JP6042121B2 - Polyamide resin composition and molded product - Google Patents

Description

  The present invention relates to a polyamide resin composition and a molded article.

  Polyamides represented by polyamide 6 and polyamide 66 (hereinafter sometimes abbreviated as “PA6” and “PA66”, respectively) and the like are excellent in molding processability, mechanical properties or chemical resistance. Widely used as various parts materials for automobiles, electric and electronic, industrial materials, industrial materials, daily products and household products.

  In the automobile industry, weight reduction of the vehicle body is required to reduce exhaust gas as an environmental effort. In order to meet this demand, polyamides are increasingly used in place of metals as exterior materials and interior materials for automobiles. Polyamide materials used for automobile exterior materials and interior materials are required to have higher levels of characteristics such as heat resistance, strength, and surface appearance. In particular, since the temperature in the engine room is also rising, the polyamide material used for the material in the engine room is increasingly required to have high heat resistance.

  In addition, in the electrical and electronic industries such as home appliances, lead-free surface mount (SMT) solder is being promoted. Polyamides used for materials such as home appliances are required to have high heat resistance that can withstand the rise in melting point of solder accompanying such lead-free soldering.

  Polyamides such as PA6 and PA66 have a low melting point, and cannot satisfy the above-described requirement for high heat resistance.

  In order to solve the problems related to the heat resistance of conventional polyamides such as PA6 and PA66, high melting point polyamides have been proposed. Specifically, a polyamide composed of terephthalic acid and hexamethylenediamine (hereinafter sometimes abbreviated as “PA6T”) has been proposed.

  However, since PA6T is a high melting point polyamide having a melting point of about 370 ° C., even if an attempt is made to obtain a molded product from PA6T by melt molding, the thermal decomposition of the polyamide occurs vigorously and a molded product having sufficient characteristics can be obtained. difficult.

  In order to solve the above-mentioned problems of PA6T, PA6T may be abbreviated to aliphatic polyamides such as PA6 and PA66, or amorphous aromatic polyamides composed of isophthalic acid and hexamethylenediamine (hereinafter abbreviated as “PA6I”). High melting point semi-aromatic polyamide (hereinafter referred to as “6T copolymer polyamide”) having terephthalic acid and hexamethylenediamine as main components, which have been made to have a melting point of about 220 to 340 ° C. Have been proposed).

  As the 6T copolymer polyamide, Patent Document 1 discloses an aromatic polyamide (hereinafter referred to as “a mixture of hexamethylene diamine and 2-methylpentamethylene diamine”), which is composed of an aromatic dicarboxylic acid and an aliphatic diamine. "May be abbreviated as" PA6T / 2MPDT ").

  Further, in contrast to an aromatic polyamide composed of an aromatic dicarboxylic acid and an aliphatic diamine, a high melting point aliphatic polyamide composed of adipic acid and tetramethylene diamine (hereinafter sometimes abbreviated as “PA46”), An alicyclic polyamide composed of an alicyclic dicarboxylic acid and an aliphatic diamine has been proposed.

  Further, in Patent Documents 2 and 3, a semi-alicyclic ring of an alicyclic polyamide (hereinafter sometimes abbreviated as “PA6C”) composed of 1,4-cyclohexanedicarboxylic acid and hexamethylenediamine and another polyamide. Group polyamides (hereinafter may be abbreviated as “PA6C copolymerized polyamides”) are disclosed.

  Patent Document 2 states that an electric and electronic member made from a semi-alicyclic polyamide containing 1 to 40% 1,4-cyclohexanedicarboxylic acid as a dicarboxylic acid unit can withstand a temperature under soldering conditions. It has been disclosed to have excellent heat resistance. Patent Document 3 discloses that an automobile part made from a polyamide composition substantially composed of units derived from an aliphatic dicarboxylic acid and an aliphatic diamine is excellent in fluidity and toughness. Yes.

  Further, Patent Document 4 discloses that a polyamide comprising a dicarboxylic acid unit containing 1,4-cyclohexanedicarboxylic acid and a diamine unit containing 2-methyl-1,8-octanediamine is light resistance, toughness, moldability, and lightness. And excellent heat resistance. Further, as a method for producing the polyamide, 1,4-cyclohexanedicarboxylic acid and 1,9-nonanediamine are reacted at 230 ° C. or lower to form a prepolymer, and the prepolymer is solid-phase polymerized at 230 ° C. to obtain a melting point of 311 A process for producing polyamides at 0C is disclosed.

  In Patent Document 5, a polyamide using 1,4-cyclohexanedicarboxylic acid having a trans / cis ratio of 50/50 to 97/3 as a raw material is excellent in heat resistance, low water absorption, light resistance, and the like. It is disclosed.

Patent Document 6 discloses a polyamide obtained by polymerizing 1,4-cyclohexanedicarboxylic acid and a diamine having a substituent branched from the main chain.
Patent Document 7 discloses a polyamide obtained by polymerizing 1,4-cyclohexanedicarboxylic acid, undecamethylenediamine, and 1,6-diaminohexane. Patent Document 8 discloses a polyamide obtained by polymerizing 1,4-cyclohexanedicarboxylic acid, 1,12-diaminododecane, and 1,6-diaminohexane.

JP-T 6-503590 Japanese National Patent Publication No. 11-512476 Special table 2001-514695 gazette Japanese Patent Laid-Open No. 9-12868 International Publication No. 2002/048239 Pamphlet International Publication No. 2009/113590 Japanese Patent Publication No. 64-2131 International Publication No. 2008/149862 Pamphlet

As described above, various polyamide resin compositions have been proposed in the past, but in recent years, when using the polyamide resin composition as a material for automobile engine room parts, etc. There is a need for polyamide resin compositions having good strength, rigidity, toughness and vibration fatigue resistance. In fields such as electrical and electronic parts, the polyamide resin composition has excellent strength, rigidity, toughness, heat resistance, moldability, and appearance when used as a material for smaller and more precise parts. There is also a need for polyamide resin compositions having dimensional stability.
However, the conventional polyamide resin compositions as disclosed in Patent Documents 1 to 8 cannot be said to have sufficient characteristics yet, and there is room for improvement.

Therefore, in the present invention, the polyamide has excellent rigidity after water absorption (water absorption rigidity), rigidity under high temperature use (rigidity during heat), good moldability, little dependency on molding conditions such as warping, and excellent appearance. It is an object to provide a resin composition and a molded product.
Furthermore, the problem to be solved by the present invention is to provide a polyamide resin composition that has a high proportion of units composed of biomass-derived raw materials (biomass plasticity) and can reduce environmental burden, and a molded product using the same. The purpose is to provide.

  As a result of intensive studies to solve the above problems, the present inventors contain a unit composed of a specific dicarboxylic acid, a unit composed of a specific diamine, and a unit composed of a specific copolymer component as constituent units, To find out that a polyamide resin composition containing a copolyamide satisfying specific conditions, glass fibers, and an inorganic filler other than the glass fibers can solve the problems of the prior art, and to complete the present invention. It came.

  That is, the present invention is as follows.

