WO2023008480A1

WO2023008480A1 - Polyamide resin composition, polyamide resin composition for three-dimensional modeling, and three-dimensional model of same

Info

Publication number: WO2023008480A1
Application number: PCT/JP2022/028939
Authority: WO
Inventors: 哲也安井; 知之中川
Original assignee: Ｕｂｅ株式会社
Priority date: 2021-07-27
Filing date: 2022-07-27
Publication date: 2023-02-02

Abstract

The present invention relates to a polyamide resin composition which contains 60% by mass to 95% by mass of a polyamide resin (A) and 5% by mass to 40% by mass of a novolac type phenolic resin (B) in 100% by mass of the polyamide resin composition, wherein: the polyamide resin (A) has a relative viscosity of 1.9 to 5.0 as determined at 25°C in accordance with JIS K6920-2; the novolac type phenolic resin (B) has a softening point temperature of 130°C or less; and the extract fraction after subjecting the polyamide resin composition to 6-hour extraction by means of a Soxhlet extraction method that uses water as a solvent is 1.5% by mass or less relative to 100% by mass of the polyamide resin composition used for the extraction. The present invention also relates to: a polyamide resin composition which contains 30% by mass to 70% by mass of a polyamide resin (A), 10% by mass to 40% by mass of a novolac type phenolic resin (B) and 5% by mass to 40% by mass of a reinforcement filler (C) in 100% by mass of the polyamide resin composition; and a polyamide resin composition for three-dimensional modeling, the polyamide resin composition containing 60% by mass to 95% by mass of a polyamide resin (A) and 5% by mass to 40% by mass of a novolac type phenolic resin (B) in 100% by mass of the polyamide resin composition for three-dimensional modeling.

Description

Polyamide resin composition, polyamide resin composition for three-dimensional modeling, and three-dimensionally modeled molding thereof

The first and second inventions relate to polyamide resin compositions. A third invention relates to a polyamide resin composition for three-dimensional modeling.

In the automotive industry, there is a tendency to replace conventional metal parts with resin parts for the purpose of reducing fuel costs, reducing the weight of the car body, preventing rust, and providing sound insulation. Among them, nylon 6 and nylon 66 are highly heat-resistant and rigid, and have a considerable track record of being used as materials for automobile parts. However, these polyamides have the disadvantage that they are susceptible to cracking when they are attacked by road deicing agents using halogenated metal salts such as calcium chloride, magnesium chloride, zinc chloride and rock salt. Several methods have been proposed to improve this drawback.

Patent Document 1 describes a polyamide resin composition containing 90 to 60% by weight of polyamide, 5 to 30% by weight of a phenolic compound, and 5 to 25% by weight of an ethylene elastomer. Polyamide having road antifreeze resistance and low water absorption An automotive underhood component made of resin is disclosed. A novolac type phenolic resin is used as the phenolic compound.

Polyamide resin compositions containing a polyamide resin and a novolak-type phenolic resin are also disclosed in Patent Documents 2 to 4.
Patent Document 2 discloses that a polyamide resin composition containing a polyamide resin and a high-molecular-weight novolak-type phenolic resin can greatly improve the glass transition temperature of the polyamide resin composition, and can be used not only in a dry state but also in a water-absorbing state. However, it is described that the mechanical strength is excellent.
Patent Document 3 describes that a polyamide resin composition obtained by adding 1 to 15% by weight of a novolac phenolic resin to a polyamide resin can increase the melt flow index.
Patent Document 4 describes that a polyamide resin composition containing a low melt viscosity polyamide resin, a low molecular weight novolac phenolic resin, and a filler has excellent melt fluidity while containing a high filler content. .

As a method of manufacturing a three-dimensional molded product, a method of manufacturing a three-dimensional modeled object using a 3D printer, which is a manufacturing device for three-dimensional modeling, is used. A 3D printer manufactures a three-dimensional object by sequentially stacking two-dimensional layers based on three-dimensional coordinate data.

In 3D printers, methods such as a hot melt deposition method (hereinafter also referred to as "FDM method"), a liquid bath photopolymerization method, an inkjet method, etc. are adopted, and among these, the FDM method is widely used.
In the FDM method, a filament-like raw material composition is continuously extruded and deposited from a nozzle portion onto an XY plane table while being heated and melted, and is further stacked in the Z-axis direction. It fuses and solidifies together as it cools.

As raw materials used in the FDM method, thermoplastic resins such as polycarbonate resins, ABS resins, polycarbonate ABS resins, polylactic acid, polyamide resins and polyamide elastomers have been used because they require melt fluidity.
On the other hand, a polyamide resin composition containing a polyamide resin composition and a novolac-type phenol resin is known as a resin composition having good melt fluidity in injection molding. (See Patent Document 3). Similar compositions are known to have low water absorption and excellent mechanical properties (see Patent Documents 1 and 2).

JP-A-60-188456 JP 2016-113603 A Japanese Patent Publication No. 2011-500875 JP-A-2003-246934

1. Problems of the First Invention In Patent Document 1, since a specific amount of the ethylene-based elastomer is contained, the mechanical properties and heat resistance of the polyamide resin composition may deteriorate. In Patent Document 2, since the novolac-type phenolic resin has a high molecular weight, the polyamide resin composition has a low fluidity, and sufficient moldability cannot be obtained in some cases. In Patent Document 3, since the content of the novolak-type phenolic resin is small, there are cases where the water absorption of the polyamide resin cannot be sufficiently suppressed. In Patent Document 4, since a polyamide resin with a low melt viscosity and a novolak-type phenolic resin with a low molecular weight are combined, the molecular weight is low and the amount of inorganic filler is large, resulting in a decrease in impact resistance.

The first invention has good calcium chloride resistance, a low extraction amount by the Soxhlet extraction method when water is used as a solvent and when methanol is used as a solvent, has insulating properties, has a low water absorption, and when water is absorbed. An object of the present invention is to provide a polyamide resin composition having good mechanical properties.

2. Problems of the Second Invention In Patent Document 1, when a specific amount of the ethylene-based elastomer is contained, the heat resistance of the polyamide resin composition may be lowered in addition to the deterioration of the adhesion to the reinforcing material. In Patent Document 2, since the novolak-type phenolic resin has a high molecular weight, the fluidity of the nylon resin composition is lowered, and sufficient moldability cannot be obtained in some cases. In Patent Document 3, since the content of the novolak-type phenolic resin is small, the polyamide resin may not sufficiently suppress water absorption. In Patent Document 4, since a polyamide resin with a low melt viscosity and a novolak-type phenolic resin with a low molecular weight are combined, the molecular weight is low and the amount of inorganic filler is large, so the impact resistance may be lowered.

A second object of the invention is to provide a polyamide resin composition that has good calcium chloride resistance, low water absorption, and excellent mechanical properties when water is absorbed.

3. Problems of the Third Invention Polycarbonate resin, ABS resin, polycarbonate ABS resin, and thermoplastic resins such as polylactic acid, polyamide resin, and polyamide elastomer, which have been used in the conventional FDM method, are thermoplastic resins in a molten state extruded from a nozzle. When the resin is solidified as a three-dimensional molded product, deformation such as warpage occurs in the molded product due to the influence of heat shrinkage, etc., and a highly accurate molded product may not be obtained.
A polyamide resin composition containing a polyamide resin composition and a novolak-type phenolic resin has been used in a molding method for injection molding, but no attempt has been made to mold it with a 3D printer.

Therefore, the third invention, when molded with a 3D printer, suppresses warping of the molded product, suppresses foaming when extruded from the nozzle, and has a good appearance and a low water absorption rate. It is an object of the present invention to provide a polyamide resin composition for three-dimensional modeling that satisfies the requirements for strength.

1. Means for Solving the Problems of the First Invention The first invention is, for example, the following [1] to [8].
[1] A polyamide resin composition containing 60 to 95% by mass of a polyamide resin (A) and 5 to 40% by mass of a novolak phenolic resin (B) in 100% by mass of the polyamide resin composition,
The polyamide resin (A) has a relative viscosity of 1.9 or more and 5.0 or less measured at 25° C. in accordance with JIS K6920-2,
The novolak-type phenol resin (B) has a softening point temperature of 130° C. or less,
The polyamide resin composition is extracted for 6 hours by a Soxhlet extraction method using water as a solvent, and the extracted amount is 1.5% by mass or less with respect to 100% by mass of the polyamide resin composition used for extraction. Resin composition.
[2] The polyamide resin composition of [1], wherein the novolak-type phenolic resin (B) is a novolac-type phenolic resin represented by the following formula (1).

(In the above formula (1), n is 1 to 200.)
[3] The polyamide resin (A) contains at least one selected from the group consisting of an aliphatic homopolyamide resin (A-1) and an aliphatic copolyamide resin (A-2) [1] or [ 2] of the polyamide resin composition.
[4] The polyamide resin composition according to any one of [1] to [3], wherein the novolac-type phenolic resin (B) has a softening point temperature of 110 to 130°C.
[5] The polyamide resin composition according to any one of [1] to [4], which contains a novolac-type phenolic resin (B) as a main component as a thermoplastic resin component other than the polyamide resin (A). .
[6] The polyamide resin composition of any one of [1] to [5] substantially free of ethylene elastomer.
[7] A molded article of the polyamide resin composition according to any one of [1] to [6].
[8] The molded article of [7], which is an automobile part.

2. Means for Solving the Problems of the Second Invention The second invention is, for example, the following (1) to (8).
(1) In 100% by mass of the polyamide resin composition, 30 to 70% by mass of the polyamide resin (A), 10 to 40% by mass of the novolak phenolic resin (B), and 5 to 40% by mass of the reinforcing filler (C) A polyamide resin composition comprising:
(2) The polyamide resin composition according to (1), wherein the novolak-type phenolic resin (B) has a softening point temperature of 130° C. or lower.
(3) The polyamide resin composition of (1) or (2), wherein the reinforcing filler (C) is at least one selected from the group consisting of glass fiber, carbon fiber and cellulose fiber.
(4) The polyamide resin composition according to any one of (1) to (3), wherein the polyamide resin composition does not substantially contain an ethylene-based elastomer.
(5) The polyamide resin (A) contains at least one selected from the group consisting of an aliphatic homopolyamide resin (A-1) and an aliphatic copolyamide resin (A-2) (1) to ( The polyamide resin composition according to any one of 4).
(6) The polyamide resin composition according to any one of (1) to (5), wherein the novolak-type phenolic resin (B) is a novolak-type phenolic resin represented by the following formula (1).

(In the above formula (1), n is 1 to 200.)
(7) A molded article of the polyamide resin composition according to any one of (1) to (6).
(8) The molded article of (7) which is an automobile part.

3. Means for Solving the Problems of the Third Invention The third invention consists of, for example, the following <1> to <8>.
<1> A polyamide resin composition for three-dimensional modeling containing 60 to 95% by mass of a polyamide resin (A) and 5 to 40% by mass of a novolak-type phenolic resin (B) in 100% by mass of a polyamide resin composition for three-dimensional modeling.
<2> The polyamide resin composition for three-dimensional modeling according to <1>, wherein the polyamide resin (A) contains an aliphatic copolymer polyamide (A-2).
<3> The three-dimensional modeling of <1>, wherein the polyamide resin (A) is at least one selected from the group consisting of polyamide 6, polyamide 6/66, polyamide 6/12 and polyamide 6/66/12. Polyamide resin composition.
<4> The polyamide resin composition for three-dimensional modeling according to any one of <1> to <3>, wherein the novolak-type phenolic resin (B) has a softening point temperature of 110 to 150°C.
<5> The water absorption rate when an ISO527 type A tensile test piece obtained by injection molding the polyamide resin composition for three-dimensional modeling is immersed in water at 40 ° C. for 24 hours, is 2.2% or less. The polyamide resin composition for three-dimensional modeling according to any one of <1> to <4>.
<6> After leaving the ISO527 type A tensile test piece obtained by three-dimensionally modeling the polyamide resin composition for three-dimensional modeling using a 3D printer under conditions of 23 ° C. and 50% RH for 24 hours. , When placed on a surface plate and one end of the width direction side is fixed with a weight, the amount of warpage of the other width direction side end from the surface of the surface plate is 30 mm or less <1> to <5> any polyamide resin composition for three-dimensional modeling.
<7> A monofilament for three-dimensional modeling obtained by molding the polyamide resin composition for three-dimensional modeling according to any one of <1> to <6>.
<8> Molded article obtained by three-dimensional modeling of the polyamide resin composition for three-dimensional modeling according to any one of <1> to <6> or the monofilament for three-dimensional modeling according to claim 7 using a 3D printer. .
<9> Use of the polyamide resin composition for three-dimensional modeling of <1> in three-dimensional modeling.
<10> A method of using the polyamide resin composition for three-dimensional modeling of <1> for three-dimensional modeling.

