resin and reinforcing fiber bundle, and the reinforcing fiber bundle is impregnated with end-modified polyamide resin, powder Powder method in which the end-modified polyamide resin is dispersed into the interstices of the fibers in the reinforcing fiber bundle, and then the powdered end-modified polyamide resin is melted and pressurized to impregnate the reinforcing fiber bundle into the end-modified polyamide resin; The modified fiber bundle is immersed in the end-modified polyamide resin, and the modified fiber bundle is end-modified polyamide resin by pressing. Drawing method of impregnating the like. The drawing method is preferred because fiber reinforced polyamide resin substrates of various types such as various thicknesses and fiber volume contents can be produced.

  The thickness of the fiber-reinforced polyamide resin substrate in the first aspect of the present invention is preferably 0.1 to 10 mm. If the thickness is 0.1 mm or more, the strength of a molded article obtained using the fiber reinforced polyamide resin substrate can be improved. 0.2 mm or more is more preferable. On the other hand, if the thickness is 1.5 mm or less, the reinforcing fiber is more easily impregnated with the terminal-modified polyamide resin. 1 mm or less is more preferable, 0.7 mm or less is more preferable, and 0.6 mm or less is more preferable.

  In the first aspect of the present invention, the volume content of the fiber-reinforced polyamide resin substrate is preferably 20 to 70% by volume. In other words, it is preferable to contain 20 to 70% by volume (20% by volume or more and 70% by volume or less) of reinforcing fibers with respect to the entire fiber reinforced polyamide resin base (100% by volume). By containing 20% by volume or more of the reinforcing fiber, the strength of the molded product obtained using the fiber-reinforced polyamide resin substrate can be further improved. 30 volume% or more is more preferable, and 40 volume% or more is further more preferable. On the other hand, by containing 70% by volume or less of reinforcing fibers, it is easier for the reinforcing fibers to be impregnated with the terminal-modified polyamide resin. 60 volume% or less is more preferable, and 55 volume% or less is further more preferable. The volume content can be adjusted to a desired range by adjusting the amount of reinforcing fiber and terminal-modified polyamide resin.

The volume fraction (V _f ) of reinforcing fibers in the fiber-reinforced polyamide resin substrate is measured for the mass W ₀ of the fiber-reinforced polyamide resin substrate, and then the fiber-reinforced polyamide resin substrate is heated in air at 500 ° C. for 30 minutes Then, the polyamide resin component is burned off, and the weight W ₁ of the remaining reinforcing fiber is measured, and can be calculated by the following equation.
V _f (volume%) = (W ₁ / ρ _f ) / {W ₁ / ρ _f + (W ₀ −W ₁ ) / ρ ₁ } × 100
ρ _f : density of reinforcing fiber (g / cm ³ )
_{r r} : Density of terminal-modified polyamide resin (g / cm ³ )

  Moreover, the fiber reinforced polyamide resin base material of embodiment of this invention can select desired impregnation according to the usage and the objective. For example, prepregs with higher impregnation, semi-impregnated semipregs, fabrics with low impregnation, etc. may be mentioned. Generally, a molding material having high impregnation property is preferable because a molded article having excellent mechanical properties can be obtained by molding in a short time.

  In the second embodiment of the present invention, as a method for impregnating a reinforcing fiber base in which discontinuous fibers are dispersed into an end modified polyamide resin, for example, an end modified polyamide resin is supplied by an extruder to impregnate the reinforcing fiber base A method of dispersing the end-modified polyamide resin of powder in a fiber layer of a reinforcing fiber base and melting it, a method of forming a film of the terminal-modified polyamide resin and laminating it on a reinforcing fiber base, a solution of the terminal-modified polyamide resin dissolved in a solvent Method of impregnating the reinforcing fiber base in the state of the present invention and then volatilizing the solvent, method of forming the end modified polyamide resin into fiber and mixing yarn with the discontinuous fiber, precursor of the terminal modified polyamide resin to the reinforcing fiber base After impregnation, polymerization is carried out to obtain a terminal-modified polyamide resin, and a method of laminating using a melt-blown nonwoven fabric, etc. may be mentioned.Although any method may be used, the method of supplying an end-modified polyamide resin by an extruder to impregnate the reinforcing fiber base has an advantage that it is not necessary to process the end-modified polyamide resin, and the powder is end-modified The method of dispersing and melting the polyamide resin in the fiber layer of the reinforcing fiber base has the advantage of being easy to impregnate, and the method of forming the terminal-modified polyamide resin into a film and laminating it with the reinforcing fiber base is of relatively good quality There is an advantage that things can be obtained.

  The thickness of the fiber-reinforced polyamide resin substrate in the second aspect of the present invention is preferably 0.1 to 10 mm. If the thickness is 0.1 mm or more, the strength of a molded article obtained using the fiber reinforced polyamide resin substrate can be improved. 1 mm or more is more preferable. On the other hand, if the thickness is 10 mm or less, the reinforcing fiber is more easily impregnated with the terminal-modified polyamide resin. 7 mm or less is more preferable, and 5 mm or less is more preferable.