[1]
(A): (a) a unit comprising an alicyclic dicarboxylic acid;
(B) a unit comprising a diamine having 10 or more carbon atoms;
(C) a unit comprising at least one copolymer component selected from the group consisting of the following (c-1) to (c-3);
(C-1) Dicarboxylic acids other than the (a) alicyclic dicarboxylic acid.
(C-2) A diamine having fewer carbon atoms than the diamine (b).
(C-3) Lactam and / or aminocarboxylic acid.
Containing,
And a copolyamide satisfying the following conditions (1) to (3):
(1) In differential scanning calorimetry according to JIS-K7121, the difference between the crystallization peak temperature T _pc-1 obtained when cooled at 20 ° C./min and the glass transition temperature T _g (T _pc-1 − T _g )
However, it is 140 degreeC or more.
(2) The ratio of carbon number to amide group number (carbon number / amide group number) is 8 or more.
(3) In differential scanning calorimetry according to JIS-K7121, the melting peak temperature T _pm obtained when the temperature is raised at 20 ° C./min and the melting peak temperature obtained when the temperature is raised again at 20 ° C./min The difference from T _pm-1 (T _pm -T _pm-1 ) is 30 ° C. or less.
(B): glass fiber;
(C): inorganic filler other than glass fiber (B) (excluding titanium oxide),
Containing,
(B): Glass fiber 1 to 100 parts by weight of (A): polyamide copolymer
Polyamide resin composition (however, containing titanium oxide ) containing 300 parts by weight, (C): 1 to 200 parts by weight of an inorganic filler other than glass fiber (B) (excluding titanium oxide) Except.)
[2]
(C): An inorganic filler other than glass fiber (B) (excluding titanium oxide),
Wollastonite, kaolin, mica, talc, calcium carbonate, magnesium carbonate, potassium titanate fiber, aluminum borate fiber, at least one inorganic filler selected from the group consisting of clay, according to the above [1] Polyamide resin composition.
[3]
Said (C): Polyamide resin as described in said [1] or [2] whose average particle diameter of inorganic fillers (except titanium oxide) other than glass fiber (B) is 0.01-38 micrometers. Composition.
[4]
The (a) alicyclic dicarboxylic acid is 1,4-cyclohexanedicarboxylic acid,
[1] The polyamide resin composition according to any one of [3].
[5]
The trans isomer ratio in the unit consisting of (a) alicyclic dicarboxylic acid is 65-80.
The polyamide resin composition according to any one of [1] to [4], wherein the polyamide resin composition is mol%.
[6]
The ratio of the amino terminal amount to the total amount of amino terminal amount and carboxyl terminal amount {amino terminal amount / (amino terminal amount + carboxyl terminal amount)} is 0.0 or more and less than 0.5, [1
] The polyamide resin composition as described in any one of [5].
[7]
(B) The polyamide resin composition according to any one of [1] to [6], wherein the diamine having 10 or more carbon atoms is decamethylenediamine.
[8]
(C-1) The polyamide resin according to any one of [1] to [7], wherein the dicarboxylic acid other than (a) the alicyclic dicarboxylic acid is an aliphatic dicarboxylic acid having 10 or more carbon atoms. Composition.
[9]
(C-1) The polyamide resin composition according to any one of [1] to [8], wherein the dicarboxylic acid other than (a) the alicyclic dicarboxylic acid is sebacic acid and / or dodecanedioic acid. object.
[10]
(C-1) The polyamide resin composition according to any one of [1] to [7], wherein the dicarboxylic acid other than the (a) alicyclic dicarboxylic acid is isophthalic acid.
[11]
(C-2) The polyamide resin composition according to any one of [1] to [10], wherein the diamine having a carbon number smaller than that of the diamine (b) is an aliphatic diamine having 4 to 7 carbon atoms. object.
[12]
In differential scanning calorimetry according to JIS-K7121, the crystallization peak temperature T _pc-1 obtained when cooled at 20 ° C./min and the crystallization peak temperature T obtained when cooled again at 50 ° C./min. The polyamide resin composition according to any one of [1] to [11], wherein a difference from _pc-2 (T _pc-1 −T _pc-2 ) is 10 ° C. or less.
[13]
The total content of all the structural units of the copolymerized polyamide (A) is 100 mol%,
c) The content of the unit consisting of at least one copolymer component selected from the group consisting of (c-1) to (c-3) above is 5.0 mol% or more and 22.5 mol% or less. [1] to [
12] The polyamide resin composition according to any one of [12].
[14]
The biomass plasticity of the copolymerized polyamide (A) is 25% or more, [
[1] The polyamide resin composition according to any one of [13].
[15]
[1] to [14], further comprising at least one component selected from the group consisting of an inorganic filler, a nucleating agent, a lubricant, a stabilizer, and a polymer other than the copolymerized polyamide (A).
] The polyamide resin composition as described in any one of.
[16]
A molded article comprising the (A) polyamide copolymer or the polyamide resin composition according to any one of [1] to [15].
[17]
[16] which is an automobile part, an electronic part, a home appliance part, an OA equipment part, or a portable equipment part.
] The molded article described in the above.

According to the present invention, the rigidity after water absorption (water absorption rigidity), the rigidity under high temperature use (heat rigidity), the moldability is good, the molding condition dependency on various moldability such as warp is small, and the appearance In addition, an excellent polyamide resin composition and molded product can be provided.
Furthermore, since the polyamide resin composition of the present invention has a high proportion (unit of biomass plasticity) of units composed of biomass-derived raw materials in the copolymerized polyamide, the environmental load can be reduced.

  Hereinafter, a mode for carrying out the present invention (hereinafter simply referred to as “the present embodiment”) will be described in detail. The following embodiments are examples for explaining the present invention, and are not intended to limit the present invention to the following contents. The present invention can be implemented with various modifications within the scope of the gist.

[Polyamide resin composition]
The polyamide resin composition of this embodiment is
(A): (a) a unit comprising an alicyclic dicarboxylic acid;
(B) a unit comprising a diamine having 8 or more carbon atoms;
(C) a unit comprising at least one copolymer component selected from the group consisting of the following (c-1) to (c-3);
(C-1) Dicarboxylic acids other than the (a) alicyclic dicarboxylic acid.
(C-2) A diamine having fewer carbon atoms than the diamine (b).
(C-3) Lactam and / or aminocarboxylic acid.
Containing,
And a copolyamide satisfying the following conditions (1) to (3):
(1) In differential scanning calorimetry according to JIS-K7121, the difference between the crystallization peak temperature T _pc-1 obtained when cooled at 20 ° C./min and the glass transition temperature T _g (T _pc-1 − T _g ) is 140 ° C. or higher.
(2) The ratio of carbon number to amide group number (carbon number / amide group number) is 8 or more.
(3) In differential scanning calorimetry according to JIS-K7121, the melting peak temperature T _pm obtained when the temperature is raised at 20 ° C./min and the melting peak temperature obtained when the temperature is raised again at 20 ° C./min The difference from T _pm-1 (T _pm -T _pm-1 ) is 30 ° C. or less.
(B): glass fiber;
(C): inorganic filler other than glass fiber (B);
Containing,
(B): 1 to 300 parts by mass of glass fiber, (C): 1 to 200 parts by mass of an inorganic filler other than glass fiber (B), relative to 100 parts by mass of (A): polyamide copolymer, Is a polyamide resin composition containing

((A) Copolymer polyamide)
The (A) copolymerized polyamide (hereinafter sometimes referred to as copolymerized polyamide (A)) used in the present embodiment is a unit comprising the following component (a), a unit comprising the following component (b), and the following component. Contains a unit consisting of (c).
(A) Alicyclic dicarboxylic acid.
(B) A diamine having 8 or more carbon atoms.
(C) At least one main copolymer component selected from the group consisting of (c-1) to (c-3) described later.

  In the present embodiment, polyamide means a polymer having an amide (—NHCO—) bond in the main chain.

  Hereinafter, the components (a), (b) and (c) will be described in detail.

<(A) Alicyclic dicarboxylic acid>
The (a) alicyclic dicarboxylic acid (hereinafter also referred to as “alicyclic dicarboxylic acid”) contained in the (A) copolymer polyamide constituting the polyamide resin composition of the present embodiment is not particularly limited. Examples thereof include alicyclic dicarboxylic acids having 3 to 10 carbon atoms in the alicyclic structure, preferably alicyclic dicarboxylic acids having 5 to 10 carbon atoms in the alicyclic structure. (A) Although it does not specifically limit as alicyclic dicarboxylic acid, For example, 1, 4- cyclohexane dicarboxylic acid, 1, 3- cyclohexane dicarboxylic acid, 1, 3- cyclopentane dicarboxylic acid etc. are mentioned.

  The (a) alicyclic dicarboxylic acid used in the present embodiment may be unsubstituted or may have a substituent.

  Although it does not specifically limit as the said substituent, For example, C1-C4 alkyl groups, such as a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, and tert-butyl group Etc.

  The (a) alicyclic dicarboxylic acid used in the present embodiment is preferably 1,4-cyclohexanedicarboxylic acid from the viewpoints of heat resistance, low water absorption, strength, rigidity, and the like.