1. Effect of the first invention The polyamide resin composition of the first invention has a low extraction amount by the Soxhlet extraction method when water is used as a solvent and when methanol is used as a solvent, and has good calcium chloride resistance and insulation. It has low water absorption and good mechanical properties when water is absorbed.

2. Effects of the Second Invention The polyamide resin composition of the second invention has good calcium chloride resistance, low water absorption, and excellent mechanical properties when water is absorbed.

3. Effect of the third invention When the polyamide resin composition for three-dimensional modeling of the third invention is molded with a 3D printer, the molded product is suppressed from warping and foaming is suppressed when extruded from the nozzle. The appearance of the molded product is good, the water absorption is low, and the strength is satisfactory.

It is a figure which shows an example of the 3D printer in 3rd invention.

As used herein, the term "substantially does not contain" means that the properties of the polyamide resin composition and the functions and properties of the molded product obtained from the polyamide resin composition are not changed. It does not exclude that it is included to the extent that it does not impair the characteristics.

1. First invention The first invention is a polyamide resin composition containing 60 to 95% by mass of a polyamide resin (A) and 5 to 40% by mass of a novolac type phenolic resin (B) in 100% by mass of the polyamide resin composition. The polyamide resin (A) has a relative viscosity of 1.9 or more and 5.0 or less measured at 25 ° C. in accordance with JIS K6920-2, and the novolak phenol resin (B) is softened. The point temperature is 130 ° C. or less, and the extracted amount when the above-mentioned polyamide resin composition is extracted for 6 hours by the Soxhlet extraction method using water as a solvent is 100% by mass of the polyamide resin composition used for extraction. It relates to a polyamide resin composition having a content of 1.5% by mass or less.

<Polyamide resin (A)>
The polyamide resin composition of the first invention contains a polyamide resin (A).
Examples of the polyamide resin (A) include an aliphatic homopolyamide resin (A-1), an aliphatic copolyamide resin (A-2), an aromatic homopolyamide resin (A-3) and an aromatic copolyamide resin (A -4). These may be used individually by 1 type, or may be used in combination of 2 or more types. Among these, from the viewpoint of moldability, the polyamide resin (A) is at least one selected from the group consisting of an aliphatic homopolyamide resin (A-1) and an aliphatic copolymerized polyamide resin (A-2). It preferably contains an aliphatic homopolyamide resin (A-1), and more preferably contains an aliphatic homopolyamide resin (A-1).

(A-1) Aliphatic Homopolyamide Resin The aliphatic homopolyamide resin (A-1) is a polyamide resin composed of one type of aliphatic constitutional unit. The aliphatic homopolyamide resin (A-1) may consist of at least one aminocarboxylic acid that is one type of lactam and a hydrolyzate of the lactam, and one type of diamine and one type of dicarboxylic acid. It may consist of a combination of Here, the combination of diamine and dicarboxylic acid is regarded as one type of monomer in combination of one type of diamine and one type of dicarboxylic acid.

Lactams include ε-caprolactam, enantholactam, undecanelactam, α-pyrrolidone, α-piperidone, laurolactam and the like.
Among these, one selected from the group consisting of ε-caprolactam, undecanelactam, and laurolactam is preferred from the viewpoint of polymerization production.
Aminocarboxylic acids include 6-aminocaproic acid, 7-aminoheptanoic acid, 9-aminononanoic acid, 11-aminoundecanoic acid, and 12-aminododecanoic acid.
Among these, one selected from the group consisting of 6-aminocaproic acid, 11-aminoundecanoic acid, and 12-aminododecanoic acid is preferable from the viewpoint of polymerization production.

Diamines include ethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, peptamethylenediamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, undecamethylenediamine, dodecamethylenediamine, tridecanediamine, and tetradecanediamine. , pentadecanediamine, hexadecanediamine, heptadecanediamine, octadecanediamine, nonadecanediamine, eicosanediamine, 2-methyl-1,8-octanediamine, 2,2,4/2,4,4-trimethylhexamethylenediamine, etc. 1,3-/1,4-cyclohexyldiamine, bis(4-aminocyclohexyl)methane, bis(4-aminocyclohexyl)propane, bis(3-methyl-4-aminocyclohexyl)methane, (3 -methyl-4-aminocyclohexyl)propane, 1,3-/1,4-bisaminomethylcyclohexane, 5-amino-2,2,4-trimethyl-1-cyclopentanemethylamine, 5-amino-1,3 , 3-trimethylcyclohexanemethylamine, bis(aminopropyl)piperazine, bis(aminoethyl)piperazine, norbornane dimethyleneamine and other alicyclic diamines.
Among these, from the viewpoint of polymerization productivity, aliphatic diamines are preferred, and hexamethylenediamine is more preferred.

Dicarboxylic acids include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecane. Aliphatic dicarboxylic acids such as dioic acid, hexadecanedioic acid, octadecanedioic acid, eicosandioic acid; 1,3-/1,4-cyclohexanedicarboxylic acid, dicyclohexanemethane-4,4'-dicarboxylic acid, norbornanedicarboxylic acid alicyclic dicarboxylic acids such as
Among these, aliphatic dicarboxylic acids are preferred, one selected from the group consisting of adipic acid, sebacic acid and dodecanedioic acid is more preferred, and adipic acid or dodecanedioic acid is even more preferred.

Specific examples of the aliphatic homopolyamide resin (A-1) include polycaprolactam (polyamide 6), polyenantholactam (polyamide 7), polyundecanelactam (polyamide 11), polylaurolactam (polyamide 12), and polyhexamethylene. adipamide (polyamide 66), polytetramethylene dodecamide (polyamide 412), polypentamethylene adipamide (polyamide 56), polypentamethylene azelamide (polyamide 59), polypentamethylene sebacamide (polyamide 510), Polypentamethylene dodecamide (Polyamide 512), Polyhexamethylene Azelamide (Polyamide 69), Polyhexamethylene Sebacamide (Polyamide 610), Polyhexamethylene Dodecamide (Polyamide 612), Polynonamethylene adipamide (Polyamide 96 ), polynonamethyleneazelamide (polyamide 99), polynonamethylenesebacamide (polyamide 910), polynonamethylenedodecanamide (polyamide 912), polydecamethyleneadipamide (polyamide 106), polydecamethyleneazelamide ( Polyamide 109), polydecamethylenedecamide (polyamide 1010), polydecamethylenedodecamide (polyamide 1012), polydodecamethyleneadipamide (polyamide 126), polydodecamethyleneazelamide (polyamide 129), polydodecamethylene sevaca amide (polyamide 1210), polydodecamethylene dodecamide (polyamide 1212), polyamide 122 and the like. The aliphatic homopolyamide resin (A-1) may be used alone or as a mixture of two or more.

Among them, the aliphatic homopolyamide resin (A-1) is preferably at least one selected from the group consisting of polyamide 6, polyamide 11, polyamide 12, polyamide 66, polyamide 610 and polyamide 612 from the viewpoint of polymerization productivity, At least one selected from polyamide 6, polyamide 11, polyamide 12, polyamide 610 and polyamide 612 is more preferred, and polyamide 6 is even more preferred.

Equipment for producing the aliphatic homopolyamide resin (A-1) includes a batch reactor, a single-vessel or multi-vessel continuous reactor, a tubular continuous reactor, a single-screw kneading extruder, and a twin-screw kneading extruder. A known polyamide manufacturing apparatus such as a kneading reaction extruder such as As a polymerization method, known methods such as melt polymerization, solution polymerization, and solid phase polymerization can be used, and polymerization can be performed by repeating normal pressure, reduced pressure, and pressurization operations. These polymerization methods can be used alone or in combination as appropriate.

The relative viscosity of the aliphatic homopolyamide resin (A-1) is measured at 25°C by dissolving 1 g of the aliphatic homopolyamide in 100 ml of 96% concentrated sulfuric acid according to JIS K 6920-2. The relative viscosity of the aliphatic homopolyamide is preferably 1.9 or more and 5.0 or less, more preferably 2.3 or more and 4.5 or less, and preferably 2.7 or more and 4.3 or less. More preferred. Furthermore, from the viewpoint of improving the effect of the present invention, 3.2 or more and 4.2 or less is particularly preferable. When the relative viscosity is within the above range, molding processability is good, and mechanical properties are also good.

The terminal amino group concentration of the aliphatic homopolyamide resin (A-1) is determined by neutralization titration after dissolving in a mixed solvent of phenol and methanol. The terminal amino group concentration of the aliphatic homopolyamide resin (A-1) is preferably 30 μmol/g or more, more preferably 30 μmol/g or more and 50 μmol/g or less.

(A-2) Aliphatic Copolyamide Resin The aliphatic copolyamide resin (A-2) is a polyamide resin composed of two or more kinds of aliphatic constitutional units. The aliphatic copolyamide resin (A-2) is a copolymer of monomers selected from the group consisting of combinations of diamines and dicarboxylic acids, lactams and aminocarboxylic acids. Here, the combination of diamine and dicarboxylic acid is regarded as one type of monomer in combination of one type of diamine and one type of dicarboxylic acid.

Examples of the diamine include those exemplified as raw materials for the aliphatic homopolyamide resin (A-1). A diamine may be used individually by 1 type, and may be used in combination of 2 or more types as appropriate. Among these, from the viewpoint of polymerization productivity, at least one selected from the group consisting of aliphatic diamines is preferable, at least one selected from the group consisting of linear aliphatic diamines is more preferable, and hexamethylenediamine is More preferred.

Examples of the dicarboxylic acid include those exemplified as raw materials for the aliphatic homopolyamide resin (A-1). One type of dicarboxylic acid may be used alone, or two or more types may be used in combination as appropriate. Among these, aliphatic dicarboxylic acids are preferred, at least one selected from the group consisting of adipic acid, sebacic acid and dodecanedioic acid is more preferred, and at least one selected from the group consisting of adipic acid and dodecanedioic acid is More preferred.

Examples of the lactam include those exemplified as raw materials for the aliphatic homopolyamide resin (A-1). One type of lactam may be used alone, or two or more types may be used in combination as appropriate.
Among these, from the viewpoint of polymerization production, at least one selected from the group consisting of ε-caprolactam, undecanelactam and laurolactam is preferred.

In addition, examples of the aminocarboxylic acid include those similar to those exemplified as raw materials for the aliphatic homopolyamide resin (A-1). One type of aminocarboxylic acid may be used alone, or two or more types may be used in combination as appropriate. Among these, at least one selected from the group consisting of 6-aminocaproic acid, 11-aminoundecanoic acid, and 12-aminododecanoic acid is preferable from the viewpoint of polymerization production.

Specific examples of the aliphatic copolymerized polyamide resin (A-2) include caprolactam/hexamethylenediaminoadipic acid copolymer (polyamide 6/66) and caprolactam/hexamethylenediaminoazelaic acid copolymer (polyamide 6/69). , caprolactam/hexamethylenediaminosebacic acid copolymer (polyamide 6/610), caprolactam/hexamethylenediaminoundecanoic acid copolymer (polyamide 6/611), caprolactam/hexamethylenediaminododecanoic acid copolymer (polyamide 6/612 ), caprolactam/aminoundecanoic acid copolymer (polyamide 6/11), caprolactam/laurolactam copolymer (polyamide 6/12), caprolactam/hexamethylenediaminoadipic acid/laurolactam copolymer (polyamide 6/66/ 12), caprolactam/hexamethylenediaminoadipic acid/hexamethylenediaminosebacic acid copolymer (polyamide 6/66/610), caprolactam/hexamethylenediaminoadipic acid/hexamethylenediaminododecanedicarboxylic acid copolymer (polyamide 6/66 /612) and other aliphatic copolyamides. The aliphatic copolyamide resin (A-2) may be used alone or as a mixture of two or more.