  Moreover, as for the volume content rate of the fiber reinforced polyamide resin base material in the 2nd aspect of this invention, 20-70 volume% is preferable. In other words, it is preferable to contain 20% by volume or more and 70% by volume or less of discontinuous fibers in the entire fiber reinforced polyamide resin base (100% by volume). By containing 20% by volume or more of the discontinuous fiber, the strength of a molded article obtained using the fiber-reinforced polyamide resin substrate can be further improved. 30 volume% or more is more preferable. On the other hand, by containing 70% by volume or less of the discontinuous fiber, the discontinuous fiber can be more easily impregnated with the terminally modified polyamide resin. 60 volume% or less is more preferable, and 50 volume% or less is more preferable. The volume content can be calculated by the above-mentioned formula (VI).

  Further, the fiber-reinforced polyamide resin base material in the second aspect of the present invention can be selected to have a desired impregnation property depending on its usage and purpose. Generally, a molding material having high impregnation property is preferable because a molded article having excellent mechanical properties can be obtained by molding in a short time.

  When manufacturing the fiber reinforced polyamide resin base material in the 2nd aspect of this invention, the method of heat-pressing using a press as a method of adjusting the said base material to desired thickness and volume content is mentioned. The press is not particularly limited as long as it can realize the temperature and pressure necessary for the impregnation of the terminal-modified polyamide resin, and a common press having a flat platen which moves up and down, and a pair of endless steel belts It is possible to use a so-called double belt press having a traveling mechanism.

  A molded article is obtained by forming one or more sheets of the fiber-reinforced polyamide resin base material in the first and second embodiments of the present invention in an arbitrary configuration and applying heat and / or pressure as necessary. Be

  As a method of applying heat and / or pressure, for example, a press-forming method in which a fiber reinforced terminal-modified polyamide resin laminated in any configuration is placed in a mold or on a press plate, and then the mold or press plate is closed and pressed. An autoclave molding method in which a molding material laminated in an arbitrary configuration is charged into an autoclave and pressurized and heated, and a molding material laminated in an arbitrary configuration is wrapped in a film or the like, and the inside is decompressed and pressurized at atmospheric pressure. A bagging method of heating in an oven, a wrapping tape method of winding a tape while applying tension to a fiber-reinforced terminal-modified polyamide resin laminated in any configuration, and heating in an oven, a fiber-reinforced terminal-modified polyamide laminated in any configuration The internal pressure is established by placing the resin in the mold and injecting gas and liquid into the core in the mold as well. Law, and the like. In particular, a molding method in which a mold is used for pressing is preferably used because a molded article having a small number of voids in a molded article to be obtained and an excellent appearance quality can be obtained.

  As a press molding method, a fiber-reinforced polyamide resin base material is disposed in advance in a mold, and pressing and heating are performed together with mold clamping, and then fiber-reinforced polyamide resin group is cooled by cooling the mold while clamping is performed. Material is cooled to obtain a molded product, or the fiber-reinforced polyamide resin substrate is heated in advance to a temperature higher than the melting temperature of the terminal-modified polyamide resin, using a heating device such as a far infrared heater, heating plate, high temperature oven, or dielectric heating. Then, with the terminal-modified polyamide resin melted and softened, place it on the mold that will be the lower surface of the mold, then close the mold and clamp it, and then press-cool it. It can be adopted. The press forming method is not particularly limited, but from the viewpoint of accelerating the molding cycle and enhancing the productivity, it is desirable to use stamping. The fiber-reinforced polyamide resin base material and molded article in the first and second embodiments of the present invention are integrated molding such as insert molding and outsert molding, corrective treatment by heating, heat welding, vibration welding, ultrasonic welding, etc. The bonding method with excellent productivity and the integration using an adhesive can be performed, and a composite can be obtained.

  The composite molded article in which the fiber reinforced polyamide resin base material in the first and second embodiments of the present invention and the molded article containing a thermoplastic resin are joined at least in part is preferable.

  There is no particular limitation on a molded article (a base for molding and a molded article) containing a thermoplastic resin integrated with the fiber reinforced polyamide resin base according to the first and second aspects of the present invention, for example, a resin material and Molded articles, metal materials and molded articles, inorganic materials and molded articles, etc. may be mentioned. Among them, resin materials and molded articles are preferable in terms of adhesive strength with the fiber-reinforced terminal-modified polyamide resin in the present invention.

  The matrix resin of the molding material and the molded article integrated with the fiber reinforced polyamide resin base in the first and second embodiments of the present invention is a fiber reinforced polyamide resin base and a resin of the same kind as the molded article It may be a different resin. In order to further increase the adhesive strength, it is preferable to use the same kind of resin. In the case of different resins, it is more preferable to provide a resin layer at the interface.

  EXAMPLES The present invention will be more specifically described below by way of Examples, but the present invention is not limited to the description of these Examples. Characteristic evaluation in each example and comparative example is performed according to the following method.

[Volume content (V _f )]
After measuring the mass W0 of the fiber-reinforced polyamide resin substrate obtained according to each example and comparative example, the fiber-reinforced polyamide resin substrate is heated in air at 500 ° C. for 30 minutes to burn off the polyamide resin component and the remaining reinforcement The mass W1 of the fiber is measured, and the volume content (V _f ) of the fiber-reinforced polyamide resin substrate is calculated by the following formula (VI).
V _f (volume%) = (W ₁ / ρ _f ) / {W ₁ / ρ _f + (W ₀ −W ₁ ) / ρ ₁ } × 100
ρ _f : density of reinforcing fiber (g / cm ³ )
_{r r} : density of terminal-modified polyamide resin (g / cm ³ ).