  As (a) alicyclic dicarboxylic acid used for this embodiment, you may use by 1 type and may be used in combination of 2 or more types.

  An alicyclic dicarboxylic acid has a geometric isomer of a trans isomer and a cis isomer. As the alicyclic dicarboxylic acid as a raw material monomer, either a trans isomer or a cis isomer may be used, or a mixture of various proportions of a trans isomer and a cis isomer may be used.

  Alicyclic dicarboxylic acids are isomerized at a high temperature to have a certain ratio, and the cis isomer has a higher water solubility in the equivalent salt with diamine than the trans isomer. The acid has a trans isomer / cis isomer ratio (molar ratio) of preferably 50/50 to 0/100, more preferably 40/60 to 10/90, and still more preferably 35/65 to 15/85. It is.

The trans / cis ratio (molar ratio) of the alicyclic dicarboxylic acid can be determined by liquid chromatography (HPLC) or nuclear magnetic resonance spectroscopy (NMR). Here, the trans isomer / cis isomer ratio (molar ratio) in the present specification is determined by ¹ H-NMR.

<(B) Diamine having 8 or more carbon atoms>
The (b) diamine having 8 or more carbon atoms contained in the (A) copolymerized polyamide constituting the polyamide resin composition of the present embodiment is not particularly limited as long as it is a diamine having 8 or more carbon atoms. Even in the linear aliphatic diamine, a substituent such as an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a tert-butyl group. It may be a branched aliphatic diamine, an alicyclic diamine, or an aromatic diamine. The number of carbon atoms in the (b) diamine having 8 or more carbon atoms used in the present embodiment is preferably 8-20, more preferably 8-15, and still more preferably 8-12.

  Although it does not specifically limit as (b) C8 or more diamine used for this embodiment, For example, octamethylenediamine, 2-methyloctamethylenediamine, nonamethylenediamine, decamethylenediamine, undecamethylenediamine, dodecamethylene Diamine, tridecamethylenediamine, 2,2,4-trimethylhexamethylenediamine, 2,4,4-trimethylhexamethylenediamine, 2-methyloctamethylenediamine, 2,4-dimethyloctamethylenediamine, metaxylylenediamine, Examples include orthoxylylenediamine and paraxylylenediamine.

  (B) The diamine having 8 or more carbon atoms used in the present embodiment is octamethylenediamine, 2-methyloctamethylenediamine, nonamethylenediamine, decamethylenediamine from the viewpoints of heat resistance, low water absorption, strength and rigidity. , Undecamethylene diamine and dodecamethylene diamine are preferable, more preferably 2-methyloctamethylene diamine, nonamethylene diamine, decamethylene diamine, undecamethylene diamine, and dodecamethylene diamine, and still more preferably decamethylene diamine, Dodecamethylenediamine, and even more preferably, decamethylenediamine from the viewpoint of increasing the crystallinity.

  As decamethylenediamine, 1,10-decamethylenediamine having a linear decane skeleton having an amino group at the 1,10-position is preferable from the viewpoint of reducing environmental burden. As 1,10-decamethylenediamine, unsubstituted 1,10-decamethylenediamine or substituted 1,10-decamethylenediamine having a substituent may be used. Although it does not specifically limit as the said substituent, For example, C1-C4 alkyl groups, such as a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, and tert-butyl group Is mentioned.

  In addition, in the (A) copolymer polyamide contained in the polyamide resin composition of the present embodiment, when combining two or more diamines having 8 or more carbon atoms as a structural unit, the diamine having the largest number of carbons is used as the component (b), Other diamines having 8 or more carbon atoms are used as component (c-2) described later. That is, the component (b) is one kind of diamine having the largest number of carbon atoms.

<(C): at least one copolymer component selected from the group consisting of (c-1) to (c-3)>
At least one copolymer component selected from the group consisting of (c): (c-1) to (c-3) constituting the (A) copolymerized polyamide contained in the polyamide resin composition of the present embodiment (hereinafter referred to as “a”). (C) may be described as a copolymerization component.) Is (c-1) a dicarboxylic acid other than (a) the alicyclic dicarboxylic acid, (c-2) a carbon number from the diamine of (b). A diamine with a small amount, and (c-3) at least one selected from the group consisting of lactams and / or aminocarboxylic acids.

  The copolymerized polyamide (A) used in the present embodiment contains a unit composed of at least one copolymer component selected from the group consisting of the above (c-1) to (c-3). , Excellent in low water absorption, low blocking property, releasability and plasticization time stability. Moreover, the polyamide resin composition of this embodiment containing a copolymerized polyamide (A) is excellent in vibration fatigue characteristics, surface appearance, and continuous productivity.

  When the copolymer polyamide (A) used in the present embodiment contains a unit composed of a dicarboxylic acid other than the above (c-1) (a) alicyclic dicarboxylic acid, it is particularly excellent in low water absorption and surface appearance. Moreover, when the copolymer polyamide (A) used for this embodiment contains the unit which consists of a diamine with less carbon number than the diamine of said (c-2) said (b), especially intensity | strength, high temperature strength, low blocking property, Excellent releasability. Furthermore, the copolymerized polyamide (A) used in the present embodiment is particularly excellent in high-temperature strength and releasability when it contains a unit consisting of the above (c-3) lactam and / or aminocarboxylic acid.

One type of (c) copolymerization component combined with (a) alicyclic dicarboxylic acid and (b) C8 or more diamine may be combined, and two or more types may be combined.
As an example of combination, (c-1), (c-2) and (c-3) can be freely combined. For example, two types from (c-1) may be used, Two types may be combined from c-2) and (c-3), or one type from (c-1) and one type from (c-2).

In the (A) copolymerized polyamide contained in the polyamide resin composition of the present embodiment, the content of the unit comprising (c) the copolymer component is 100 mol in total of the content of all the structural units of the copolymerized polyamide (A). % Is preferably 5.0 mol% or more and 22.5 mol% or less, more preferably 7.5 mol% or more and 20.0 mol% or less, and further preferably 10.0 mol% or more and 18.25 mol% or less. 0 mol% or less.
(C) Copolymer polyamide (A) excellent in strength, high-temperature strength, low water absorption, low blocking property, releasability and plasticizing time stability by adjusting the content of the unit comprising the copolymer component within the above range. It can be. Moreover, the polyamide resin composition of this embodiment containing the copolymerized polyamide (A) is excellent in vibration fatigue characteristics, surface appearance, and continuous productivity.

<(C-1) Dicarboxylic acid other than (a) alicyclic dicarboxylic acid>
The (c-1) dicarboxylic acid other than the (a) alicyclic dicarboxylic acid used in the present embodiment is not particularly limited, and examples thereof include aliphatic dicarboxylic acids and aromatic dicarboxylic acids.

  Examples of the aliphatic dicarboxylic acid include, but are not limited to, for example, malonic acid, dimethyl malonic acid, succinic acid, 2,2-dimethyl succinic acid, 2,3-dimethyl glutaric acid, 2,2-diethyl succinic acid, 2, 3-diethylglutaric acid, glutaric acid, 2,2-dimethylglutaric acid, adipic acid, 2-methyladipic acid, trimethyladipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, tetradecanedioic acid, Examples thereof include linear or branched aliphatic dicarboxylic acids having 3 to 20 carbon atoms such as hexadecanedioic acid, octadecanedioic acid, eicosanedioic acid, and diglycolic acid.

  The aromatic dicarboxylic acid is not particularly limited, and examples thereof include terephthalic acid, isophthalic acid, naphthalene dicarboxylic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, 5-methylisophthalic acid, and 5-sodium sulfoisophthalic acid. Or an aromatic dicarboxylic acid having 8 to 20 carbon atoms which is unsubstituted or substituted with various substituents.

  Although it does not specifically limit as various substituents, For example, halogens, such as a C1-C4 alkyl group, a C6-C10 aryl group, a C7-C10 arylalkyl group, a chloro group, and a bromo group Groups, silyl groups having 1 to 6 carbon atoms, and sulfonic acid groups and salts thereof such as sodium salts.