Among these, at least one selected from the group consisting of polyamide 6/66, polyamide 6/12 and polyamide 6/66/12 is preferable from the viewpoint of suppressing the water absorption rate of the molded product and maintaining the mechanical strength, At least one selected from the group consisting of polyamide 6/66 and polyamide 6/66/12 is more preferred, and polyamide 6/66 is particularly preferred.

Examples of the production apparatus and polymerization method for the aliphatic copolyamide resin (A-2) are the same as those exemplified in the section for the aliphatic homopolyamide resin (A-1).

The relative viscosity of the aliphatic copolyamide resin (A-2) is determined by dissolving 1 g of the aliphatic copolyamide in 100 ml of 96% concentrated sulfuric acid in accordance with JIS K 6920-2, from the viewpoint of moldability and mechanical properties. , the relative viscosity measured at 25 ° C. is preferably 1.9 or more and 5.0 or less, more preferably 2.3 or more and 4.5 or less, and 2.7 or more and 4.3 or less. More preferred. Furthermore, from the viewpoint of improving the effect of the present invention, 3.2 or more and 4.2 or less is particularly preferable. When the relative viscosity is within the above range, molding processability is good, and mechanical properties are also good.

The terminal amino group concentration of the aliphatic copolyamide resin (A-2) is determined by neutralization titration after dissolving in a mixed solvent of phenol and methanol. The terminal amino group concentration of the aliphatic copolymerized polyamide resin (A-2) is preferably 30 μmol/g or more, more preferably 30 μmol/g or more and 50 μmol/g or less. When the terminal amino group concentration is within the above range, it is preferable from the viewpoint of adhesion to reinforcing materials and adhesion to other resins.

(A-3) Aromatic homopolyamide resin Aromatic homopolyamide resin (A-3) is an aromatic polyamide resin consisting of one type of structural unit derived from an aromatic monomer component, for example, aliphatic dicarboxylic acid and an aromatic diamine, an aromatic dicarboxylic acid and an aliphatic diamine, or an aromatic dicarboxylic acid and an aromatic diamine as raw materials, and are obtained by polycondensation thereof. Here, the combination of diamine and dicarboxylic acid is regarded as one type of monomer in combination of one type of diamine and one type of dicarboxylic acid.

Examples of the aliphatic diamine and aliphatic dicarboxylic acid used as raw materials include those exemplified as the starting materials for the aliphatic homopolyamide resin (A-1). Examples are also included.
Examples of aromatic diamines include meta-xylylenediamine and para-xylylenediamine, and examples of aromatic dicarboxylic acids include naphthalenedicarboxylic acid, terephthalic acid, isophthalic acid, and phthalic acid.

Specific examples of the aromatic homopolyamide resin (A-3) include polynonamethylene terephthalamide (polyamide 9T), polyhexamethylene terephthalamide (polyamide 6T), polyhexamethylene isophthalamide (polyamide 6I), polyxyl and lenadipamide (polyamide MXD6). The aromatic homopolyamide resin (A-3) may be used singly or as a mixture of two or more.

Examples of the production apparatus and polymerization method for the aromatic homopolyamide resin (A-3) are the same as those exemplified in the section for the aliphatic homopolyamide resin (A-1).

The degree of polymerization of (A-3) aromatic homopolyamide resin in the present invention is not particularly limited, but from the viewpoint of moldability and mechanical properties, (A-3) aromatic copolymerization is performed according to JIS K 6920-2. The relative viscosity of the polyamide measured at a resin temperature of 25 ° C. is preferably 1.9 or more and 5.0 or less, more preferably 2.3 or more and 4.5 or less, and 2.7 or more and 4.3 or less is more preferable. Furthermore, from the viewpoint of improving the effect of the present invention, 3.2 or more and 4.2 or less is particularly preferable.

(A-4) Aromatic copolymerized polyamide resin Aromatic polyamide is an aromatic polyamide resin containing at least one aromatic monomer component, for example, an aliphatic dicarboxylic acid and an aromatic diamine, an aromatic dicarboxylic acid and A polyamide resin obtained by polycondensation of an aliphatic diamine or an aromatic dicarboxylic acid and an aromatic diamine as raw materials. Among the above aromatic polyamide resins, the aromatic copolyamide resin (A-4) is a polyamide resin composed of two or more structural units. Here, the combination of diamine and dicarboxylic acid is regarded as one type of monomer in combination of one type of diamine and one type of dicarboxylic acid.

Examples of the aliphatic diamine and aliphatic dicarboxylic acid used as raw materials include those exemplified as the starting materials for the aliphatic homopolyamide resin (A-1). Examples are also included. These aliphatic diamines and aliphatic dicarboxylic acids may be used singly or in combination of two or more.

Examples of aromatic diamines include meta-xylylenediamine and para-xylylenediamine, and examples of aromatic dicarboxylic acids include naphthalenedicarboxylic acid, terephthalic acid, isophthalic acid, and phthalic acid.
These aromatic diamines and aromatic dicarboxylic acids may be used singly or in combination of two or more.

In addition, the aromatic copolyamide resin may contain structural units derived from lactams and aminocarboxylic acids. The same ones as those mentioned above can be mentioned.
These lactams and aminocarboxylic acids may be used singly or in combination of two or more.

Specific examples of the aromatic copolymerized polyamide resin (A-4) include (polyamide 66/6T), polyhexamethylene terephthalamide/polycaproamide copolymer (polyamide 6T/6), polyhexamethylene adipamide/ Polyhexamethylene isophthalamide copolymer (polyamide 66/6I), polyhexamethylene isophthalamide/polycaproamide copolymer (polyamide 6I/6), polydodecanamide/polyhexamethylene terephthalamide copolymer (polyamide 12/6T), polyhexamethylene azide Pamide/polyhexamethylene terephthalamide/polyhexamethylene isophthalamide copolymer (polyamide 66/6T/6I), polyhexamethylene adipamide/polycaproamide/polyhexamethylene isophthalamide copolymer (polyamide 66/6/6I), polyhexamethylene terephthalamide/polyhexamethylene isophthalamide copolymer (polyamide 6T/6I), polyhexamethylene terephthalamide/poly(2-methylpentamethylene terephthalamide) copolymer (polyamide 6T/M5T), and the like. The aromatic copolyamide resin (A-4) may be used alone or in combination of two or more. Among these, polyamide 6T/6I is preferred.

Examples of the production apparatus and polymerization method for the aromatic copolyamide resin (A-4) are the same as those exemplified in the section for the aliphatic homopolyamide resin (A-1).

The degree of polymerization of the aromatic copolyamide resin (A-4) in the present invention is not particularly limited, but from the viewpoint of molding processability and mechanical properties, according to JIS K 6920-2, (A-4) aromatic copolyamide resin The relative viscosity of the polymerized polyamide measured at a resin temperature of 25° C. is preferably 1.9 or more and 5.0 or less, more preferably 2.3 or more and 4.5 or less, and 2.7 or more and 4.3 More preferably: Furthermore, from the viewpoint of improving the effect of the present invention, 3.2 or more and 4.2 or less is particularly preferable. When the relative viscosity is within the above range, molding processability is good, and mechanical properties are also good.

The terminal amino group concentration of the aromatic copolymerized polyamide resin (A-4) is determined by neutralization titration after dissolving in a mixed solvent of phenol and methanol. The terminal amino group concentration of the aromatic copolyamide resin (A-4) is preferably 20 μmol/g or more and 60 μmol/g or less. When the terminal amino group concentration is within the above range, it is preferable from the viewpoint of adhesion to reinforcing materials and adhesion to other resins.

The polyamide resin (A) in the first invention has a relative viscosity of 1.9 or more and 5.0 measured at 25°C by dissolving 1 g of polyamide in 100 ml of 96% concentrated sulfuric acid in accordance with JIS K-6920-2. or less, preferably 2.3 or more and 4.5 or less, more preferably 2.7 or more and 4.3 or less. Furthermore, from the viewpoint of improving the effects of the present invention, it is more preferably 3.2 or more and 4.2 or less. When the relative viscosity is within the above range, molding processability is good, and mechanical properties are also good.

The polyamide resin (A) is composed of two or more polyamide resins having different relative viscosities (e.g., at least one aliphatic homopolyamide resin (A-1) and at least one aliphatic copolymerized polyamide resin (A-2) When containing, the relative viscosity in the polyamide resin (A) is preferably measured with the above content, but if the relative viscosity of each polyamide resin and its mixing ratio are known, the relative viscosity of each mixing An average value calculated by summing the values obtained by multiplying the ratios may be used as the relative viscosity of the polyamide resin (A).

The terminal amino group concentration of the polyamide resin (A) in the first invention is preferably in the range of 30 μmol / g or more, preferably 30 μmol / g, as the terminal amino group concentration obtained by neutralization titration by dissolving in a mixed solvent of phenol and methanol. A more preferable range is 50 μmol/g or less. Within the above range, sufficient moldability and mechanical properties can be obtained.

The polyamide resin (A) is composed of two or more polyamide resins having different terminal amino group concentrations (e.g., at least one aliphatic homopolyamide resin (A-1) and at least one aliphatic copolymerized polyamide resin (A- When 2)) is included, the terminal amino group concentration in the polyamide resin (A) is preferably measured by the above-mentioned neutralization measurement, but the terminal amino group concentration and the mixing ratio of each polyamide resin are known. If there is, the terminal amino group concentration of the polyamide resin (A) may be the average value calculated by summing the values obtained by multiplying the respective terminal amino group concentrations by the mixture ratios.

The polyamide resin (A) in the first invention is preferably at least one selected from the group consisting of polyamide 6, polyamide 6/66, polyamide 6/12 and polyamide 6/66/12, and polyamide 6 is more preferred.

The polyamide resin (A) in the first invention is 60 to 95% by mass in 100% by mass of the polyamide resin composition, preferably 65 to 90% by mass, more preferably 65 to 85% by mass, more preferably 70 to 80% by mass. % by mass. If the content of the polyamide resin (A) is less than the above range, moldability will be poor, and if it is more than the above range, the water absorption rate of the molded product will increase and the calcium chloride resistance will decrease.

<Novolak-type phenolic resin (B)>
The polyamide resin composition of the first invention contains a novolak-type phenolic resin (B).
Examples of the novolak-type phenolic resin (B) in the first invention include those produced by condensation polymerization of phenols and aldehydes in the presence of an acidic catalyst. However, it is preferable not to contain resol-type phenol-formaldehyde produced by condensation polymerization of phenols and aldehydes in the presence of an alkaline catalyst.

Examples of phenols used in the production of the novolak-type phenolic resin (B) include phenol, cresol, trimethylphenol, xylenol, resorcinol, catechol, butylphenol, octylphenol, nonylphenol, phenylphenol, dihydroxybenzene, bisphenol A, and naphthol. monohydric or polyhydric phenols such as and substituted products thereof. These may be used individually by 1 type, or may be used in combination of 2 or more type. Among these, phenol and cresol are preferred, and phenol is more preferred.

Specific examples of aldehydes used in the production of the novolak-type phenolic resin (B) include formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, glyoxal, n-propanal, n-butanal, isopropanal, isobutyraldehyde, 3 -methyl-n-butanal, benzaldehyde, p-tolylaldehyde, 2-phenylacetaldehyde and the like, and these may be used alone or in combination of two or more. Among these, formaldehyde and acetaldehyde are preferred, and formaldehyde is more preferred.

Examples of acidic catalysts include, but are not limited to, oxalic acid, hydrochloric acid, sulfuric acid, phosphoric acid, acetic acid, p-toluenesulfonic acid, phenolsulfonic acid, formic acid, maleic acid, zinc acetate, and zinc octylate.

Among such novolak-type phenolic resins (B), phenol-formaldehyde resins represented by the following formula (1) are preferable from the viewpoint of mechanical properties and heat resistance.

In the above formula (1), n is preferably 1-200, more preferably 1-50, even more preferably 5-20.