[Relative viscosity (η _r )]
The relative viscosity of an end-modified polyamide resin or polyamide resin obtained by each of the Examples and Comparative Examples is measured using an Ostwald viscometer at 25 ° C. with a 98% sulfuric acid solution with a resin concentration of 0.01 g / mL.

[Molecular weight]
Dissolve 2.5 mg of the terminally modified polyamide resin or polyamide resin obtained according to each example and comparative example in 4 ml of hexafluoroisopropanol (0.005 N-triflurroacetic acid sodium added), obtain the resulting solution with a 0.45 μm filter Filter. Using the resulting solution, the number average molecular weight (Mn) and the weight average molecular weight (Mw) (weight average molecular weight before melting and retention) are measured by GPC measurement. The measurement conditions are shown below.
Pump: e-Alliance GPC system (manufactured by Waters)
Detector: Differential Refractometer Waters 2414 (made by Waters)
Column: Shodex HFIP-806M (two) + HFIP-LG
Solvent: Hexafluoroisopropanol (0.005 N-sodium trifluoroacetate added)
Flow rate: 1 mL / min
Sample injection volume: 0.1 mL
Temperature: 30 ° C
Molecular weight reference material: polymethyl methacrylate.

[Amino terminal group amount [NH ₂ ]]
After accurately weighing 0.5 g of terminally modified polyamide resin or polyamide resin obtained according to each example and comparative example and adding 25 mL of phenol / ethanol mixed solution (ratio: 83.5 / 16.5 mass ratio) and dissolving at room temperature Tymol blue is used as an indicator and titrated with 0.02 N hydrochloric acid to determine the amount of amino end groups (mol / t).

[Carboxyl terminal group amount [COOH]]
0.5 g of terminally modified polyamide resin or polyamide resin obtained according to each example and comparative example is precisely weighed, and 20 mL of benzyl alcohol is added and dissolved at a temperature of 195 ° C., and then 0.02 N with phenolphthalein as an indicator. The amount of carboxyl end group (mol / t) is determined by titration at 195 ° C. using an ethanol solution of potassium hydroxide.

[Identification of terminal structure, and determination of the content of terminal structure of general formula (I) and the content of terminal structure of general formula (II)]
About the terminal modified polyamide resin obtained by an Example and a comparative example or a polyamide resin, ¹ H-NMR measurement is implemented using JEOL Co., Ltd. product FT-NMR: JNM-AL400. First, using deuterated sulfuric acid as a measurement solvent, a solution with a sample concentration of 50 mg / mL is prepared. The ¹ H-NMR measurement of the polyamide resin is carried out at an integration number of 256 times. Peaks derived from R ¹ in the terminal structure represented by the general formula (I) and R ³ in the terminal structure represented by the general formula (II) and peaks derived from repeating structural units of the polyamide resin skeleton are identified. The integrated intensity of each peak was calculated, and the content [I] of the terminal structure represented by the general formula (I) in the terminal modified polyamide resin from the calculated integrated intensity and the number of hydrogen atoms in each structural unit The content [II] (mol / t, mass%) of the terminal structure represented by mol / t, mass%) (content before retention) and the general formula (II) is respectively calculated.

[Melting point]
Using a differential scanning calorimeter (DSC Q20) manufactured by TA Instruments, 5 to 7 mg of the terminally modified polyamide resin or polyamide resin obtained according to each example and comparative example is weighed, and the temperature rising rate from 20 ° C. in a nitrogen atmosphere. The temperature is raised to 250 ° C. at 20 ° C./min. Let Tm (melting point) be the peak of the endothermic peak that appears when the temperature is raised.

Melt viscosity
The terminally modified polyamide resin or polyamide resin obtained according to each example and comparative example was dried in an 80 ° C. vacuum dryer for 12 hours or more. As measuring apparatus for molten viscosity, capillary flow meter (Co. Toyo Seiki Seisakusho, Capillograph 1C type) using a diameter 0.5 mm, at an orifice of length 5 mm, melting point + 60 ° C., shear rate 9,728Sec ^- Melt viscosity (melt viscosity before residence) is measured under the condition ¹ . However, in order to melt the terminally modified polyamide resin or the polyamide resin, measurement is carried out after being held for 5 minutes. The smaller the melt viscosity value, the higher the fluidity.

[Melt viscosity retention rate]
The end-modified polyamide resin or polyamide resin obtained by each Example and Comparative Example is dried in an 80 ° C. vacuum dryer for 12 hours or more. Using a capillary flow meter (Capirograph Model 1C, manufactured by Toyo Seiki Seisakusho Co., Ltd.), melt retention at a melting point + 60 ° C for 60 minutes with an orifice of 0.5 mm in diameter and 5 mm in length, shear rate 9,728 sec ^-1 The melt viscosity (melt viscosity after retention) is measured under the following conditions. From the melt viscosity (melt viscosity before staying) and melt viscosity (melt viscosity after staying), the melt viscosity retention [%] is calculated from (melt viscosity after staying / melt viscosity before staying) × 100.