  (C-1) The dicarboxylic acid other than (a) the alicyclic dicarboxylic acid used in the present embodiment is preferably aliphatic in terms of heat resistance, fluidity, toughness, low water absorption, strength, rigidity, and the like. Dicarboxylic acids, more preferably aliphatic dicarboxylic acids having 6 or more carbon atoms.

  Among these, (c-1) the dicarboxylic acid other than the (a) alicyclic dicarboxylic acid is preferably an aliphatic dicarboxylic acid having 10 or more carbon atoms from the viewpoint of heat resistance and low water absorption.

The aliphatic dicarboxylic acid having 10 or more carbon atoms is not particularly limited, and examples thereof include sebacic acid, dodecanedioic acid, tetradecanedioic acid, hexadecanedioic acid, octadecanedioic acid, and eicosanedioic acid.
Among these, as the (c-1) dicarboxylic acid other than the (a) alicyclic dicarboxylic acid, sebacic acid and / or dodecanedioic acid are preferable from the viewpoint of heat resistance and the like.

In addition, (c-1) dicarboxylic acid other than (a) alicyclic dicarboxylic acid used in the present embodiment is aromatic in terms of heat resistance, fluidity, toughness, low water absorption, strength, rigidity, and the like. A dicarboxylic acid is also preferably used, and more preferably an aromatic dicarboxylic acid having 8 or more carbon atoms.
(C-1) As the dicarboxylic acid other than the (a) alicyclic dicarboxylic acid, isophthalic acid is particularly preferable from the viewpoint of heat resistance, fluidity, surface appearance, and the like.

  Furthermore, (c-1) the dicarboxylic acid other than the (a) alicyclic dicarboxylic acid is a trivalent or higher valent group such as trimellitic acid, trimesic acid, and pyromellitic acid within a range not impairing the object of the present embodiment. A polyvalent carboxylic acid may be included.

  As the polyvalent carboxylic acid, one kind may be used, or two or more kinds may be used in combination.

(A) Alicyclic dicarboxylic acid, and (c-1) Ratio of (a) alicyclic dicarboxylic acid in dicarboxylic acid other than (a) alicyclic dicarboxylic acid ((a) / [(a) + (C-1)] mol%) is not particularly limited, but is preferably 50 to 100 mol%, more preferably 60 to 100 mol%, still more preferably 70 to 100 mol%.
Copolymer polyamide having excellent strength, high temperature strength, low water absorption, low blocking property, releasability and plasticizing time stability when the ratio of (a) alicyclic dicarboxylic acid is 50 to 100 mol%. (A). Moreover, the polyamide resin composition of this embodiment containing the copolymerized polyamide (A) is excellent in vibration fatigue characteristics, surface appearance, and continuous productivity.

  The dicarboxylic acid used in the present embodiment is not limited to the compounds described as the dicarboxylic acid, and may be a compound equivalent to the dicarboxylic acid.

  The compound equivalent to the dicarboxylic acid is not particularly limited as long as it can be a dicarboxylic acid structure similar to the dicarboxylic acid structure derived from the dicarboxylic acid, and examples thereof include anhydrides and halides of dicarboxylic acids.

<(C-2) Diamine with Less Carbon Number than Diamine in (b)>
(C-2) The diamine having a carbon number smaller than that of the diamine (b) used in the present embodiment is not particularly limited as long as it is a diamine having a carbon number smaller than that of the diamine (b). , Alicyclic diamines and aromatic diamines.

  The aliphatic diamine is not particularly limited. For example, ethylene diamine, propylene diamine, tetramethylene diamine, pentamethylene diamine, hexamethylene diamine, heptamethylene diamine, octamethylene diamine, nonamethylene diamine, decamethylene diamine, undecamethylene. Linear aliphatic diamines such as diamine, dodecamethylenediamine, and tridecamethylenediamine, 2-methylpentamethylenediamine, 2,2,4-trimethylhexamethylenediamine, 2,4,4-trimethylhexamethylenediamine, 2 -Branched aliphatic diamines such as methyloctamethylenediamine and 2,4-dimethyloctamethylenediamine.

  The alicyclic diamine (also referred to as alicyclic diamine) is not particularly limited, and examples thereof include 1,4-cyclohexanediamine, 1,3-cyclohexanediamine, and 1,3-cyclopentanediamine. Can be mentioned.

  The aromatic diamine is an aromatic diamine and is not particularly limited, and examples thereof include metaxylylenediamine, orthoxylylenediamine, paraxylylenediamine, and the like.

  (C-2) The diamine having a smaller number of carbon atoms than the diamine (b) used in the present embodiment is preferably aliphatic in terms of heat resistance, fluidity, toughness, low water absorption, strength and rigidity. A diamine and an alicyclic diamine, more preferably an aliphatic diamine having 4 to 13 carbon atoms, still more preferably an aliphatic diamine having 4 to 10 carbon atoms, still more preferably 4 to 4 carbon atoms. 7 aliphatic diamines.

Furthermore, (c-2) the diamine having a smaller number of carbon atoms than the diamine (b) may contain a trivalent or higher polyvalent aliphatic amine such as bishexamethylenetriamine within the range not impairing the object of the present embodiment. Good.
One kind of the polyvalent aliphatic amine may be used alone, or two or more kinds may be used in combination.

  A component (c-2) may be used individually by 1 type, and may be used in combination of 2 or more type.

  (B) Ratio of diamine having 8 or more carbon atoms and (c-2) diamine having 8 or more carbon atoms in diamine having less carbon number than diamine (b) (mol%; (b) / [(B) + (c-2)]) is not particularly limited, but is preferably 40 to 100 mol%, more preferably 50 to 100 mol%, still more preferably 60 to 100 mol%. (B) Copolymer having excellent strength, high temperature strength, low water absorption, low blocking property, releasability and plasticizing time stability when the proportion of the diamine having 8 or more carbon atoms is 40 to 100 mol%. Polyamide (A) can be used. Moreover, the polyamide resin composition of this embodiment containing the copolymerized polyamide (A) is excellent in vibration fatigue characteristics, surface appearance, and continuous productivity.

(Content ratio of dicarboxylic acid and diamine)
When obtaining the copolymerized polyamide (A) used in the present embodiment, the addition amount of the dicarboxylic acid and the addition amount of the diamine are preferably around the same molar amount. Specifically, the amount of diamine escaped from the reaction system during the polymerization reaction is also considered in terms of the molar ratio, and the molar amount of the diamine is 0.9 to 1 with respect to the molar amount 1 of the entire dicarboxylic acid. .2, preferably 0.95 to 1.1, and more preferably 0.98 to 1.05.

<(C-3) Lactam and / or aminocarboxylic acid>
The (c-3) lactam and / or aminocarboxylic acid used in this embodiment means a lactam and / or aminocarboxylic acid that can be condensed (condensed).

  When the copolymerized polyamide (A) used in the present embodiment contains (c-3) a unit consisting of lactam and / or aminocarboxylic acid, (c-3) lactam and / or aminocarboxylic acid is A lactam having 4 to 14 carbon atoms and / or an aminocarboxylic acid having 4 to 14 carbon atoms is preferable, and a lactam having 6 to 12 carbon atoms and / or an aminocarboxylic acid having 6 to 12 carbon atoms is more preferable.

  Although it does not specifically limit as a lactam, For example, a butyrolactam, pivalolactam, (epsilon) -caprolactam, a caprilolactam, an enantolactam, undecanolactam, a laurolactam (dodecanolactam), etc. are mentioned.

  Among these, as the lactam, from the viewpoint of toughness, ε-caprolactam, undecanolactam, laurolactam and the like are preferable, and ε-caprolactam and laurolactam are more preferable.

  The aminocarboxylic acid is not particularly limited, and examples thereof include ω-aminocarboxylic acid and α, ω-amino acid which are compounds in which the lactam is ring-opened.

The aminocarboxylic acid is preferably a linear or branched saturated aliphatic carboxylic acid having 4 to 14 carbon atoms substituted with an amino group at the ω position, and is not particularly limited. For example, 6-aminocaproic acid, 11 -Aminoundecanoic acid, 12-aminododecanoic acid, etc. are mentioned, As a paracarboxylic acid, paraaminomethylbenzoic acid etc. are mentioned.
Among these, as the aminocarboxylic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid and the like are more preferable from the viewpoint of low water absorption and toughness.