The number average molecular weight of the novolak-type phenolic resin (B) in the first invention is preferably 500 to 5,000, more preferably 700 to 3,000, more preferably 1,000 to 3,000, from the viewpoint of moldability and heat resistance. is particularly preferred. The number average molecular weight is the number average molecular weight calculated based on the hydroxyl value measured according to JIS K 1557. Specifically, the hydroxyl value is measured and calculated using (56.1 × 1000 × valence) / hydroxyl value by the terminal group determination method (in this formula, the unit of hydroxyl value is [mgKOH / g] is). In the above formula, the valence is the number of hydroxyl groups in one molecule.

The softening point temperature of the novolak-type phenolic resin (B) in the first invention is 130°C or less, preferably 110 to 130°C, more preferably 120 to 130°C. The softening point temperature is a value determined by ring and ball method softening point measurement based on JIS K6910. When the softening point temperature of the novolac-type phenol resin (B) is within the above range, moldability is improved.

Commercially available products of such novolac-type phenolic resins include HF-4M, NC58, H-1 manufactured by Meiwa Kasei, and RHENOSIN (registered trademark) PR95 manufactured by LANXESS.

The novolak-type phenolic resin (B) is contained in an amount of 5 to 40% by mass, preferably 10 to 30% by mass, in 100% by mass of the polyamide resin composition in the first invention. If the amount of the novolac-type phenolic resin is less than the above range, the water absorption rate of the molded article increases and the resistance to calcium chloride deteriorates. If the content of the novolak-type phenolic resin is more than the above range, the heat resistance and mechanical properties of the polyamide composition will deteriorate.

<Additive>
Depending on the purpose, etc., the polyamide resin composition may contain optional components such as dyes, pigments, fibrous reinforcing materials, particulate reinforcing materials, plasticizers, antioxidants, heat-resistant agents, foaming agents, weathering agents, crystal nucleating agents, crystals Accelerators, releasing agents, lubricants, antistatic agents, flame retardants, auxiliary flame retardants, colorants, and other functional imparting agents may be contained as appropriate.
The optional additive may be contained in an amount of preferably 0.01 to 1% by mass, more preferably 0.05 to 0.5% by mass, based on 100% by mass of the polyamide resin composition.

The polyamide resin composition of the first invention may contain a thermoplastic resin other than the polyamide resin (A) and the novolak-type phenol resin (B). Thermoplastic resins other than the polyamide resin (A) and the novolak-type phenolic resin (B) are preferably 2% by mass or less in 100% by mass of the polyamide resin composition from the viewpoint of mechanical properties and moldability, and 0.1 mass % is more preferable, and not containing is even more preferable. That is, the polyamide resin composition of the first invention preferably contains a novolak-type phenol resin (B) as a main component as a thermoplastic resin other than the polyamide resin (A), and a thermoplastic resin other than the polyamide resin (A) It preferably contains 90% by mass or more of the novolac-type phenolic resin (B), more preferably 95% by mass or more, based on 100% by mass of the resin.
Moreover, it is preferable that the polyamide resin composition of the first invention does not substantially contain an ethylene-based elastomer. If an ethylene-based elastomer is contained, the heat resistance may be lowered.

<Method for producing polyamide resin composition>
The method for producing the polyamide resin composition is not particularly limited, and for example, the following method can be applied.
For mixing the polyamide resin (A), the novolak-type phenolic resin (B), and other optional components, a known melt-kneader such as a single-screw or twin-screw extruder, a Banbury mixer, a kneader, and a mixing roll is used. Used. For example, using a twin-screw extruder, after blending all the raw materials, a method of melt-kneading, a method of blending a part of the raw materials, melt-kneading, further blending the remaining raw materials and melt-kneading, or part Any method may be used, such as a method of mixing the remaining raw materials using a side feeder during melt-kneading after blending the raw materials.

<Characteristics of Polyamide Resin Composition>
The extracted amount when the polyamide resin composition of the first invention is extracted for 6 hours by the Soxhlet extraction method using water as a solvent is 1.5% by mass or less with respect to 100% by mass of the polyamide resin composition used for extraction. and preferably 1.2% by mass or less.
When the polyamide resin composition of the first invention is extracted for 3 hours by the Soxhlet extraction method using methanol as a solvent, the extracted amount is 7.5% by mass or less with respect to 100% by mass of the polyamide resin composition used for extraction. and more preferably 6.8% by weight or less.
The extraction method used was the Soxhlet extraction method. The extractable amount was determined by the formula: (mass of polyamide resin composition before boiling—mass of residue after vacuum drying after boiling)/mass of polyamide resin composition before boiling.
Such hot water extraction amount and hot methanol extraction amount can be adjusted by appropriately adjusting the selection of the novolak resin and the blending amount of each component.
If the amount extracted by the Soxhlet extraction method using water or methanol as the solvent is larger than the above range, the polyamide resin and novolak resin will decompose from the molded article, resulting in a large amount of monomers eluting. , the molded product becomes brittle and the monomer bleeds out on the surface of the molded product.

[Molded article of polyamide resin composition and use thereof]
The polyamide resin composition of the first invention can be suitably used for producing injection-molded articles by injection molding, extrusion-molded articles by extrusion molding, blow-molded articles by blow molding, and rotomolded articles by rotational molding. Since the polyamide resin composition has good injection moldability, it can be suitably used for injection-molded articles.

The method of manufacturing an injection-molded product from a polyamide resin composition by injection molding is not particularly limited, and a known method can be used. For example, a method conforming to ISO294-1 is taken into consideration.

The method for producing an extruded product from the polyamide resin composition by extrusion molding is not particularly limited, and known methods can be used.
It is also possible to obtain a multi-layered structure by co-extrusion with polyolefin such as polyethylene or other thermoplastic resin, followed by blow molding. In that case, it is possible to provide an adhesive layer between the polyamide resin composition layer and another thermoplastic resin layer such as polyolefin. In the case of multilayer structures, the polyamide resin composition of the present invention can be used for both the outer layer and the inner layer.

The method for producing a blow-molded product from a polyamide resin composition by blow molding is not particularly limited, and a known method can be used. In general, blow molding may be carried out after the parison is formed using an ordinary blow molding machine. The preferred resin temperature during parison formation is preferably in the range of 10° C. to 70° C. higher than the melting point of the polyamide resin composition.

The method for producing a rotomolded article by rotomolding from a polyamide resin composition is not particularly limited, and a known method can be used. For example, the method described in International Publication 2019/054109 is taken into consideration.

Injection-molded products by injection molding, extrusion-molded products by extrusion molding, blow-molded products by blow molding, and rotational-molded products by rotational molding include, but are not limited to, spoilers, air intake ducts, intake manifolds, resonators, fuel tanks, Automotive parts such as gas tanks, hydraulic oil tanks, fuel filler tubes, fuel delivery pipes, and various other hoses, tubes, and tanks; mechanical parts such as power tool housings and pipes; - Suitable for various applications such as electronic parts, household/office supplies, building material-related parts, and furniture parts. Among these, the polyamide resin composition is preferably used for automobile parts because of its excellent resistance to calcium chloride.　

In addition, since the polyamide resin composition has excellent gas barrier properties, it is suitably used for molded articles that come into contact with high-pressure gas, such as tanks, tubes, hoses, and films that come into contact with high-pressure gas. The type of gas is not particularly limited, and includes hydrogen, nitrogen, oxygen, helium, methane, butane, propane, etc. Gases with low polarity are preferred, and hydrogen, nitrogen, and methane are particularly preferred.

It is also possible to obtain a multilayer structure by co-extrusion with polyolefins such as polyethylene or other thermoplastic resins, followed by blow molding. In that case, it is also possible to provide an adhesive layer between the polyamide resin composition layer and another thermoplastic resin layer such as polyolefin. In the case of multilayer structures, the polyamide resin composition of the present invention can be used for both the outer layer and the inner layer.

2. Second Invention The second invention comprises 100% by mass of the polyamide resin composition, 30 to 70% by mass of the polyamide resin (A), 10 to 40% by mass of the novolak phenolic resin (B), and a reinforcing filler (C ) relates to a polyamide resin composition containing 5 to 40% by mass.

<Polyamide resin (A)>
The polyamide resin composition of the second invention contains a polyamide resin (A).
Examples of the polyamide resin (A) include an aliphatic homopolyamide resin (A-1), an aliphatic copolyamide resin (A-2), an aromatic homopolyamide resin (A-3) and an aromatic copolyamide resin (A -4). These may be used individually by 1 type, or may be used in combination of 2 or more types. Among these, from the viewpoint of mechanical properties and molding processability, the polyamide resin (A) is selected from the group consisting of aliphatic homopolyamide resin (A-1) and aliphatic copolymerized polyamide resin (A-2). It preferably contains at least one, and more preferably contains an aliphatic homopolyamide resin (A-1).

(A-1) Aliphatic homopolyamide resin The definition of the aliphatic homopolyamide resin (A-1) is the same as in the first invention, and the aliphatic homopolyamide resin (A-1) is the first invention and Similar resins may be mentioned.

Among them, the aliphatic homopolyamide resin (A-1) is selected from the group consisting of polyamide 6, polyamide 11, polyamide 12, polyamide 66, polyamide 610 and polyamide 612 from the viewpoint of the polymerization productivity of the aliphatic homopolyamide resin. At least one is preferred, at least one selected from polyamide 6, polyamide 11, polyamide 12, polyamide 610 and polyamide 612 is more preferred, and polyamide 6 is even more preferred.
The production apparatus and polymerization method for the aliphatic homopolyamide resin (A-1) are also the same as in the first invention.

The relative viscosity of the aliphatic homopolyamide resin (A-1) is measured at 25°C by dissolving 1 g of the aliphatic homopolyamide in 100 ml of 96% concentrated sulfuric acid in accordance with JIS K 6920-2. The relative viscosity of the aliphatic homopolyamide is preferably 1.9 to 5.0, more preferably 2.1 to 4.5, even more preferably 2.3 to 4.2. Furthermore, from the viewpoint of improving the effects of the present invention, 2.3 to 3.4 are particularly preferable. When the relative viscosity is within the above range, molding processability is good, and mechanical properties are also good.

The terminal amino group concentration of the aliphatic homopolyamide resin (A-1) is determined by neutralization titration after dissolving in a mixed solvent of phenol and methanol. The terminal amino group concentration of the aliphatic homopolyamide resin (A-1) is preferably 30 μmol/g or more, more preferably 30 μmol/g or more and 110 μmol/g or less.

(A-2) Aliphatic Copolyamide Resin The definition of the aliphatic copolyamide resin (A-2) is the same as in the first invention, and the aliphatic copolyamide resin (A-2) is the first and resins similar to those of the invention.

Among these, at least one selected from the group consisting of polyamide 6/66, polyamide 6/12 and polyamide 6/66/12 is preferable from the viewpoint of suppressing the water absorption rate of the molded product and maintaining the mechanical strength, At least one selected from the group consisting of polyamide 6/66 and polyamide 6/66/12 is more preferred, and polyamide 6/66 is particularly preferred.
The production apparatus and polymerization method for the aliphatic copolyamide resin (A-2) are also the same as in the first invention.

The relative viscosity of the aliphatic copolyamide resin (A-2) is determined by dissolving 1 g of the aliphatic copolyamide in 100 ml of 96% concentrated sulfuric acid in accordance with JIS K 6920-2, from the viewpoint of moldability and mechanical properties. , the relative viscosity measured at 25° C. is preferably 1.9 to 5.0, more preferably 2.1 to 4.5, even more preferably 2.3 to 4.2. Furthermore, from the viewpoint of improving the effects of the present invention, 2.3 to 3.4 are particularly preferable. When the relative viscosity is within the above range, molding processability is good, and mechanical properties are also good.

The terminal amino group concentration of the aliphatic copolyamide resin (A-2) is determined by neutralization titration after dissolving in a mixed solvent of phenol and methanol. The terminal amino group concentration of the aliphatic copolyamide resin (A-2) is preferably 30 μmol/g or more, more preferably 30 μmol/g or more and 70 μmol/g or less. When the terminal amino group concentration is within the above range, it is preferable from the viewpoint of adhesion to reinforcing materials and adhesion to other resins.

(A-3) Aromatic homopolyamide resin The definition of the aromatic homopolyamide resin (A-3) is the same as in the first invention, and the aromatic homopolyamide resin (A-3) is the same as in the first invention. Similar resins may be mentioned.
The production apparatus and polymerization method for the aromatic homopolyamide resin (A-3) are also the same as in the first invention.