[Weight average molecular weight retention]
The terminally modified polyamide resin or polyamide resin obtained by each Example and Comparative Example is dried in an 80 ° C. vacuum dryer for 12 hours or more. Melt retention is performed at a melting point of + 60 ° C. for 60 minutes with an orifice having a diameter of 0.5 mm and a length of 5 mm using a capillary flow meter (Capirograph 1C type, manufactured by Toyo Seiki Seisakusho Co., Ltd.). The weight average molecular weight (Mw) (weight average molecular weight after retention) of the terminally modified polyamide resin or the polyamide resin after melt retention is measured by the same GPC measurement as the above-described molecular weight measurement method. From the weight average molecular weight (weight average molecular weight before melting and retention) and the weight average molecular weight (weight average molecular weight after retention) measured by the above-mentioned method, weight average molecular weight retention by (weight average molecular weight after retention / weight average molecular weight before retention) × 100 Calculate the rate [%].

[Content retention rate]
The terminally modified polyamide resin or polyamide resin obtained according to each example and comparative example was dried in an 80 ° C. vacuum dryer for 12 hours or more. Melt retention is performed at a melting point of + 60 ° C. for 60 minutes with an orifice having a diameter of 0.5 mm and a length of 5 mm using a capillary flow meter (Capirograph 1C type, manufactured by Toyo Seiki Seisakusho Co., Ltd.). The content of the terminal structure represented by the general formula (I) in the terminal-modified polyamide resin [ ¹ H-NMR measurement similar to the above-mentioned terminal structure content measuring method] for the terminal-modified polyamide resin or polyamide resin after melt retention I] (mol / t) (content after retention) is calculated. Content of terminal structure [I] (mol / t) (content before residence) represented by the general formula (I) measured by the aforementioned method and content of terminal structure represented by the general formula (I) [ From I (mol / t) (content after residence), the content retention ratio is calculated by (content after residence / content before residence) × 100.

[Weight loss rate]
The terminally modified polyamide resin or polyamide resin obtained according to each example and comparative example was dried in an 80 ° C. vacuum dryer for 12 hours or more. 20 mg of an arbitrary part is cut out and held for 40 minutes at a temperature of + 60 ° C. of the terminal modified polyamide resin or polyamide resin under nitrogen gas atmosphere using a thermogravimetric analyzer (manufactured by Perkin Elmer, TGA 7), weight loss before and after heat treatment Measure the rate [%].

[Tensile elongation at break]
The terminally modified polyamide resin or polyamide resin obtained according to each example and comparative example was dried in an 80 ° C. vacuum dryer for 12 hours or more. Using IS55EPN injection molding machine manufactured by Toshiba Machine Co., Ltd., the cylinder temperature is set to the melting point (Tm) + 60 ° C of the terminal modified polyamide resin or polyamide resin, the mold temperature is set to 80 ° C, and the injection time and pressure holding time are combined. A test specimen for evaluation of ASTM No. 4 dumbbell with a specimen thickness of 1/25 inch (about 1.0 mm) is injection molded under a molding cycle condition of 10 seconds and a cooling time of 10 seconds. The obtained ASTM No. 4 dumbbell-shaped test piece is subjected to "Tensilon" (registered trademark) UTA-2.5T (manufactured by Orientec Co., Ltd.), according to ASTM-D638 under an atmosphere of 23 ° C. and 50% humidity. Conduct a tensile test at a strain rate of 10 mm / min to measure the tensile elongation at break.

[Impregnability and thermal stability]
The cross section in the thickness direction of the fiber-reinforced polyamide resin substrate obtained by each of Examples and Comparative Examples is observed as follows. A sample in which a fiber-reinforced terminal-modified polyamide resin is embedded in an epoxy resin is prepared, and the sample is polished until the cross section in the thickness direction of the fiber-reinforced terminal-modified polyamide resin can be observed well. The polished sample was photographed at a magnification of 400 using a hyper depth color 3D shape measurement microscope VHX-9500 (controller unit) / VHZ-100R (measurement unit) (manufactured by Keyence Corporation). The imaging range is a range of thickness of fiber reinforced terminal-modified polyamide resin × width 500 μm. In the photographed image, the area of the portion occupied by the resin and the area of the portion which is a void (void) are determined, and the impregnation rate is calculated by the following equation.
Impregnation rate (%) = 100 × (total area occupied by resin) / {(total area occupied by resin) + (total area occupied by void)}

Since the voids are reduced when the impregnating ability and the thermal stability are high, and the voids are increased when at least one of the impregnating ability and the thermal stability is low, the impregnating ability and the thermal stability of the fiber-reinforced polyamide resin substrate are This impregnation rate is used as a judgment standard, and it evaluates in the following two steps, and makes a pass a pass. The fiber-reinforced polyamide resin base material in the first embodiment was produced at a processing temperature of melting point + 30 ° C., 60 ° C., 100 ° C. The fiber-reinforced polyamide resin substrate in the second embodiment is produced at a processing temperature of melting point + 10 ° C., 20 ° C., 30 ° C.
Good: The impregnation rate is 98% or more.
Poor: The impregnation rate is less than 98%.

[Surface quality]
The surface quality of the fiber-reinforced terminal-modified polyamide resin or fiber-reinforced polyamide resin substrate obtained by each of the examples and the comparative examples is visually observed. The surface quality is evaluated in the following two steps, and good is regarded as passing.
Good: Discoloration of matrix resin, no exposure of reinforcing fiber Poor: Discoloration of matrix resin, surface of reinforcing resin, fiber reinforced polyamide resin base material in the first embodiment has a melting point of + 30 ° C., 60 Manufactured at a processing temperature of 100 ° C. The fiber-reinforced polyamide resin substrate in the second embodiment is produced at a processing temperature of melting point + 10 ° C., 20 ° C., 30 ° C.