  When (c-3) lactam and / or aminocarboxylic acid is used in obtaining the copolymerized polyamide (A) used in the present embodiment, the amount (mol%) of (c-3) is not particularly limited. (A) alicyclic dicarboxylic acid, (b) diamine having 8 or more carbon atoms, (c-1) dicarboxylic acid, (c-2) diamine, and (c-3) lactam and / or aminocarboxylic acid Preferably, they are 0.5 mol% or more and 20 mol% or less, and more preferably 2 mol% or more and 18 mol% or less with respect to the molar amount of each monomer. (C-3) Copolymer polyamide having excellent heat resistance, low water absorption, strength, releasability, etc., when the addition amount of lactam and / or aminocarboxylic acid is 0.5 mol% or more and 20 mol% or less. (A).

In addition, in this embodiment, each content of each structural unit in copolymer polyamide (A) can be measured by < ¹ > H-NMR, and it measures in detail by the method as described in the below-mentioned Example. be able to.

(End sealant)
In this embodiment, when polymerizing the copolymerized polyamide (A), in addition to the components (a) to (c), a known end-capping agent can be further added for molecular weight adjustment.
The end capping agent is not particularly limited, and examples thereof include monocarboxylic acids, monoamines, acid anhydrides such as phthalic anhydride, monoisocyanates, monoacid halides, monoesters, and monoalcohols. From the viewpoint of thermal stability, monocarboxylic acids and monoamines are preferred.
In addition, when the copolymerized polyamide (A) is polymerized, a unit composed of the end capping agent is formed in the copolymer polyamide by further adding a terminal capping agent in addition to the components (a) to (c). Is done.
As the terminal blocking agent, one kind may be used, or two or more kinds may be used in combination.

  The monocarboxylic acid that can be used as the end-capping agent is not particularly limited as long as it has reactivity with an amino group. For example, formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid Aliphatic monocarboxylic acids such as lauric acid, tridecylic acid, myristic acid, palmitic acid, stearic acid, pivalic acid, and isobutyric acid; alicyclic monocarboxylic acids such as cyclohexanecarboxylic acid; and benzoic acid, toluic acid, α -Aromatic monocarboxylic acids such as naphthalenecarboxylic acid, β-naphthalenecarboxylic acid, methylnaphthalenecarboxylic acid, and phenylacetic acid;

  As monocarboxylic acid, you may use by 1 type and may be used in combination of 2 or more types.

  The monoamine that can be used as the end-capping agent is not particularly limited as long as it has reactivity with a carboxyl group. For example, methylamine, ethylamine, propylamine, butylamine, hexylamine, octylamine, decylamine, stearyl Aliphatic monoamines such as amine, dimethylamine, diethylamine, dipropylamine, and dibutylamine; alicyclic monoamines such as cyclohexylamine and dicyclohexylamine; and aromatic monoamines such as aniline, toluidine, diphenylamine, and naphthylamine; It is done.

  Monoamines may be used alone or in combination of two or more.

[Characteristics of copolymerized polyamide (A)]
(Isomer ratio)
In the copolymerized polyamide (A) used in the present embodiment, the unit consisting of (a) an alicyclic dicarboxylic acid exists as a geometric isomer of a trans isomer and a cis isomer.

  In the copolymerized polyamide (A) used in the present embodiment, the trans isomer ratio in the unit consisting of (a) the alicyclic dicarboxylic acid is in the whole unit consisting of the alicyclic dicarboxylic acid in the copolymerized polyamide (A). Represents a ratio that is a trans isomer. The trans isomer ratio is preferably 50 to 85 mol%, more preferably 50 to 80 mol%, and still more preferably 65 to 80 mol%.

  As the raw material (a) alicyclic dicarboxylic acid, it is preferable to use an alicyclic dicarboxylic acid having a trans isomer / cis isomer ratio (molar ratio) of 50/50 to 0/100 as described above. On the other hand, in the copolymerized polyamide (A), the trans isomer ratio in the unit comprising (a) the alicyclic dicarboxylic acid is within the above range, that is, preferably 50 to 85 mol%, more preferably 50 to 80 mol%. More preferably, it is 65 to 80 mol%.

  When the trans isomer ratio is within the above range, the copolymer polyamide (A) has high melting point, toughness, strength, rigidity, and plasticity time stability, and also has a high Tg thermal rigidity. Ordinarily, it has the property of simultaneously satisfying fluidity, which is a property contrary to heat resistance, and high crystallinity. Moreover, the polyamide resin composition of this embodiment containing the copolymerized polyamide (A) is excellent in surface appearance and continuous productivity.

The method for controlling the trans isomer ratio in the unit comprising the (a) alicyclic dicarboxylic acid in the copolymerized polyamide (A) is not particularly limited, but for example, polymerization of the copolymerized polyamide (A) Examples thereof include a method and a method for controlling polymerization conditions. When producing the copolymerized polyamide (A) by the hot melt polymerization method, it is preferable to maintain the molten state until the polymerization is completed. In order to maintain a molten state, it is preferable to produce it under polymerization conditions suitable for the constituent components of the copolymerized polyamide (A). Specifically, for example, the polymerization pressure is controlled to a high pressure of 23 to 50 kg / cm ² (gauge pressure), preferably 25 kg / cm ² (gauge pressure) or more, and the pressure in the tank is atmospheric pressure while heating is continued. Examples include a method of reducing pressure while taking 30 minutes or more until the gauge pressure becomes 0 kg / cm ² .

In this embodiment, the trans isomer ratio in the copolymerized polyamide (A) is such that, for example, 30-40 mg of the copolymerized polyamide (A) is dissolved in 1.2 g of hexafluoroisopropanol deuteride, and the resulting solution is It can obtain | require by measuring by < ¹ > H-NMR. Specifically, in the case of 1,4-cyclohexanedicarboxylic acid, a peak area of 1.98 ppm derived from the trans isomer and 1.77 ppm and 1.86 ppm derived from the cis isomer in ¹ H-NMR measurement. The trans isomer ratio can be determined from the ratio to the peak area.

(Degree of bioplastic)
The biomass plasticity of the copolymerized polyamide (A) used in this embodiment is preferably 25% or more. Biomass plasticity means the ratio of the unit comprised by the raw material derived from biomass among copolymer polyamide (A), and can be computed by the method described in the following Example. A more preferable bioplastic degree is 30% or more.
The upper limit of the degree of biomass plasticity of the copolymerized polyamide according to the present embodiment is not particularly limited. Is preferably lower.

The biomass-derived raw material as used herein means a monomer that can be synthesized using a component such as a plant as a starting material among the components (a) to (c) that are components of the copolymerized polyamide (A). .
Although it does not specifically limit as a raw material derived from biomass, For example, it synthesize | combines from the component of a sebacic acid, a decamethylenediamine, 11-amino undecanoic acid which can be synthesize | combined from the ricinoleic acid triglyceride which is a main component of a castor oil, and the component of a sunflower seed. Examples include azelaic acid that can be synthesized, pentamethylenediamine, and γ-aminobutyric acid that can be synthesized from cellulose.

  Since biomass-derived raw materials are accumulated by absorbing carbon dioxide in the atmosphere by photosynthesis, even when carbon dioxide is released into the atmosphere by combustion after using plastics made from these, Since it is carbon dioxide originally present in the atmosphere, the concentration of carbon dioxide in the atmosphere does not increase.

  Therefore, the high degree of biomass plasticity in the copolymerized polyamide (A) is very effective for reducing the environmental load. The method for increasing the biomass plasticity of the copolymerized polyamide (A) is not particularly limited. For example, when the copolymerized polyamide (A) is produced, there is a method for increasing the blending ratio of the above-described biomass-derived raw materials. Can be mentioned.

(Sulfuric acid relative viscosity)
The molecular weight of the copolymerized polyamide (A) used in the present embodiment is based on sulfuric acid relative viscosity ηr at 25 ° C.