The degree of polymerization of the aromatic homopolyamide resin (A-3) is not particularly limited, but from the viewpoint of molding processability and mechanical properties, the resin temperature of the aromatic copolymerized polyamide (A-3) according to JIS K 6920-2 The relative viscosity measured at 25° C. is preferably 1.9 to 5.0, more preferably 2.1 to 4.5, even more preferably 2.3 to 4.2. Furthermore, from the viewpoint of improving the effects of the present invention, 2.3 to 3.4 are particularly preferable. When the relative viscosity is within the above range, molding processability is good, and mechanical properties are also good.

(A-4) Aromatic Copolyamide Resin The definition of the aromatic copolyamide resin (A-4) is the same as in the first invention, and the aromatic copolyamide resin (A-4) is the first and resins similar to those of the invention. Among these, polyamide 6T/6I is preferred.
The production apparatus and polymerization method for the aromatic copolyamide resin (A-4) are also the same as in the first invention.

The degree of polymerization of the aromatic copolyamide resin (A-4) in the present invention is not particularly limited, but from the viewpoint of molding processability and mechanical properties, the aromatic copolyamide resin (A- The relative viscosity of 4) measured at a resin temperature of 25° C. is preferably 1.9 to 5.0, more preferably 2.1 to 4.5, and 2.3 to 4.2. is more preferred. Furthermore, from the viewpoint of improving the effects of the present invention, 2.3 to 3.4 are particularly preferable. When the relative viscosity is within the above range, molding processability is good, and mechanical properties are also good.

The polyamide resin (A) in the second invention is obtained by dissolving 1 g of polyamide in 100 ml of 96% concentrated sulfuric acid in accordance with JIS K 6920-2, and having a relative viscosity of 1.9 to 5.0 measured at 25 ° C. is preferably 2.1 to 4.5, and even more preferably 2.3 to 4.2. Furthermore, from the viewpoint of improving the effects of the present invention, 2.3 to 3.4 are particularly preferable. When it is within the above range, the moldability is good and the mechanical properties are excellent.

When the polyamide resin (A) contains two or more types of polyamide resins with different relative viscosities, the method of determining the relative viscosity is the same as in the first invention.

The terminal amino group concentration of the polyamide resin (A) in the second invention is dissolved in a mixed solvent of phenol and methanol and obtained by neutralization titration. A more preferable range is 110 μmol/g or more. Within this range, sufficient moldability and mechanical properties can be obtained.

When the polyamide resin (A) contains two or more polyamide resins with different terminal amino group concentrations, the method for determining the terminal amino group concentration is the same as in the first invention.

The polyamide resin (A) in the second invention is preferably at least one selected from the group consisting of polyamide 6, polyamide 6/66, polyamide 6/12 and polyamide 6/66/12, and polyamide 6 is more preferred.

The polyamide resin (A) in the second invention is contained in an amount of 30-70% by mass, preferably 35-65% by mass, more preferably 40-60% by mass in 100% by mass of the polyamide resin composition. If the content of the polyamide resin (A) is less than the above range, moldability will be poor, and if it is more than the above range, the water absorption rate of the molded product will increase and the calcium chloride resistance will decrease.

<Novolak-type phenolic resin (B)>
The polyamide resin composition of the second invention contains a novolak-type phenolic resin (B).
As the novolak-type phenolic resin (B) in the second invention, the same ones as in the first invention can be mentioned. That is, the phenols, aldehydes and acidic catalysts used in the production of the novolak-type phenolic resin (B) are the same as in the first invention.

The number average molecular weight of the novolak-type phenolic resin (B) is preferably 500 to 5,000, more preferably 700 to 3,000, and particularly preferably 1,000 to 3,000, from the viewpoint of moldability and heat resistance. The method for measuring the number average molecular weight is the same as in the first invention.

The softening point temperature of the novolak-type phenolic resin (B) in the second invention is preferably 130°C or less, more preferably 110°C to 130°C, even more preferably 120°C to 130°C. The softening point temperature is a value determined by ring and ball method softening point measurement based on JIS K6910. When the softening point temperature of the novolak-type phenol resin (B) is within the above range, moldability is improved.

Commercially available products of such novolak-type phenolic resins include HF-4M, NC58, H-1 manufactured by Meiwa Kasei, and RHENOSIN (registered trademark) PR95 manufactured by LANXESS.

The novolac-type phenol resin (B) is contained in an amount of 10 to 40% by mass, preferably 10 to 30% by mass, in 100% by mass of the polyamide resin composition of the second invention. If the amount of the novolac-type phenolic resin is less than the above range, the water absorption rate of the molded article increases and the resistance to calcium chloride deteriorates. If the content of the novolak-type phenolic resin is more than the above range, the heat resistance and mechanical properties of the polyamide composition will deteriorate.

<Reinforcing filler (C)>
The polyamide resin composition of the second invention contains a reinforcing filler (C).
The reinforcing filler (C) in the second invention may be either an inorganic filler or an organic filler, such as glass fiber, carbon fiber, cellulose fiber, flaky glass, mica, talc, kaolin, clay, alumina, and various metal foils. etc. The shape may be fibrous, plate-like, or granular. Among them, at least one selected from the group consisting of glass fiber, carbon fiber and cellulose fiber is preferable from the viewpoint of improving the mechanical properties without reducing the flexibility of the molded article. The reinforcing filler (C) may be used alone or in combination of two or more.

The reinforcing filler (C) may be surface-treated with a surface treatment agent. Furthermore, in order to improve workability, these surface treatment agents may be aggregated or granulated. Surface treatment agents include various coupling agents such as silane coupling agents, titanium coupling agents, aluminum coupling agents, and zirconia coupling agents; water glass, methyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, Examples include starch, polyvinyl alcohol, acrylic resins, epoxy resins, phenol resins, polyvinyl acetate, polyurethane resins, epoxy compounds, isocyanate compounds, colloidal silica, colloidal alumina, fatty acids, surfactants, and the like. The surface treatment agents may be used alone or in combination of two or more.

The surface treatment agent may be applied to the reinforcing filler (C) in advance, dried and subjected to surface treatment or convergence treatment, or may be added simultaneously with the reinforcing filler (C) during preparation of the resin composition. good. When the polyamide resin and the reinforcing filler (C) are blended and melt-kneaded to produce a polyamide resin composition, the reinforcing filler (C) in the resin composition is completely unraveled even if it is as it is. It may be broken into individual particles, may be partially unraveled and partly left as it is, or the individual unraveled particles may be further pulverized.

When the reinforcing filler (C) is glass fiber, the raw material glass fiber may have an average fiber diameter of 4 to 25 μm, for example. From the viewpoint of the dimensional stability and mechanical properties of molded articles made from the composition, the average fiber diameter is preferably 6 to 23 μm, and for example, those having an average fiber diameter of 10 to 23 μm can be used.

The glass fibers may be used alone or in combination of two or more. Two or more types of glass fibers having different average fiber diameters may be used. Examples of combinations of glass fiber diameters include (C1) glass fibers with an average fiber diameter of 6 to 11 μm and (C2) glass fibers with an average fiber diameter of 13 to 25 μm.

The raw material glass fiber length (cut length) is not particularly limited, and preferably cut chopped strands of 1 mm to 50 mm can be used, and 3 mm to 10 mm is more preferable from the viewpoint of productivity.
The average fiber length of the glass fibers in the polyamide resin composition is not particularly limited, and preferably 50 μm to 1,000 μm can be used, and 100 μm to 500 μm is more preferable from the viewpoint of dimensional stability of the molded product. It is preferably 200 μm to 400 μm, more preferably 200 μm to 400 μm.

The above values for the average fiber diameter of the glass fiber and the raw glass fiber length (cut length) are the values before melting and kneading with the polyamide. The value of the average fiber length of the glass fibers in the polyamide resin composition is the value after melt-kneading with the polyamide. The value after melt-kneading takes into consideration the case where at least part of the glass fibers are broken and dispersed in the composition during the melt-kneading of raw materials in the production process of the polyamide composition.

The average fiber diameter of the raw material glass fiber and the raw material glass fiber length (cut length) can be observed using an optical microscope. The average fiber diameter of the raw material glass fiber (B) and the raw material glass fiber length (cut length) may be catalog values.
The average fiber length of the glass fibers in the polyamide resin composition can be observed with an optical microscope after the polyamide resin is dissolved in the polyamide resin composition using sulfuric acid and separated from the glass fibers. About 1,000 arbitrarily selected glass fibers are measured from the observed image using image analysis software, and the average value is determined to be the average fiber length.
Commercially available glass fibers include ECS 03T-249H, ECS 03T-275H, and the like, manufactured by Nippon Electric Glass Co., Ltd.

Commercial products of glass flakes include Nippon Sheet Glass Co., Ltd. product names "E glass flake (registered trademark) REF-160A (average thickness: 5 μm, average particle size: 160 μm)", "E glass flake (registered trademark) REF -600A (average thickness: 5 μm, average particle size: 600 μm)”, Nippon Sheet Glass Co., Ltd. product name “C glass flake (registered trademark) RCF-160A (average thickness: 5 μm, average particle size: 160 μm)”, “ C glass flake (registered trademark) RCF-600A (average thickness: 5 μm, average particle size: 600 μm)”, Nippon Sheet Glass Co., Ltd. product name “Fine flake (registered trademark) MEG160FY-M01 (average thickness: 0.7 μm, average particle size: 160 μm)” and the like.

The reinforcing filler (C) is contained in an amount of 5 to 40% by mass, preferably 10 to 35% by mass, more preferably 15 to 30% by mass in 100% by mass of the polyamide resin composition of the second invention. If the amount of the reinforcing filler compounded is less than the above range, the mechanical properties are deteriorated, and if it exceeds the above range, moldability becomes difficult.

<Additive>
Optional additives and their content in the polyamide resin composition are the same as in the first invention.

The polyamide resin composition of the second invention may contain a thermoplastic resin other than the polyamide resin (A) and the novolak-type phenolic resin (B). Thermoplastic resins other than the polyamide resin (A) and the novolac phenolic resin (B) are preferably 2% by mass or less in 100% by mass of the polyamide resin composition from the viewpoint of not impairing the mechanical properties, and 0.1 Less than mass % is more preferable, and not containing is even more preferable. That is, the polyamide resin composition of the second invention preferably contains a novolak-type phenol resin (B) as a main component as a thermoplastic resin other than the polyamide resin (A), and a thermoplastic resin other than the polyamide resin (A) It preferably contains 90% by mass or more of the novolac-type phenolic resin (B), more preferably 95% by mass or more, based on 100% by mass of the resin.

Also, the polyamide resin composition of the second invention preferably does not substantially contain an ethylene-based elastomer. If an ethylene-based elastomer is contained, the mechanical properties and heat resistance may deteriorate. Ethylene-based elastomers also include ethylene-based ionomers.

<Method for producing polyamide resin composition>
The production method of the polyamide resin composition of the second invention is the same as the production method of the first invention.

[Molded article of polyamide resin composition and use thereof]
The polyamide resin composition of the second invention can be suitably used for producing injection-molded articles by injection molding, extrusion-molded articles by extrusion molding, blow-molded articles by blow molding, and rotomolded articles by rotational molding. Its manufacturing method is the same as that of the first invention.
The use of the molded product is also the same as in the first invention. Among these, the polyamide resin composition is preferably used for automobile parts because of its excellent resistance to calcium chloride.

3. Third Invention The third invention is a three-dimensional molding containing 60 to 95% by mass of a polyamide resin (A) and 5 to 40% by mass of a novolak phenolic resin (B) in 100% by mass of a polyamide resin composition for three-dimensional modeling. The present invention relates to a polyamide resin composition for modeling (hereinafter also referred to as "polyamide resin composition").
As used herein, "three-dimensional modeling" refers to modeling by a 3D printer.

<<Polyamide resin composition for three-dimensional modeling>>
<Polyamide resin (A)>
A polyamide resin composition for three-dimensional modeling according to a third aspect of the invention contains a polyamide resin (A).
Examples of the polyamide resin (A) include an aliphatic homopolyamide resin (A-1), an aliphatic copolyamide resin (A-2), an aromatic homopolyamide resin (A-3) and an aromatic copolyamide resin (A -4). These may be used individually by 1 type, or may be used in combination of 2 or more types. Among these, from the viewpoint of molding processability, the polyamide resin (A) is at least one selected from the group consisting of aliphatic homopolyamide resin (A-1) and aliphatic copolymerized polyamide resin (A-2). Preferably, it contains an aliphatic copolymerized polyamide resin (A-2).