[material]
In Examples and Comparative Examples, the following materials are used as raw materials.
・ Carbon fiber bundle: Toray Industries, Inc. T700S-12K
-Ε-caprolactam: Wako Pure Chemical Industries, Ltd., Wako special grade.
-Hexamethylene diamine: Wako Pure Chemical Industries, Ltd. product, Wako first grade.
-Adipic acid: manufactured by Wako Pure Chemical Industries, Ltd., Wako special grade.
Sebacic acid: manufactured by Wako Pure Chemical Industries, Ltd., Wako first grade.

[Terminal Modification Compound Represented by General Formula (III)]
Terminal modifying compound 1: terminal modifying compound in which -X- in the general formula (III) is -NH- and the number average molecular weight is Mn 1,000-Terminal modifying compound 2: General formula (III)- Terminal modifying compound and terminal modifying compound in which X- is -NH- and the number average molecular weight is Mn 2,000: General formula (III)-X- is -NH- and the number average molecular weight is Mn 600 Certain terminal modifying compounds.

[Terminal Modification Compound Represented by General Formula (IV)]
-Benzoic acid: Wako Pure Chemical Industries, Ltd., reagent special grade-Acetic acid: Wako Pure Chemical Industries, Ltd., reagent special grade-Stearic acid: Wako Pure Chemical Industries, Ltd., reagent special grade-Cerotic acid: Tokyo Kasei Manufactured by Kogyo Co., Ltd.

Example 1
20 g of ε-caprolactam, 20 g of ion exchange water, 1.6 g of Compound 1 for terminal modification, and 0.14 g of benzoic acid are charged in a reaction vessel and sealed, followed by nitrogen substitution. The set temperature of the heater at the outer periphery of the reaction vessel is set to 290 ° C., and heating is started. After the pressure in the can reaches 1.0 MPa, the pressure in the can is maintained at 1.0 MPa while releasing the water out of the system, and the temperature is raised until the temperature in the can reaches 240.degree. After the temperature in the can reaches 240 ° C, the set temperature of the heater is changed to 270 ° C, and the pressure in the can is adjusted to normal pressure over 1 hour (temperature in the can at normal pressure: 243 ° C) . Subsequently, the terminal-modified polyamide 6 resin is obtained (maximum reaching temperature: 253 ° C.) by holding for 240 minutes while flowing nitrogen in the can (nitrogen flow). Subsequently, the terminally modified polyamide 6 resin obtained is subjected to Soxhlet extraction with ion-exchanged water to remove the unreacted terminal modifying compound. The relative viscosity of the terminal-modified polyamide 6 resin thus obtained is 1.81, the weight average molecular weight is 30000, the melting point (Tm) is 220 ° C., and the melt viscosity is 5.5 Pa · s. Further, other physical properties are shown in Table 1.

  Sixteen bobbins on which carbon fiber bundles are wound are prepared, and the carbon fiber bundles are continuously fed from the bobbins through the yarn path guides. The continuously delivered carbon fiber bundle is impregnated in the impregnation die with the terminally modified polyamide 6 resin obtained by the above-mentioned method, which is quantitatively supplied from the filled feeder. The carbon fiber impregnated with the end-modified polyamide 6 resin in the impregnation die is continuously drawn from the nozzle of the impregnation die at a drawing speed of 1 m / min using a take-up roll. The temperature at which the carbon fiber is pulled out is called the processing temperature. The drawn carbon fiber bundle passes through a cooling roll to cool and solidify the end-modified polyamide 6 resin, and is wound on a winding machine as a continuous fiber-reinforced polyamide resin substrate. The fiber-reinforced polyamide resin substrate obtained has a thickness of 0.3 mm and a width of 50 mm, the reinforcing fiber direction is arranged in one direction, the volume content is 30%, and the number average fiber length is 15 mm. Get the material. The fiber reinforced polyamide resin substrate obtained is subjected to the above evaluation. The evaluation results are shown in Table 1.

[Examples 2-38, Comparative Examples 1-4]
After changing the raw materials to the composition shown in Tables 1 to 5 and setting the pressure in the can to normal pressure, change the time (nitrogen flow time) to keep holding nitrogen flowing in the can to the times shown in Tables 1 to 5 A terminally modified polyamide 6 resin is obtained in the same manner as in Example 1 except for the above. A fiber-reinforced polyamide resin base is carried out in the same manner as in Example 1 except that the terminally modified polyamide 6 resin obtained in each Example and Comparative Example is used instead of the terminally modified polyamide 6 resin obtained in Example 1 Get The physical properties of the resulting terminal-modified polyamide 6 resin and the physical properties of the fiber-reinforced polyamide resin substrate are shown in Tables 1 to 5.