The sulfuric acid relative viscosity ηr at 25 ° C. of the copolymerized polyamide (A) used in the present embodiment is preferably 1.5 to 7.0 in terms of mechanical properties such as toughness, strength and rigidity, and moldability, More preferably, it is 1.7-6.0, More preferably, it is 1.9-5.5.
As a method for controlling the sulfuric acid relative viscosity ηr at 25 ° C. of the copolymerized polyamide (A) within the above range, for example, a diamine as an additive at the time of hot melt polymerization of the copolymerized polyamide (A) and an end-capping agent Examples thereof include a method of controlling the addition amount and polymerization conditions.

  The measurement of the sulfuric acid relative viscosity ηr at 25 ° C. of the copolymerized polyamide (A) can be performed according to JIS-K6920 as described in the following examples.

(Melting peak temperature)
The melting peak temperature (melting point) T _pm-1 of the copolymerized polyamide (A) used in this embodiment is preferably 280 ° C. or higher, more preferably 280 ° C. or higher and 330 ° C. or lower, from the viewpoint of heat resistance. More preferably, it is 300 degreeC or more and 330 degrees C or less, More preferably, it is 310 degreeC or more and 325 degrees C or less.
A copolymerized polyamide (A) having a melting peak temperature T _pm-1 of 330 ° C. or lower is preferable because thermal decomposition in melt processing such as extrusion and molding can be suppressed.
As a method for controlling the melting peak temperature (melting point) T _pm-1 of the copolymerized polyamide (A) within the above range, for example, the constituent components of the copolymerized polyamide (A) are the above components (a) to (c). And a method of controlling the blending ratio of the copolymer component to the above-described range.

(Melting peak temperature (melting point), crystallization peak temperature, crystallization enthalpy)
In this embodiment, the melting peak temperature (melting point), the crystallization peak temperature, and the crystallization enthalpy of the copolymerized polyamide (A) can be measured by differential scanning calorimetry (DSC) according to JIS-K7121. . Specifically, it can be measured as follows.
As the measuring device, Diamond-DSC manufactured by PERKIN-ELMER can be used.
The measurement conditions are such that about 10 mg of the sample is heated from 50 ° C. to 350 ° C. at a temperature increase rate of 20 ° C./min in a nitrogen atmosphere. The endothermic peak that appears at this time is the melting peak, and the peak that appears on the highest temperature side is the melting peak temperature _Tpm .
Subsequently, after being kept at 350 ° C. for 3 minutes, it is cooled from 350 ° C. to 50 ° C. at a cooling rate of 20 ° C./min. The exothermic peak appearing at this time is defined as a crystallization peak, the crystallization peak temperature is _defined as T _pc-1 , and the crystallization peak area is defined as a crystallization enthalpy. Subsequently, after maintaining at 50 ° C. for 3 minutes, the temperature is increased again from 50 ° C. to 350 ° C. at a temperature increase rate of 20 ° C./min.
The endothermic peak appearing at this time and appearing on the highest temperature side is defined as melting peak temperature T _pm-1, and the endothermic peak appearing on the lowest temperature side is defined as melting peak temperature T _pm-2 .
When there is one endothermic peak appearing at this time, the endothermic peaks are defined as melting peak temperatures T _pm-1 and T _pm-2 (T _pm-1 = T _pm-2 ). Further, after being kept at 350 ° C. for 3 minutes, it is cooled from 350 ° C. to 50 ° C. at a cooling rate of 50 ° C./min. The crystallization peak temperature appearing at this time is _defined as T _pc-2 .

The copolymerized polyamide (A) used in this embodiment has a difference (T _pm -T _pm-1 ) between the melting peak temperature T _pm and the melting peak temperature T _pm-1 of 30 ° C. or less, and 0-20 The temperature is preferably in the range of 0 ° C., more preferably in the range of 0 to 10 ° C.
In the copolymerized polyamide (A), the smaller the difference between the melting peak temperature T _pm and the melting peak temperature T _pm-1 (T _pm -T _pm-1 ), the smaller the (a) alicyclic ring in the copolymerized polyamide (A). This means that the part derived from the group dicarboxylic acid has a thermodynamically stable structure.
The copolymerized polyamide (A) in which the difference (T _pm -T _pm-1 ) between the melting peak temperature T _pm and the melting peak temperature T _pm-1 is in the above range is excellent in plasticization time stability. Moreover, the polyamide resin composition containing the copolymerized polyamide (A) is excellent in surface appearance and continuous productivity.
In the copolymerized polyamide (A), as a method for controlling the difference between the melting peak temperature _Tpm and the melting peak temperature _Tpm-1 ( _Tpm - _Tpm-1 ) within the above range, for example, a copolymerized polyamide ( The component (A) is the components (a) to (c) described above, the blending ratio of the copolymer component is in the above-described range, and is derived from the (a) alicyclic dicarboxylic acid in the copolymer polyamide (A). The method of controlling the trans isomer ratio in a part within the range of 65-80 mol% is mentioned.

The melting peak temperature T _pm-2 of the copolymerized polyamide (A) used in the present embodiment is preferably 270 ° C. or higher, more preferably in the range of 270 to 320 ° C., from the viewpoint of heat resistance. More preferably, it is in the range of ˜310 ° C.
As a method for controlling the melting peak temperature (melting point) T _pm-2 of the copolymerized polyamide (A) within the above range, for example, the constituent components of the copolymerized polyamide (A) may be the above components (a) to (c). And a method of controlling the blending ratio of the copolymer component to the above-described range.

Further, in the copolymerized polyamide (A) used in this embodiment, the difference (T _pm-1 -T _pm-2 ) between the melting peak temperature T _pm-1 and the melting peak temperature T _pm-2 is 30 ° C. or less. It is preferable that it is within a range of 10 to 20 ° C. When the difference (T _pm-1 -T _pm-2 ) between the melting peak temperature T _pm-1 and the melting peak temperature T _pm-2 in the copolymerized polyamide (A) is within the above range, release properties and low blocking are achieved. From the viewpoint of sex.
As a method of controlling the difference (T _pm-1 -T _pm-2 ) between the melting peak temperature T _pm-1 and the melting peak temperature T _pm-2 in the copolymerized polyamide (A) within the above range, for example, Examples include a method in which the constituent components of the polymerized polyamide (A) are the above components (a) to (c) and the blending ratio of the copolymer components is controlled within the above-described range.

The crystallization peak temperature T _pc-1 of the copolymerized polyamide (A) used in the present embodiment is preferably 250 ° C. or higher, more preferably 260 ° C. or higher and 300 ° C. from the viewpoint of low blocking properties and releasability. It is as follows.
As a method for controlling the crystallization peak temperature T _pc-1 of the copolymerized polyamide (A) within the above range, for example, the components of the copolymerized polyamide (A) are the above components (a) to (c), Examples thereof include a method of controlling the blending ratio of the copolymer component within the above-described range.

The crystallization peak temperature T _pc-2 of the copolymerized polyamide (A) used in the present embodiment is preferably 240 ° C. or more from the viewpoint of low blocking properties and releasability, and is in the range of 240 to 280 ° C. It is more preferable.
As a method for controlling the crystallization peak temperature T _pc-2 of the copolymerized polyamide (A) within the above range, for example, the components of the copolymerized polyamide (A) are the above components (a) to (c), Examples thereof include a method of controlling the blending ratio of the copolymer component within the above-described range.

Furthermore, in the copolymerized polyamide (A) used in the present embodiment, the difference (T _pc-1 −T _pc-2 ) between the crystallization peak temperature T _pc-1 and the crystallization peak temperature T _pc-2 is 10 ° C. or less. It is preferable that
In the copolymerized polyamide (A), the smaller the difference (T _pc-1 -T _pc-2 ) between the crystallization peak temperature T _pc-1 and the crystallization peak temperature T _pc-2 , the faster the crystallization speed becomes. It means that the crystal structure of the polymerized polyamide is stable.
When the difference (T _pc-1 -T _pc-2 ) between the crystallization peak temperature T _pc-1 and the crystallization peak temperature T _pc-2 in the copolymerized polyamide (A) is within the above range, low blocking property, It is preferable from the viewpoint of releasability.
As a method for controlling the difference (T _pc-1 -T _pc-2 ) between the crystallization peak temperature T _pc-1 and the crystallization peak temperature T _pc-2 in the copolymerized polyamide (A) within the above range, for example, And a method of controlling the blending ratio of the copolymer component within the above-described range by using the components (a) to (c) as components of the copolymer polyamide (A). In order to reduce (T _pc-1 -T _pc-2 ) and to make the copolymer polyamide (A) have a stable crystal structure, the components (a) to (a) which are constituent components of the copolymer polyamide (A) are used. c) The number of carbon atoms of the component is set to an even number, the carbon chain is linear, and the ratio of the number of carbons to the number of amide groups in the copolymerized polyamide (A) (carbon number / amide group number) is 8 or more. It is preferable to make it less than 9.