Among these, from the viewpoint of suppressing the water absorption rate of the molded product, suppressing the warp foaming of the molded product manufactured by the 3D printer and maintaining the mechanical strength, polyamide 6/66, polyamide 6/12 and polyamide 6/66/ At least one selected from the group consisting of 12 is preferred, at least one selected from the group consisting of polyamide 6/12 and polyamide 6/66/12 is more preferred, and polyamide 6/66/12 is particularly preferred.

The production apparatus and polymerization method for the aliphatic copolyamide resin (A-2) are also the same as in the first invention.

The relative viscosity of the aliphatic copolyamide resin (A-2) is determined by dissolving 1 g of the aliphatic copolyamide in 100 ml of 96% concentrated sulfuric acid in accordance with JIS K 6920-2, from the viewpoint of moldability and mechanical properties. and the relative viscosity measured at 25° C. is preferably from 2.3 to 5.0, more preferably from 2.4 to 5.0, even more preferably from 2.4 to 4.5. 4 or more and 4.2 or less is particularly preferable.

The terminal amino group concentration of the aliphatic copolyamide resin (A-2) is determined by neutralization titration after dissolving in a mixed solvent of phenol and methanol. The terminal amino group concentration of the aliphatic copolymerized polyamide resin (A-2) is preferably 30 μmol/g or more, more preferably 30 μmol/g or more and 50 μmol/g or less. When the terminal amino group concentration is within the above range, it is preferable from the viewpoint of adhesiveness to other resins.

(A-1) Aliphatic homopolyamide resin The definition of the aliphatic homopolyamide resin (A-1) is the same as in the first invention, and the aliphatic homopolyamide resin (A-1) is the first invention and Similar resins may be mentioned.
Among them, the aliphatic homopolyamide resin (A-1) is preferably at least one selected from the group consisting of polyamide 6, polyamide 11, polyamide 12, polyamide 66, polyamide 610 and polyamide 612 from the viewpoint of polymerization productivity, At least one selected from polyamide 6, polyamide 11, polyamide 12, polyamide 610 and polyamide 612 is more preferred, and polyamide 6 is even more preferred.

The production apparatus and polymerization method for the aliphatic homopolyamide resin (A-1) are also the same as in the first invention.

The relative viscosity of the aliphatic homopolyamide resin (A-1) is measured at 25°C by dissolving 1 g of the aliphatic homopolyamide in 100 ml of 96% concentrated sulfuric acid according to JIS K 6920-2. The relative viscosity of the aliphatic homopolyamide is preferably from 2.3 to 5.0, more preferably from 2.4 to 5.0, even more preferably from 2.4 to 4.5. Furthermore, from the viewpoint of improving the effects of the present invention, it is particularly preferable to be 2.4 or more and 4.2 or less. When it is 2.3 or more, molding processing is easier, and when it is 5.0 or less, better mechanical properties of the polyamide resin can be maintained.

The terminal amino group concentration of the aliphatic homopolyamide resin (A-1) is determined by neutralization titration after dissolving in a mixed solvent of phenol and methanol. The terminal amino group concentration of the aliphatic homopolyamide resin (A-2) is preferably 30 μmol/g or more, more preferably 30 μmol/g or more and 50 μmol/g or less.

The degree of polymerization of the aromatic copolyamide resin (A-4) in the present invention is not particularly limited, but the relative viscosity measured at 25 ° C. according to JIS K 6920-2 is , is preferably 2.3 or more and 5.0 or less, more preferably 2.4 or more and 5.0 or less, further preferably 2.4 or more and 4.5 or less, and particularly preferably 2.4 or more and 4.2 or less .

The terminal amino group concentration of the aromatic copolymerized polyamide resin (A-4) is determined by neutralization titration after dissolving in a mixed solvent of phenol and methanol. The terminal amino group concentration of the aromatic copolyamide resin (A-4) is preferably 20 μmol/g or more and 60 μmol/g or less.

The degree of polymerization of (A-3) the aromatic homopolyamide resin in the present invention is not particularly limited, but the relative viscosity measured at 25° C. according to JIS K 6920-2 is, from the viewpoint of molding processability and mechanical properties, It is preferably 2.3 or more and 5.0 or less, more preferably 2.4 or more and 5.0 or less, still more preferably 2.4 or more and 4.5 or less, and particularly preferably 2.4 or more and 4.2 or less.

The polyamide resin (A) in the third invention is preferably at least one selected from the group consisting of polyamide 6, polyamide 6/66, polyamide 6/12 and polyamide 6/66/12, and polyamide 6 is more preferred.

The polyamide resin (A) in the third invention is obtained by dissolving 1 g of the polyamide resin in 100 ml of 96% concentrated sulfuric acid in accordance with JIS K 6920-2, and having a relative viscosity of 2.3 or more measured at 25 ° C.5. It is preferably 0 or less, more preferably 2.4 or more and 5.0 or less, and even more preferably 2.4 or more and 4.5 or less. Furthermore, from the viewpoint of improving the effects of the present invention, it is particularly preferable to be 2.4 or more and 4.2 or less. When it is 2.3 or more, molding is easier. Moreover, when it is 5.0 or less, better mechanical properties of the polyamide resin can be obtained.

The terminal amino group concentration of the polyamide resin (A) in the third invention is dissolved in a mixed solvent of phenol and methanol and obtained by neutralization titration. The range of 110 μmol/g or more is more preferable, and the range of 30 μmol/g or more and 70 μmol/g or less is even more preferable. If it is 30 μmol/g or more, the adhesiveness to the reinforcing material is good, and sufficient melt viscosity and impact resistance can be obtained. In addition, when the amount is 110 μmol/g or less, molding processability is good.

The polyamide resin (A) in the third invention is 60 to 95% by mass, preferably 65 to 95% by mass, more preferably 65 to 85% by mass, more preferably 100% by mass of the polyamide resin composition for three-dimensional modeling. is contained in an amount of 70 to 85% by mass, particularly preferably 70 to 78% by mass. If the content of the polyamide resin (A) is less than the above range, the mechanical properties of the polyamide resin are reduced. is large and there is a lot of bubbling.

<Novolak-type phenolic resin (B)>
A polyamide resin composition for three-dimensional modeling according to a third invention contains a novolak-type phenolic resin (B).
As the novolac-type phenolic resin (B) in the third invention, the same ones as in the first invention can be mentioned. That is, the phenols, aldehydes and acidic catalysts used in the production of the novolak-type phenolic resin (B) are the same as in the first invention.

The number average molecular weight of the novolac-type phenolic resin (B) in the third invention is preferably 100 to 20,000, more preferably 300 to 15,000, from the viewpoint of moldability and heat resistance. The method for measuring the number average molecular weight is the same as in the first invention.

The softening point temperature of the novolac-type phenolic resin (B) in the third invention is preferably 50 to 250°C, more preferably 70 to 200°C, and even more preferably 110 to 150°C, from the viewpoint of moldability and heat resistance. , 110-130° C. is particularly preferred, and 120-130° C. is most preferred. The softening point temperature is a value determined by ring and ball method softening point measurement based on JIS K6910.

In 100% by mass of the polyamide resin composition for three-dimensional modeling of the third invention, the novolak phenolic resin (B) is 5 to 40% by mass, preferably 5 to 35% by mass, more preferably 22 to 30% by mass. be If the amount of the novolak-type phenolic resin is less than the above range, the water absorption rate of the molded product increases, and the molded product produced by the three-dimensional modeling apparatus has large warpage and foaming due to water absorption. If the content of the novolak-type phenolic resin is more than the above range, the mechanical properties of the polyamide itself are impaired.

<Additive>
The polyamide resin composition for three-dimensional modeling of the third invention may contain dyes, pigments, fibrous reinforcing materials, particulate reinforcing materials, plasticizers, antioxidants, heat-resistant agents, and foaming agents as optional components depending on the purpose. , a weathering agent, a crystal nucleating agent, a crystallization accelerator, a releasing agent, a lubricant, an antistatic agent, a flame retardant, a flame retardant auxiliary, a coloring agent, and other function-imparting agents.
The optional additive is contained in an amount of preferably 0 to 35% by mass, more preferably 0.05 to 30% by mass, based on 100% by mass of the polyamide resin composition for three-dimensional modeling.

The polyamide resin composition for three-dimensional modeling of the third invention may contain resins other than the polyamide resin (A) and the novolac-type phenolic resin (B). Resins other than the polyamide resin (A) and the novolak-type phenolic resin (B) are preferably contained in an amount of 0 to 20% by mass.

<Method for producing a polyamide resin composition for three-dimensional modeling>
The method for producing the polyamide resin composition for three-dimensional modeling according to the third invention is the same as the method for producing the polyamide resin composition according to the first invention.

<Characteristics of polyamide resin composition for three-dimensional modeling>
When the polyamide resin composition for three-dimensional modeling of the third invention contains polyamide 6 according to ISO 527, molding temperature: 250 ° C., mold temperature: 40 ° C., polyamide resin (A) contains polyamide 6. If not included, the type A tensile test piece obtained by injection molding at a molding temperature of 220 ° C and a mold temperature of 40 ° C is stored at room temperature so as not to absorb water after molding, and then the initial mass (W0) is Measured, immersed in water at 40 ° C. for 24 hours, wiped off the attached moisture after removal, measured the mass (W1), and the water absorption calculated by ((W1-W0) / W0) × 100 is 2.2% or less. is preferable, and 2.0% or less is more preferable.
Thus, the polyamide resin composition for three-dimensional modeling has a reduced water absorption rate.

A type A tensile test piece obtained by three-dimensionally shaping the polyamide resin composition for three-dimensional shaping of the third invention into a shape according to the shape of ISO527 using a 3D printer at 23 ° C. and under 50% RH conditions After leaving it for 24 hours, place the test piece on the surface plate, fix one end of the width direction side with a weight of 30 mm width and 200 g, and warp up from the surface plate surface of the other width direction side end The amount of warpage obtained by measuring the amount with a finger is preferably 30 mm or less, more preferably 20 mm or less.
As described above, the polyamide resin composition for three-dimensional modeling suppresses warpage of a molded article obtained by three-dimensional modeling using a 3D printer, and can provide a molded article with good accuracy.

<Filament for 3D printing>
A filament for three-dimensional modeling is produced using the polyamide resin composition for three-dimensional modeling. The method for producing the filament for three-dimensional modeling is not particularly limited, but the polyamide resin composition for three-dimensional modeling is molded by a known molding method such as extrusion molding, or the filament is used as it is during the production of the polyamide resin composition for three-dimensional modeling. It can be obtained by a method such as
Specifically, as a method for producing a filament for three-dimensional modeling from a polyamide resin composition for three-dimensional modeling, for example, when obtaining a filament for three-dimensional modeling by extrusion molding, the conditions are the polyamide for three-dimensional modeling It is preferable to carry out the treatment at a temperature which is 5 to 100° C., preferably 10 to 80° C. higher than the melting point or glass transition temperature (Tg) of the resin composition.

The diameter of the filament for 3D modeling is determined by the device, but in the case of the 1.75 mm specification, the range of 1.65 to 1.85 mm is preferable. In the case of 3.00 mm specification, 2.90 to 3.10 mm is preferable.

A blocking agent may be applied or coated on the surface of the three-dimensional modeling filament to prevent blocking between the three-dimensional modeling filaments before melting.

Examples of blocking agents that can be used here include silicone-based blocking agents, inorganic fillers such as talc, and fatty acid metal salts. These blocking agents may be used alone or in combination of two or more.

Preferred forms of the filament include a wound body in which the filament is wound around a bobbin or the like, and a cartridge in which the filament is stored in a container.

<Three-dimensional modeling method>
Three-dimensional modeling is performed by modeling a polyamide resin composition for three-dimensional modeling or a filament for three-dimensional modeling (hereinafter also referred to as "material for three-dimensional modeling") with a 3D printer, which is a three-dimensional model manufacturing device. Molded bodies can be produced.