[Example 39]
9.46 g of hexamethylene diamine, 11.92 g of adipic acid, 20 g of ion-exchanged water, 1.6 g of the compound 1 for terminal modification and 0.14 g of benzoic acid are charged in a reaction vessel, sealed, and purged with nitrogen. The set temperature of the heater at the outer periphery of the reaction vessel is set to 290 ° C., and heating is started. After the pressure in the can reaches 1.75 MPa, the pressure in the can is maintained at 1.75 MPa while releasing the water out of the system, and the temperature in the can is raised to 260 ° C. After the temperature in the can reaches 260 ° C, the set temperature of the heater is changed to 290 ° C, and the pressure in the can is adjusted to normal pressure over 1 hour (temperature in the can at normal pressure: 270 ° C) . Subsequently, the terminal-modified polyamide 66 resin is obtained (maximum reaching temperature: 275 ° C.) by holding for 240 minutes while flowing nitrogen in the can (nitrogen flow). Here, the obtained polyamide resin contains a terminal-modified polyamide 66 resin having the structure shown in Example 1 at the end.

  A fiber-reinforced polyamide 66 resin base is obtained using the obtained terminal-modified polyamide 66 resin in the same manner as in Example 1 except that the processing temperature is 320 ° C. The physical properties of the terminally modified polyamide 66 resin obtained and the physical properties of the fiber-reinforced polyamide 66 resin substrate are shown in Table 6.

[Example 40]
7.74 g of hexamethylene diamine, 13.46 g of sebacic acid, 20 g of ion-exchanged water, 1.6 g of Compound 1 for terminal modification and 0.14 g of benzoic acid are charged in a reaction vessel, sealed, and purged with nitrogen. The set temperature of the heater at the outer periphery of the reaction vessel is set to 290 ° C., and heating is started. After the pressure in the can reaches 1.0 MPa, the pressure in the can is maintained at 1.0 MPa while releasing the water out of the system, and the temperature is raised until the temperature in the can reaches 240.degree. After the temperature in the can reaches 240 ° C, the set temperature of the heater is changed to 290 ° C, and the pressure in the can is adjusted to normal pressure over 1 hour (temperature in the can at normal pressure: 243 ° C) . Subsequently, the terminal-modified polyamide 610 resin is obtained (maximum reached temperature: 253 ° C.) by holding for 240 minutes while flowing nitrogen in the can (nitrogen flow). Here, the polyamide resin obtained is one including a terminal-modified polyamide 610 resin having the structure shown in Example 1 below at the end.

  A fiber-reinforced polyamide 610 resin substrate is obtained using the obtained terminal-modified polyamide 610 resin in the same manner as in Example 1 except that the processing temperature is 280 ° C. The physical properties of the resulting terminal-modified polyamide 610 resin and the physical properties of the fiber-reinforced polyamide 610 resin substrate are shown in Table 6.

[Example 41]
A terminally modified polyamide resin is obtained in the same manner as in Example 1. The resulting terminally modified polyamide resin is charged into an extruder, melt-kneaded, and then extruded from a film die into a film to obtain a resin film.

The carbon fiber used as the reinforcing fiber is cut to a fiber length of 15 mm and introduced into an air laid apparatus to obtain a mat-like reinforcing fiber base of 100 g / m ² in fabric weight.

  The above-mentioned reinforcing fiber base and resin film are laminated so that the content of carbon fiber is 30% by volume and the thickness is 1.0 mm, and the mold temperature (processing temperature) is charged into a mold heated to 250 ° C. . Subsequently, after heating and pressing at a pressure of 3 MPa for 10 minutes, cooling pressing is performed at a pressure of 3 MPa to obtain a fiber-reinforced polyamide resin substrate having a volume content of 30%. The fiber reinforced polyamide resin substrate obtained is subjected to the above evaluation. The evaluation results are shown in Table 7.

[Examples 42 to 78, Comparative Examples 5 to 8]
After changing the raw materials to the composition shown in Tables 7 to 11 and setting the pressure in the can to normal pressure, change the time (nitrogen flow time) kept while flowing nitrogen in the can to the times shown in Tables 7 to 11 A terminally modified polyamide 6 resin is obtained in the same manner as in Example 41 except for the above. A fiber-reinforced polyamide resin base material is carried out in the same manner as in Example 41 except that the terminally modified polyamide 6 resin obtained in each Example and Comparative Example is used instead of the terminally modified polyamide 6 resin obtained in Example 41. Get The physical properties of the resulting terminal-modified polyamide 6 resin and the physical properties of the fiber-reinforced polyamide resin substrate are shown in Tables 7 to 11.

[Example 79]
A terminally modified polyamide 66 resin is obtained in the same manner as in Example 39. A fiber-reinforced polyamide 610 resin substrate is obtained using the obtained terminal-modified polyamide 66 resin in the same manner as in Example 41 except that the processing temperature is set to 290 ° C. The physical properties of the resulting terminal-modified polyamide 66 resin and the physical properties of the fiber-reinforced polyamide 610 resin substrate are shown in Table 12.

[Example 80]
In the same manner as in Example 40, a terminally modified polyamide 610 resin is obtained. A fiber-reinforced polyamide 610 resin substrate is obtained using the obtained terminal-modified polyamide 610 resin in the same manner as in Example 41 except that the processing temperature is set to 250 ° C. The physical properties of the resulting terminal-modified polyamide 610 resin and the physical properties of the fiber-reinforced polyamide 610 resin substrate are shown in Table 12.