The crystallization enthalpy of the copolymerized polyamide (A) used in the present embodiment is preferably 10 J / g or more, more preferably 15 J / g or more, from the viewpoints of heat resistance, low blocking properties, and releasability. More preferably, it is 20 J / g or more. Although the upper limit of the crystallization enthalpy of the copolymer polyamide (A) used for this embodiment is not specifically limited, For example, it is 100 J / g or less.
As a method for controlling the crystallization enthalpy of the copolymerized polyamide (A) within the above range, for example, the ratio of the number of carbons to the number of amide groups (carbon number / amide group number) in the copolymerized polyamide (A) is 8 or more. And a method of controlling the blending ratio of the copolymer component within the above-mentioned range by using the components (a) to (c) as components of the copolymer polyamide (A).

(Tg)
The glass transition temperature Tg of the copolymerized polyamide (A) used in the present embodiment is preferably 90 ° C. or higher and 170 ° C. or lower, more preferably 90 ° C. or higher and 140 ° C. or lower, and further preferably 100 ° C. or higher and 140 ° C. or lower. It is. By setting the glass transition temperature Tg to 90 ° C. or higher, a copolymerized polyamide (A) having excellent heat resistance and chemical resistance can be obtained. Moreover, by setting the glass transition temperature to 170 ° C. or lower, a molded product having a good surface appearance can be obtained from the copolymerized polyamide (A).
As a method for controlling the glass transition temperature Tg of the copolymerized polyamide (A) within the above range, for example, the components (a) to (c) are used as the components of the copolymerized polyamide (A), and the components of the copolymerized component are blended. Examples include a method of controlling the ratio within the above-described range.

  In the present embodiment, the glass transition temperature Tg can be measured by differential scanning calorimetry (DSC) according to JIS-K7121. Specifically, it can measure by the method as described in the Example mentioned later.

The copolymerized polyamide (A) used in the present embodiment has a difference (T _pc) between the crystallization peak temperature T _pc-1 obtained when cooled at 20 ° C./min and the glass transition temperature Tg in differential scanning calorimetry. ₋₁ −Tg) is 140 ° C. or higher, preferably 145 ° C. or higher, more preferably 150 ° C. or higher.
In the copolymerized polyamide (A), the larger the difference (T _pc-1 -Tg) between the crystallization peak temperature T _pc-1 and the glass transition temperature Tg, the wider the temperature range that can be crystallized. ) Is stable.
The copolymerized polyamide (A) having a difference between the crystallization peak temperature T _pc-1 and the glass transition temperature Tg (T _pc-1 -Tg) of 140 ° C. or more is excellent in low blocking property and releasability. Although the upper limit of the difference (T _pc-1 -Tg) between the crystallization peak temperature T _pc-1 and the glass transition temperature Tg is not particularly limited, it is, for example, 300 ° C. or less.

As a method for controlling the difference (T _pc-1 -Tg) between the crystallization peak temperature T _pc-1 and the glass transition temperature Tg in the copolymerized polyamide (A), for example, the constituent components of the copolymerized polyamide (A) are: A method of controlling the blending ratio of the copolymer component within the above-described range as the above components (a) to (c) can be mentioned.
In order to increase (T _pc-1 -Tg) and to make the copolymer polyamide (A) have a stable crystal structure, the number of carbon atoms of the copolymer components (a) to (c) should be an even number. In addition, it is preferable that the carbon chain is linear, or the ratio of carbon number to amide group number (carbon number / amide group number) in the copolymerized polyamide (A) is 8 or more and less than 9.

(Polymer end)
The polymer terminal of the copolymerized polyamide (A) used in this embodiment is classified and defined as follows.
That is, 1) amino terminal, 2) carboxyl terminal, 3) terminal by a sealant, and 4) other terminal.
The polymer terminal of the copolymerized polyamide (A) means a terminal part of a polymer chain obtained by polymerizing dicarboxylic acid and diamine by an amide bond. The polymer terminal of the copolymerized polyamide (A) is one or more of these terminals 1) to 4).

1) The amino terminal is a polymer terminal to which an amino group (—NH ₂ group) is bonded, and is derived from a raw material diamine.
2) The carboxyl end is a polymer end to which a carboxyl group (—COOH group) is bonded, and is derived from the raw material dicarboxylic acid.
3) The terminal by a sealing agent is the terminal of the polymer sealed with the terminal sealing agent added at the time of superposition | polymerization, for example, carboxylic acid or amine.
4) The other terminal is a polymer terminal not classified in the above 1) to 3), and is not particularly limited. Examples include the generated terminal.

In the copolymerized polyamide (A) used in this embodiment, the ratio of the amino terminal amount to the total amount of amino terminal amount and carboxyl terminal amount {amino terminal amount / (amino terminal amount + carboxyl terminal amount)} is not particularly limited. However, it is preferably 0.0 or more and less than 0.5. More preferably, it is 0.15-0.5, More preferably, it is 0.3-0.5, More preferably, it is 0.3-0.4.
By setting the ratio of the amino terminal amount to the total amount of the amino terminal amount and the carboxyl terminal amount in the copolymerized polyamide (A) to 0.0 or more and less than 0.5, the strength, toughness, and heat of the copolymerized polyamide (A) are increased. While maintaining the stability and hydrolysis resistance, and the color tone and vibration fatigue properties of the polyamide resin composition containing the copolymerized polyamide, it is possible to further suppress a decrease in color tone due to thermal degradation of the polyamide resin composition. .

  As a method of controlling the ratio {amino terminal amount / (amino terminal amount + carboxyl terminal amount)} of amino terminal amount to total amount of amino terminal amount and carboxyl terminal amount in copolymerized polyamide (A), for example, copolymerized polyamide Examples thereof include a method of controlling the addition amount of the diamine and the end-capping agent as additives during the hot melt polymerization (A) and the polymerization conditions.

  The amount of amino terminal bound to the polymer terminal can be measured by neutralization titration. Specifically, 3.0 g of polyamide is dissolved in 100 mL of 90% by mass phenol aqueous solution, and the resulting solution is titrated with 0.025N hydrochloric acid, and the amino terminal amount is determined based on the titration result. The end point is determined from the indicated value of the pH meter.

  The amount of carboxyl terminal bound to the polymer terminal can be measured by neutralization titration. Specifically, 4.0 g of polyamide is dissolved in 50 mL of benzyl alcohol, and the resulting solution is titrated with 0.1N NaOH, and the carboxyl end amount is determined based on the titration result. The end point is determined from the discoloration of the phenolphthalein indicator.

  Using the amino terminal amount and the carboxy terminal amount, the ratio of the amino terminal group to the total amount of the amino terminal amount and the carboxyl terminal amount of the copolymer polyamide {amino terminal amount / (amino terminal amount + carboxyl terminal amount)} can be calculated. .

(Carbon number / amide group)
In the copolymerized polyamide (A) used in the present embodiment, the ratio of carbon number to amide group number (carbon number / amide group number) is 8 or more from the viewpoint of low water absorption, preferably 8.2 or more and less than 9. is there.
The ratio of the number of carbon atoms to the number of amide groups (carbon number / amide group number) is an index indicating the amino group concentration of the copolymerized polyamide (A).
By setting the ratio of the number of carbon atoms to the number of amide groups (carbon number / amide group number) within the above range, the strength, high-temperature strength, low water absorption, low blocking property, releasability, and plasticization time stability were excellent. A copolymerized polyamide (A) and a copolymerized polyamide composition excellent in vibration fatigue characteristics, surface appearance, and continuous productivity can be provided.