There are no particular restrictions on the 3D printer, but an FDM method device is preferred. As shown in FIG. 1, the FDM 3D printer usually comprises a raw material supply unit, a gear 2, a tube 3, a nozzle 4 with a heater 6, and a table 5. The heater and nozzle may be separate.

In the FDM 3D printer, the material for three-dimensional modeling is drawn out from the raw material supply unit, fed into the tube 3 by a pair of opposing gears 2, heated and melted by the heater 6, and pushed out from the nozzle 4.

The temperature for heating and melting the three-dimensional modeling material is not particularly limited, but the melting point or glass transition temperature (Tg) of the polyamide resin composition for three-dimensional modeling or higher, and the melting point or glass transition temperature (Tg) + 300 ° C. or less is preferable, and specifically, the temperature is preferably set by adding 5 to 100° C., preferably 10 to 80° C. to the melting point or glass transition temperature (Tg).

The molten three-dimensional modeling material extruded from the nozzle 4 is a two-dimensional layer obtained by slicing the three-dimensional coordinate data based on the three-dimensional coordinate data, and the table 5 defines the XY axis directions. By stacking these two-dimensional layers on top of each other and successively stacking these two-dimensional layers in the Z-axis direction, a three-dimensionally shaped compact can be obtained.

The molding speed is preferably 10-100 mm/sec.

<Uses of compacts obtained by three-dimensional modeling>
The use of the molded body obtained by three-dimensional modeling of the polyamide resin composition for three-dimensional modeling or the filament for three-dimensional modeling is not particularly limited, but spoilers, air intake ducts, intake manifolds, resonators, fuel tanks, gas tanks, Hydraulic oil tanks, fuel filler tubes, fuel delivery pipes, other automotive parts such as hoses, tubes, and tanks, electric tool housings, mechanical parts such as pipes, electrical and electronic parts such as tanks, tubes, hoses, films, etc. Suitable for various applications such as parts, household/office supplies, building material-related parts, and furniture parts.

In addition, since the polyamide resin composition for three-dimensional modeling has excellent gas barrier properties, it is suitably used for molded articles that come into contact with high-pressure gas, such as tanks, tubes, hoses, and films that come into contact with high-pressure gas. The type of gas is not particularly limited, and includes hydrogen, nitrogen, oxygen, helium, methane, butane, propane, etc. Gases with low polarity are preferred, and hydrogen, nitrogen, and methane are particularly preferred.

1. EXAMPLES OF THE FIRST INVENTION Hereinafter, the first invention will be described in more detail with reference to examples and comparative examples, but the present invention is not limited to these examples.

The measurement methods in Examples and Comparative Examples are as follows.
<Relative viscosity>
It is a value measured at 25° C. by dissolving 1 g of polyamide in 100 ml of 96% concentrated sulfuric acid according to JIS K6920-2.

<Softening point temperature>
The softening point temperature is a value determined by ring and ball method softening point measurement based on JIS K6910.

<Hot water extraction amount>
After the polyamide resin composition was boiled with hot water for 6 hours by the Soxhlet extraction method using water as a solvent, the hot water was removed and the residue was dried in a vacuum dryer at 90° C. for 16 hours. Weigh the amount of residue, subtract the mass of the residue after vacuum drying after boiling from the mass of the polyamide resin composition before boiling, and divide the loss by the mass of the polyamide resin composition before boiling. It was set as the hot water extractable amount per 100% by mass of the resin composition.

<Hot methanol extraction amount>
After boiling the polyamide resin composition with hot methanol for 3 hours by a Soxhlet extraction method using methanol as a solvent, the hot methanol was removed and the residue was dried in a vacuum dryer at 90° C. for 16 hours. Weigh the amount of residue, subtract the mass of the residue after vacuum drying after boiling from the mass of the polyamide resin composition before boiling, and divide the loss by the mass of the polyamide resin composition before boiling. It was taken as the hot methanol extract per 100% by mass of the resin composition.

<Calcium chloride resistance>
An ISO TYPE-A test piece obtained by injection molding a polyamide resin composition was used. A gauze was placed on the test piece, a saturated calcium chloride solution was applied to the test piece, and the test piece was left at 80° C. and 90% RH for 24 hours for pretreatment. After heating the pretreated test piece in an oven at 100 ° C. for 2 hours, a test in which it is left in a constant temperature bath at 80 ° C. and 90% RH for 20 hours is performed as one cycle. The presence or absence of cracks in the test piece was observed with a scope VHX-5000 and evaluated according to the following criteria.
◯: no cracks occurred in the test piece ×: cracks occurred in the test piece.
A sample in which no cracks occurred after one cycle was regarded as acceptable.

<Dielectric constant and dielectric loss tangent>
Using an injection molding machine FANUC T-100D, a mold clamping force of 100 tons, a screw diameter of 36 mm, a cylinder temperature of 250 ° C., a mold temperature of 40 ° C., and an injection speed of 50 mm / sec. A flat plate of 70 mm×2 mm thickness was prepared. This flat plate was immersed in water at 40° C. for 7 days and used as a test piece. Impedance analyzer Agilent 4294A (manufactured by Agilent Technologies Inc.) and fixture Agilent 16451B (manufactured by Agilent Technologies Inc.) were used as dielectric constant measuring devices. The electrode contact method was used for the measurement, and the value of the dielectric loss tangent was obtained at 10 GHz.

<Mechanical properties after water absorption>
An ISO TYPE-A test piece of the polyamide resin composition was immersed in water at 40° C. for 168 hours, and the following mechanical properties were measured using the pretreated test piece. The water absorption was calculated from the difference in mass of the test piece before and after immersion.
(1) Tensile yield stress and tensile fracture nominal strain after water absorption
Using the test piece soaked in water at 40°C for 168 hours, the tensile strength was measured at 23°C according to ISO527 using a tensile tester model 5567 manufactured by Instron.
(2) Flexural strength and flexural modulus after water absorption Using a test piece that has been soaked in water at 40°C for 168 hours, it is measured at 23°C using an Instron tensile tester model 5567 in accordance with ISO 178. measured in

[Examples 1 to 5, Comparative Examples 1 to 4]
Each component described in Table 1 is melt-kneaded with a twin-screw kneader TEX44HCT, a cylinder diameter of 44 mm L / D35, a cylinder temperature of 250 ° C., a screw rotation of 160 rpm, and a discharge rate of 50 kg / hrs, to obtain the desired polyamide resin composition pellet. was made.
The unit of composition in the table is % by mass, and the total resin composition is 100% by mass.

The components listed in Table 1 used the following.
PA6: Polyamide 6, relative viscosity 3.36 (manufactured by UBE Corporation)
PA6/66: Polyamide 6/66, relative viscosity 4.05, polyamide 6 85 mol%, polyamide 66 15 mol% (manufactured by UBE Corporation)
Novolak-type phenolic resin (1): softening point temperature: 102° C., product name HF-4M (manufactured by Meiwa Kasei), structure represented by formula (1), n=about 6.7
Novolac-type phenolic resin (2): softening point temperature: 125°C, product name NC58 (manufactured by Meiwa Kasei), structure represented by formula (1), n = about 14.6

From the results in Table 1, in Examples 1 to 5, the extraction amount with hot water is 1.5% by mass or less, the calcium chloride resistance is good, the insulation is good, the water absorption is low, and the water absorption is low. A polyamide resin composition having excellent mechanical properties is obtained.
Comparing Examples 1 to 5 with Comparative Examples 3 and 4, when the polyamide resin composition contains a specific amount of novolac-type phenolic resin within a specific range of softening point temperature, the amount of novolak-type phenolic resin is higher than that of the polyamide resin alone. , water absorption, calcium chloride resistance, insulation and mechanical properties.
Comparing Examples 1 to 5 with Comparative Examples 1 and 2, when the amount extracted with hot water exceeds 1.5% by mass, the mechanical properties of the polyamide resin composition deteriorate. Moreover, when the hot water extraction amount and the hot methanol extraction amount are large in this way, bleeding out to the surface of the molded article occurs.
Comparing Examples 1, 3 and 4 with Comparative Examples 1 and 2, when the novolac phenol resin (1) is used and the content is 20% by mass or more, the extraction amount with hot water is 1. 0.5% by mass is exceeded. From Examples 2 to 4, when the novolak phenol resin (2) was used, the content was within the range of the first invention, and the extraction amount with hot water was 1.5% by mass or less. I understand.
A comparison of Examples 2 to 4 reveals that, within the scope of the present invention, when the amount of novolac-type phenolic resin added is large, the flexural modulus is high, the water absorption is low, and the insulation and calcium chloride resistance are better. Recognize.

2. EXAMPLES OF THE SECOND INVENTION Hereinafter, the second invention will be described in more detail with reference to examples and comparative examples, but the present invention is not limited to these examples.

<Calcium chloride resistance>
An ISO TYPE-A test piece obtained by injection molding a polyamide resin composition was used. A gauze was placed on the test piece, a saturated calcium chloride solution was applied to the test piece, and the test piece was left at 80° C. and 90% RH for 24 hours for pretreatment. After heating the test piece after pretreatment in an oven at 100 ° C. for 2 hours, a test in which it was left in a constant temperature bath at 80 ° C. and 90% RH for 20 hours was performed as one cycle. Using VHX-5000, the presence or absence of cracks in the test piece was observed and evaluated according to the following criteria.
◯: no cracks occurred in the test piece ×: cracks occurred in the test piece.
A sample in which no cracks occurred after one cycle was regarded as acceptable.

<Mechanical properties after water absorption>
An ISO TYPE-A test piece obtained by injection molding a polyamide resin composition was immersed in water at 40° C. for 168 hours, and the following mechanical properties were measured using the pretreated test piece. The water absorption was calculated by dividing the difference in mass of the test piece before and after immersion by the mass before immersion.
(1) Tensile yield stress and nominal tensile fracture strain after water absorption Using the test piece that has been soaked in water at 40°C for 168 hours, according to ISO 527, at 23°C using an Instron tensile tester model 5567 It was measured.
(2) Flexural modulus and flexural strength after water absorption Measured at 23°C using a test piece that had been soaked in water at 40°C for 168 hours and using an Instron tensile tester model 5567 in accordance with ISO 178. bottom.
(3) Bending elasticity retention after water absorption The bending elasticity retention after water absorption is the bending elasticity after water absorption relative to the bending elasticity before water absorption (=(bending elasticity after water absorption/bending elasticity before water absorption). × 100) The flexural modulus before water absorption was measured using an ISO TYPE-A test piece obtained by injection molding a polyamide resin composition in accordance with ISO 178 using a tensile tester model 5567 manufactured by Instron. Measured at 23°C.

[Examples 6 to 11, Comparative Examples 5 to 10]
Each component described in Table 2 is melt-kneaded with a twin-screw kneader TEX44HCT, a cylinder diameter of 44 mm L / D35, a cylinder temperature of 250 ° C., a screw rotation of 160 rpm, and a discharge rate of 50 kg / hrs, to obtain the desired polyamide resin composition pellet. was made.
Table 2 shows the results.
The unit of composition in the table is % by mass, and the total resin composition is 100% by mass.

The components listed in Table 2 used the following.
PA6 (1): Polyamide 6, relative viscosity 2.47 UBE PA6 (2): Polyamide 6, relative viscosity 3.36 UBE PA6/66: Polyamide 6/66, relative viscosity 3.04, polyamide 6 85 mol%, polyamide 66 15 mol% (manufactured by UBE Corporation)
Novolak-type phenolic resin (1): softening point temperature: 102° C., product name HF-4M (manufactured by Meiwa Kasei), structure represented by formula (1), n=about 6.7
Novolac-type phenolic resin (2): softening point temperature: 125°C, product name NC58 (manufactured by Meiwa Kasei), structure represented by formula (1), n = about 14.6
Glass fiber (1): Product name ECS 03T-249H Cut length 3 mm, average fiber diameter 10.5 μm (catalog value) (manufactured by Nippon Electric Glass)
Glass fiber (2): Product name ECS 03T-275H Cut length 3 mm, average fiber diameter 10.5 μm (catalog value) (manufactured by Nippon Electric Glass)

From the results in Table 2, it can be seen that Examples 6 to 11 have good calcium chloride resistance and mechanical properties after water absorption.
Comparative Examples 5 to 7 are examples in which the resin composition does not contain a novolak-type phenolic resin or, even if it does contain it, is less than the scope of the present invention. In addition, mechanical properties such as bending strength are also inferior to those of the examples.
Comparative Examples 8 to 10 are examples in which the resin composition does not contain glass fiber, but it can be seen that the mechanical properties are inferior to those of the examples. Moreover, as in Comparative Example 9, when the amount of the polyamide resin is larger than that of the Examples, the resistance to calcium chloride is also inferior.