  The terminal-modified polyamide resin obtained in Examples 1 to 80 is a polyamide resin containing the terminal structure represented by the general formula (I). The polyamide resins obtained in Comparative Examples 1 to 3 and 5 to 7 are polyamide resins not including the terminal structure represented by the general formula (I).

  The continuous fiber reinforced polyamide resin base material obtained using the polyamide resin containing the terminal structure represented by general formula (I) according to comparison with Examples 1 to 40 and Comparative Examples 1 to 3 has an impregnating property and a retention time of melting. It is understood that the thermal stability of the present invention is excellent, and the reduction of the void and the improvement of the surface quality can be achieved.

  According to the comparison of Examples 41 to 80 and Comparative Examples 5 to 7, the discontinuous fiber reinforced polyamide resin substrate obtained by using the polyamide resin containing the terminal structure represented by the general formula (I) has an impregnating property and a melt retention. It is understood that the thermal stability at the time is excellent, and reduction of voids and improvement of surface quality can be achieved.

  The fiber-reinforced polyamide resin base material and the molded article thereof according to the first and second aspects of the present invention make good use of their excellent properties to make aircraft parts, automobile parts, electric and electronic parts, building members, various containers, daily goods, daily life It can be used for various uses such as sundries and hygiene products. The fiber-reinforced polyamide resin substrate and the molded article thereof according to the embodiment of the present invention are, among others, aircraft engine peripheral parts that are required to be impregnated, heat aging resistance and surface appearance, parts exterior parts for aircraft, automobile body parts vehicle frame It is particularly preferably used for automobile engine peripheral parts, automobile underhood parts, automobile gear parts, automobile interior parts, automobile exterior parts, intake / exhaust parts, engine cooling water system parts, automobile electric parts, and electric / electronic parts applications. Specifically, the fiber-reinforced terminal-modified polyamide resin of the embodiment of the present invention and molded products thereof include aircraft engine peripheral parts such as fan blades, landing gear pods, winglets, spoilers, edges, ladders, elevators, failings, Aircraft related parts such as ribs, various seats, front seats, underbodies, various pillars, various members, various frames, various beams, various supports, various car bodies such as various rails, various hinges, engine covers, air intake pipes, timing Automobile engine peripheral parts such as belt cover, intake manifold, filler cap, throttle body, cooling fan, cooling fan, radiator tank top and base, cylinder head cover, oil pan Brake piping, tubes for fuel piping, automobile underhood parts such as exhaust gas system parts, gears, actuators, bearing retainers, bearing cages, chain guides, automobile gear parts such as chain tensioners, shift lever brackets, steering lock brackets, key cylinders , Door inner handle, door handle cowl, indoor mirror bracket, air conditioner switch, instrument panel, console box, glove box, steering wheel, trim and other automobile interior parts, front fender, rear fender, fuel lid, door panel, cylinder head cover, door mirror Stay, tailgate panel, license garnish, roof rail, engine mount bracket, rear -Rear spoiler, trunk lid, locker molding, molding, lamp housing, front grille, mud guard, automobile exterior parts such as side bumpers, air intake manifold, intercooler inlet, turbocharger, exhaust pipe cover, inner bush, bearing retainer, engine Engine cooling water system parts such as mounts, engine head covers, resonators and throttle bodies, chain covers, thermostat housings, outlet pipes, radiator tanks, oil generators, delivery pipes, connectors and wire harness connectors, motor parts , Automotive electrical components such as lamp socket, sensor car switch, combination switch, As electric and electronic parts, for example, generators, motors, transformers, current transformers, voltage regulators, rectifiers, resistors, inverters, relays, contacts for power, switches, circuit breakers, switches, knife switches, etc. Pole rods, motor cases, TV housings, laptop housings and internal parts, CRT display housings and internal parts, printer housings and internal parts, mobile terminal housings and internal parts such as mobile phones, mobile personal computers, hand-held type mobiles, ICs and LEDs Correspondence housing, capacitor base plate, fuse holder, various gears, various cases, electrical parts such as cabinets, connectors, SMT compatible connectors, card connectors, jacks, coils, coil bobbins, sensors, LED lamps, sockets, resistors, relays , Relay case, reflector, small switch, power supply component, coil bobbin, capacitor, varicon case, optical pickup chassis, oscillator, various terminal boards, transformer, plug, printed circuit board, tuner, speaker, microphone, headphone, small motor, magnetic It is preferably used for head parts, power modules, Si power modules, SiC power modules, semiconductors, liquid crystals, FDD carriages, FDD chassis, motor brush holders, transformer members, parabola antennas, electronic parts such as computer related parts, and the like.

Claims (16)