3. Examples of the Third Invention Hereinafter, the third invention will be described in more detail with reference to examples and comparative examples, but the present invention is not limited to these examples.

A test piece used for the measurement was prepared by the following method.
(1) Test piece preparation by injection molding Polyamide resin composition is injection molded according to ISO 527, polyamide 6 at a cylinder temperature of 250 ° C and a mold temperature of 40 ° C, and other copolymer polyamides at a cylinder temperature of 220 ° C. , and a mold temperature of 40°C, type A tensile test pieces were prepared.

(2) Modeling by 3D printer (2-1) Creation of filament Using an extruder, the polyamide resin composition is extruded from a cylinder temperature of 230 ° C. and a nozzle diameter of 3 mm. to create a filament for use in a 3D printer.
(2-2) Modeling by a 3D printer A 3D printer manufactured by Mutoh Industries Co., Ltd., trade name: Value3D MagiX MF-2200D was used with a nozzle diameter of 0.5 mm, a nozzle heater of 240°C, a table temperature of 110°C, and a lamination pitch of 0.5°C. Using the filament obtained in (2-1) at 3 mm, modeling speed 72 mm/sec, without cooling fan, the molten filament is sequentially stacked on the table based on the three-dimensional coordinate data. and obtained a modeled product.

Numerical values described in Examples and Table 3 were measured by the following methods.
(3) Measuring method <relative viscosity>
It is a value measured at 25° C. by dissolving 1 g of polyamide in 100 ml of 96% concentrated sulfuric acid according to JIS K6920-2.

<Water absorption rate>
A type A tensile test piece obtained by injection molding the polyamide resin composition under the conditions of (1) above was stored at room temperature so as not to absorb water after molding, and then the initial mass (W0) was measured. Next, when the test piece after the drying treatment was immersed in water at 40°C for 24 hours and in water at 80°C for 24 hours, the weight (W1) was measured by wiping off the adhering moisture after removal. , ((W1−W0)/W0)×100 was used as the water absorption.

<Warpage amount of 3D printer model>
The polyamide resin composition was shaped according to the shape of ISO527 according to the 3D printer modeling method of (2) above, and the obtained test piece was left under conditions of 23° C. and 50% RH for 24 hours. Next, when the test piece is placed on a surface plate and one end of the width direction side is fixed with a weight of 30 mm in width and 200 g, the amount of warping from the surface of the surface plate for the other end of the width direction side was measured with a finger square.

<Bubbling state from 3D printer nozzle>
The polyamide resin composition was made into filaments by the method (2-1) above. The obtained filaments were left under conditions of 23° C. and 50% RH for 24 hours, 100 hours and 240 hours, and used as humidity-conditioning filaments after 24 hours, 100 hours and 240 hours.
A humidity-controlled filament was supplied to the 3D printer at a feeding speed of 300 mm/min, and the state of foaming of the resin coming out of the nozzle of the 3D printer was visually confirmed.
Foaming was evaluated according to the following criteria.
x: A lot of foaming was observed △: A little foaming was observed O: No foaming was observed A case in which no foaming was observed when the humidity-conditioned filament was used after 24 hours was evaluated as acceptable.

<Mechanical properties of 3D printer models>
For the mechanical properties in the Z-axis direction, the polyamide resin composition was molded according to ISO 178 in accordance with the molding method using a 3D printer described in (2) above, and a tensile tester model 5567 manufactured by Instron The tensile strength and nominal tensile strain at break were measured under the conditions of distance between chucks: 20 mm and test speed: 5 mm/min.
For the mechanical properties in the XY axis direction, the polyamide resin composition was molded into a type A test piece shape according to ISO 527 according to the molding method using a 3D printer described in (2) above, and an Instron tension test was performed. Using a testing machine model 5567, the tensile strength and tensile nominal strain at break were measured under the conditions of distance between chucks: 115 mm and test speed: 5 mm/min.
The XY axis direction refers to the surface of the table being shaped, and the Z axis direction refers to a direction perpendicular to the plane defined by the XY axes.

[Examples 12-21, Comparative Examples 11-14]
Each component listed in Table 3 was melt-kneaded using a twin-screw kneader ZSK32McPlus (manufactured by Coperion), L/D 48, screw diameter 32 mm, cylinder temperature 230°C, screw rotation speed 200 rpm, and discharge rate 50 kg/h. , pellets of the polyamide resin composition were produced.
From the obtained pellets, the test piece of (1) and the shaped article of (2) were prepared.
The unit of composition in the table is % by mass, and the total resin composition is 100% by mass.

The components listed in Table 3 used the following.
PA6 (1): Polyamide 6, relative viscosity 2.47 (manufactured by UBE Corporation)
PA6 (2): Polyamide 6, relative viscosity 3.37 (manufactured by UBE Corporation)
PA6/66: Polyamide 6/66, relative viscosity 4.05, polyamide 6 85 mol%, polyamide 66 15 mol% (manufactured by UBE Corporation)
PA6/12: Polyamide 6/12, relative viscosity 3.87, polyamide 6 80 mol%, polyamide 12 20 mol% (manufactured by UBE Corporation)
PA6/66/12: Polyamide 6/66/12, relative viscosity 4.05, polyamide 6 80 mol%, polyamide 66 10 mol%, polyamide 12 10 mol% (manufactured by UBE Corporation)
Novolak-type phenolic resin (1): softening point temperature: 102° C., product name HF-4M (manufactured by Meiwa Kasei), structure represented by formula (1), n=about 6.7
Novolac-type phenolic resin (2): softening point temperature: 125°C, product name NC58 (manufactured by Meiwa Kasei), structure represented by formula (1), n = about 14.6

When the polyamide resin compositions of Examples 12 to 21 were molded with a 3D printer, the warpage of the molded product was suppressed, and foaming when extruded from the nozzle was suppressed, resulting in a good appearance and a high water absorption rate. It is low and the strength is satisfactory.
In particular, the polyamide resin compositions of Examples 19 to 21 containing the aliphatic copolyamide exhibited more suppressed warpage of molded articles and high strength.
Comparing Examples 14 and 15, it can be seen that warping is more suppressed when a polyamide resin having a relative viscosity within a specific range is used.
Comparing Example 12 and Example 16, it can be seen that when the softening point temperature of the novolac-type phenolic resin is within a specific range, warpage is further suppressed.
Comparing Examples 12-14 with Examples 16-18, it can be seen that when the softening point temperature of the novolac-type phenolic resin is within a specific range, the strength is higher.

The polyamide resin composition of the first invention has good calcium chloride resistance, insulating properties, low water absorption, and good mechanical properties when water is absorbed, so that it can be suitably used for automobile parts.
The polyamide resin composition of the second invention has good calcium chloride resistance, low water absorption, and excellent mechanical properties when water is absorbed, so that it can be suitably used for various parts, especially automobile parts.
The polyamide resin composition for three-dimensional modeling of the third invention is suitably used for modeling with a 3D printer.

1 filament 2 gear 3 tube 4 nozzle 5 table 6 heater 7 FDM method 3D printer

This application claims priority based on Japanese Patent Application No. 2021-122547, Japanese Patent Application No. 2021-122591 and Japanese Patent Application No. 2021-122613. The contents of the entire disclosure of Japanese Patent Application No. 2021-122547, Japanese Patent Application No. 2021-122591 and Japanese Patent Application No. 2021-122613 are cited by reference.

Claims

A polyamide resin composition containing 60 to 95% by mass of a polyamide resin (A) and 5 to 40% by mass of a novolak phenolic resin (B) in 100% by mass of the polyamide resin composition,
The polyamide resin (A) has a relative viscosity of 1.9 or more and 5.0 or less measured at 25° C. in accordance with JIS K6920-2,
The novolak-type phenol resin (B) has a softening point temperature of 130° C. or less,
The polyamide resin composition is extracted for 6 hours by a Soxhlet extraction method using water as a solvent, and the extracted amount is 1.5% by mass or less with respect to 100% by mass of the polyamide resin composition used for extraction. Resin composition.
In 100% by mass of the polyamide resin composition, 30 to 70% by mass of the polyamide resin (A), 10 to 40% by mass of the novolac phenol resin (B), and 5 to 40% by mass of the reinforcing filler (C) Polyamide resin containing Composition.
A polyamide resin composition for three-dimensional modeling containing 60 to 95% by mass of a polyamide resin (A) and 5 to 40% by mass of a novolac-type phenolic resin (B) in 100% by mass of a polyamide resin composition for three-dimensional modeling.
Any one of claims 1 to 3, wherein the polyamide resin (A) contains at least one selected from the group consisting of an aliphatic homopolyamide resin (A-1) and an aliphatic copolyamide resin (A-2). The polyamide resin composition according to item 1.
The polyamide resin (A) is at least one selected from the group consisting of polyamide 6, polyamide 6/66, polyamide 6/12 and polyamide 6/66/12, according to any one of claims 1 to 3. A polyamide resin composition as described.
The polyamide resin composition according to claim 2, wherein the novolak-type phenolic resin (B) has a softening point temperature of 130°C or lower.
The polyamide resin composition according to claim 3, wherein the novolak-type phenolic resin (B) has a softening point temperature of 110 to 150°C.
The polyamide resin composition according to any one of claims 1 to 3, wherein the novolac-type phenolic resin (B) has a softening point temperature of 110 to 130°C.
The polyamide resin composition according to any one of claims 1 to 3, wherein the novolak-type phenolic resin (B) has a softening point temperature of 120 to 130°C.
The polyamide resin composition according to any one of claims 1 to 3, wherein the novolak-type phenol resin (B) is a novolak-type phenol resin represented by the following formula (1).

(In the above formula (1), n is 1 to 200.)
The polyamide resin composition according to claim 1 or 2, wherein the polyamide resin composition contains a novolac-type phenolic resin (B) as a main component as a thermoplastic resin component other than the polyamide resin (A).
The polyamide resin composition according to claim 1 or 2, which does not substantially contain an ethylene elastomer.
The polyamide resin composition according to claim 1, wherein the polyamide resin (A) has a relative viscosity of 3.2 or more and 4.2 or less measured at 25°C in accordance with JIS K6920-2.
The polyamide resin composition according to claim 2, wherein the reinforcing filler (C) is at least one selected from the group consisting of glass fiber, carbon fiber and cellulose fiber.
The polyamide resin composition according to claim 2, which contains 10 to 35% by mass of the reinforcing filler (C) in 100% by mass of the polyamide resin composition.
The water absorption rate when an ISO527 type A tensile test piece obtained by injection molding the polyamide resin composition for three-dimensional modeling is immersed in water at 40 ° C. for 24 hours, is 2.2% or less. The polyamide resin composition for three-dimensional modeling according to claim 3.
An ISO527 type A tensile test piece obtained by three-dimensionally modeling the polyamide resin composition for three-dimensional modeling using a 3D printer is left for 24 hours under conditions of 23 ° C. and 50% RH, and then a surface plate 3. The three-dimensional according to claim 3, wherein when one end of the width direction side is fixed with a weight, the amount of warpage from the surface plate surface of the other width direction side end is 30 mm or less Polyamide resin composition for modeling.
A molded article of the polyamide resin composition according to claim 1 or 2.
The molded article according to claim 18, which is an automobile part.
A monofilament for three-dimensional modeling obtained by molding the polyamide resin composition for three-dimensional modeling according to claim 3.
A molded article obtained by three-dimensionally modeling the polyamide resin composition for three-dimensional modeling according to claim 3 or the monofilament for three-dimensional modeling according to claim 20 using a 3D printer.
Use of the polyamide resin composition for three-dimensional modeling according to claim 3 in three-dimensional modeling.
A three-dimensional modeling method, wherein the polyamide resin composition for three-dimensional modeling according to claim 3 is three-dimensionally modeled using a 3D printer.