A fiber-reinforced polyamide resin base material comprising a continuous reinforcing fiber or a reinforcing fiber base in which discontinuous reinforcing fibers are dispersed is impregnated with a polyamide resin, wherein the polyamide resin is at least a polymer constituting the polyamide resin A terminal-modified polyamide resin having a structure composed of a structural unit different from the repeating structural unit constituting the main chain of the polymer at the terminal group of the polymer, wherein the terminal-modified polyamide resin has the following general formula (I The fiber reinforced polyamide resin base material which contains the terminal structure represented by 1.) in 1-20 mass%.
_{^{-X- (R 1 -O) m -H}} (I)
In the above general formula (I), m represents a range of 2 to 100. R ¹ represents a divalent hydrocarbon group having 2 to 10 carbon atoms. -X- is _{-NH -, - N (CH 3} ) - or - (C = O) - represents a. The m R ^{1 s} contained in the general formula (I) may be the same or different. The fiber reinforced polyamide resin base material according to claim 1, wherein the terminal modified polyamide resin further contains 0.1 to 5% by mass of a terminal structure represented by the following general formula (II).
-Y-R ³ (II)
In the general formula (II), ^{R 3} represents a monovalent hydrocarbon group having 1 to 30 carbon atoms. When X in the general formula (I) is -NH- or -N (CH ₃ )-, -Y- in the general formula (II) represents-(C = O)-and the general formula (I) for, the Y in the general formula (II) -NH- or -N (CH ₃₎ - - X is the - (C = O) represents the.   The fiber reinforced polyamide resin base according to claim 1 or 2, wherein the reinforcing fibers are continuously arranged in one direction or discontinuous fibers having a number average fiber length of 3 to 100 mm.   The fiber reinforced polyamide resin base material according to any one of claims 1 to 3, wherein the reinforcing fiber contains carbon fiber and contains 20 to 70% by volume of the reinforcing fiber.   The terminal-modified polyamide resin contains a total of 60 to 250 [mol / t] of the terminal structure represented by the general formula (I) and the terminal structure represented by the general formula (II), and The ratio ((I) / (II)) of the content [mol / t] of the terminal structure represented by I) and the content [mol / t] of the terminal structure represented by the general formula (II) is 0 The fiber-reinforced polyamide resin substrate according to any one of claims 1 to 4, which is from 3 to 2.5.   The terminal modified polyamide resin contains a total of 50 to 150 [mol / t] of an amino terminal group and a carboxyl terminal group, and the content [mol / t] of the amino terminal group and the content [mol / t of the carboxyl terminal group] The fiber-reinforced polyamide resin substrate according to any one of claims 1 to 5, wherein the ratio of (amino end group / carboxyl end group) is 0.5 to 2.5. The relative viscosity (η _r ) at 25 ° C. of a 98% sulfuric acid solution having a resin concentration of 0.01 g / mL of the terminal-modified polyamide resin is 1.3 to 3.0 according to any one of claims 1 to 6. Fiber-reinforced polyamide resin base material.   The fiber reinforced polyamide resin base material according to any one of claims 1 to 7, wherein a weight average molecular weight Mw of the terminal modified polyamide resin measured by gel permeation chromatography is 15,000 to 50,000. The fiber reinforced polyamide resin base material according to any one of claims 1 to 8, wherein the melt viscosity of the terminally modified polyamide resin under conditions of a melting point + 60 ° C and a shear rate of 9,728 sec- ¹ is 30 Pa · s or less.   Content retention ratio of the terminal structure represented by the general formula (I) before and after 60 minutes of melting point + 60 ° C. of the terminal-modified polyamide resin ((Content after residence / content before residence) × 100) The fiber reinforced polyamide resin base material according to any one of claims 1 to 9, wherein 80% or more.   The terminal-modified polyamide resin has a weight-average molecular weight retention ((after-retention weight average molecular weight / pre-retention weight average molecular weight) × 100) of 80% to 120% before and after the 60 minutes of retention under the condition of melting point + 60 ° C. The fiber reinforced polyamide resin base material in any one of 1-10.   The melt viscosity retention ((post-retention melt viscosity / pre-retention melt viscosity) × 100) of the terminal-modified polyamide resin before and after 60 minutes of retention under conditions of melting point + 60 ° C. is 80% to 120%. The fiber reinforced polyamide resin base material in any one of.   The fiber-reinforced polyamide resin base material according to any one of claims 1 to 12, wherein a weight reduction rate of the terminally modified polyamide resin before and after retention for 40 minutes under a nitrogen atmosphere at a melting point + 60 ° C is 4% or less. When polymerizing an amino acid, a lactam, and / or a diamine and a dicarboxylic acid, the terminal modifying compound represented by the following general formula (III) is 1 to 20 mass based on the total of the amino acid, lactam, diamine and dicarboxylic acid %, And a terminal-modified polyamide resin containing 1 to 20% by mass of a terminal structure represented by the following general formula (I) is obtained by bonding a terminal-modifying compound to the terminal of the polyamide resin, and continuously The process for producing a fiber-reinforced polyamide resin substrate according to any one of claims 1 to 13, comprising at least a step of impregnating the end-modified polyamide resin in the reinforced fiber in which the reinforcing fiber is dispersed or in the reinforcing fiber base in which discontinuous reinforcing fibers are dispersed. Method.
H-X- (R ¹ -O) _m -H (III)
_{^{-X- (R 1 -O) m -H}} (I)
In the above general formulas (III) and (I), m represents a range of 2 to 100. R ¹ represents a divalent hydrocarbon group having 2 to 10 carbon atoms. The general case expression is (III), -X- is _{-NH -, - N (CH 3} ) - or -O (C = O) - represents a. The general case expression is (I), -X- is _{-NH -, - N (CH 3} ) - or - (C = O) - represents a. The m R ^{1 s} contained in the general formula (III) may be the same or different.   The molded article containing the fiber reinforced polyamide resin base material in any one of Claims 1-13.   The composite molded article in which the fiber reinforced polyamide resin base material in any one of Claims 1-13 and the molded article containing a thermoplastic resin were joined at least in part.