  As a method for controlling the ratio of the number of carbon atoms to the number of amide groups (carbon number / amide group number) in the copolymerized polyamide (A), for example, the constituent components of the copolymerized polyamide (A) are the components (a) to (c) And a method of controlling the blending ratio of the copolymer component within the above-described range.

  The index indicating the amino group concentration (the number of carbon atoms / the number of amide groups) can be obtained by calculating the average value of the number of carbon atoms per amide group in the copolymer polyamide (A). Specifically, it can be determined by the method described in Examples described later.

[Production method of copolymerized polyamide (A)]
Although it does not specifically limit as a manufacturing method of copolyamide (A) used for this embodiment, For example, (a) alicyclic dicarboxylic acid mentioned above, (b) C8 or more diamine, (c) Examples include a method for producing a copolymerized polyamide, which includes a step of polymerizing a predetermined copolymer component.

The method for producing the copolymerized polyamide (A) used in the present embodiment preferably further includes a step of increasing the degree of polymerization of the copolymerized polyamide.
As a manufacturing method of the copolyamide of this embodiment, the process of adding terminal blocker is included. It is preferable to add terminal blocker at the time of copolymerization.

Although it does not specifically limit as a specific manufacturing method of the copolyamide (A) used for this embodiment, For example, various methods are mentioned so that it may illustrate below:
1) A method in which an aqueous solution or a suspension of water of a dicarboxylic acid, a diamine salt or a mixture thereof is heated and polymerized while maintaining a molten state (hereinafter sometimes referred to as “hot melt polymerization method”).
2) A method of increasing the degree of polymerization while maintaining the solid state of the polyamide obtained by the hot melt polymerization method at a temperature below the melting point (hereinafter sometimes abbreviated as “hot melt polymerization / solid phase polymerization method”).
3) A method of polymerizing using a dicarboxylic acid halide component equivalent to a dicarboxylic acid and a diamine component (“solution method”).
Among them, a production method including a hot melt polymerization method is preferable, and when the copolymerized polyamide (A) is produced by the hot melt polymerization method, it is preferable to maintain a molten state until the polymerization is completed. In order to maintain a molten state, it is preferable to produce it under polymerization conditions suitable for the constituent components of the copolymerized polyamide (A). For example, the polymerization pressure in the hot melt polymerization method is controlled to a high pressure of 23 to 50 kg / cm ² (gauge pressure), preferably 25 kg / cm ² (gauge pressure) or more. For example, a method of decreasing the pressure while taking 30 minutes or more until atmospheric pressure (gauge pressure is 0 kg / cm ² ) can be mentioned. The copolymerized polyamide (A) obtained by such a production method can satisfy the characteristics such as the trans isomer ratio described above.

  In the method for producing the copolymerized polyamide (A) used in the present embodiment, from the viewpoint of improving the melting point and ensuring the fluidity of the copolymerized polyamide (A), (a) fat in the obtained copolymerized polyamide (A) It is preferable to carry out the polymerization while maintaining the trans isomer ratio in a unit comprising a cyclic dicarboxylic acid at 50 to 85% or less. In particular, by maintaining the trans isomer ratio at 60 to 80% or less, more preferably 65 to 80%, it is further excellent in color tone, tensile elongation and plasticization time stability, and has a high melting point copolymer polyamide (A ) Can be obtained. Moreover, the copolymerized polyamide composition containing the copolymerized polyamide (A) is excellent in surface appearance and continuous productivity.

  In the method for producing the copolyamide (A) used in the present embodiment, in order to increase the degree of polymerization and increase the melting point of the copolyamide (A), the heating temperature is increased and / or the heating time is increased. May be lengthened. In that case, there is a possibility that the tensile elongation is lowered due to coloring of the copolymerized polyamide (A) by heating or thermal degradation. In addition, the rate of increase in molecular weight may be significantly reduced.

  By copolymerizing the copolymer polyamide (A) while maintaining the trans isomer ratio in the whole unit comprising the (a) alicyclic dicarboxylic acid in the copolymer polyamide (A) at 80% or less, It is possible to prevent a decrease in tensile elongation and a decrease in plasticization time stability due to coloring and thermal deterioration, and a decrease in surface appearance and continuous productivity of the polyamide resin composition containing the copolymerized polyamide (A). Can be prevented.

  As a method for producing the copolyamide (A) used in the present embodiment, a method of producing a copolyamide by 1) a hot melt polymerization method and 2) a hot melt polymerization / solid phase polymerization method is preferable. With such a production method, it is easy to maintain the trans isomer ratio in the whole unit consisting of (a) alicyclic dicarboxylic acid in the copolymerized polyamide (A) at 80% or less, The resulting copolymerized polyamide (A) is excellent in color tone and plasticization time stability. Furthermore, the polyamide resin composition containing the copolymerized polyamide (A) is excellent in surface appearance and continuous productivity.

  In the method for producing the copolyamide (A) used in the present embodiment, the polymerization form may be a batch type or a continuous type.

  The polymerization apparatus is not particularly limited, and examples thereof include known apparatuses such as an autoclave type reactor, a tumbler type reactor, and an extruder type reactor such as a kneader.

  Although it does not specifically limit as a more specific manufacturing method of the copolymerization polyamide (A) used for this embodiment, For example, a copolymerization polyamide can be manufactured with the batch type hot-melt-polymerization method described below.

  Although it does not specifically limit as a method of manufacturing copolyamide (A) by a batch type hot-melt-polymerization method, For example, the following methods are mentioned. When producing the copolymerized polyamide (A) by the hot melt polymerization method, it is preferable to maintain the molten state until the polymerization is completed. In order to maintain a molten state, it is preferable to produce it under polymerization conditions suitable for the constituent components of the copolymerized polyamide (A).

About 40-60 mass% aqueous solution containing the component (the said (a)-(c) component, and arbitrary other components) of copolymerization polyamide (A) is used at 110-180 degreeC containing water as a solvent. In a concentration tank operated at a temperature and a pressure of about 0.35 to 6 kg / cm ² (gauge pressure), it is concentrated to about 65 to 90% by mass to obtain a concentrated solution. The concentrated solution is then transferred to an autoclave and heating is continued until the pressure in the vessel is about 23-50 kg / cm ² (gauge pressure). Thereafter, the pressure is maintained at about 23 to 50 kg / cm ² (gauge pressure) while removing water and / or gas components. Here, in order to maintain the molten state, a pressure suitable for the constituent component of the copolymerized polyamide is preferable. Especially when a diamine having a large carbon number is used, the pressure in the container is 25 kg / cm ² (gauge pressure) or more. It is preferable that When the temperature in the container reaches about 250 to 350 ° C., the pressure in the container is reduced to atmospheric pressure (gauge pressure is 0 kg / cm ² ). Here, in order to maintain a molten state, it is preferable to reduce the pressure while continuing heating and taking 30 minutes or more. By reducing the pressure to atmospheric pressure and then reducing the pressure as necessary, by-product water can be effectively removed. Thereafter, pressurization is performed with an inert gas such as nitrogen to extrude the polyamide melt as a strand. The final temperature of the resin temperature (liquid temperature) is preferably higher by 10 ° C. or more than T _pm-1 in order to maintain a molten state. The strand can be cooled and cut to obtain copolymerized polyamide pellets.

[Polyamide resin composition]
The polyamide resin composition of the present embodiment contains the above-described copolymer polyamide (A), glass fiber (B), and inorganic filler (C) other than glass fiber.

((B) Glass fiber)
The polyamide resin composition of the present embodiment contains (B) glass fiber and (C) inorganic filler other than glass fiber (B), so that it has low water absorption such as heat resistance, toughness, fluidity, and rigidity. In addition to these properties, strength, rigidity after water absorption (water absorption rigidity), high temperature without impairing the properties of the copolymerized polyamide (A) excellent in properties, low blocking properties, releasability and plasticization time stability Excellent rigidity under use (rigidity during heating), less dependence on molding conditions such as warping, and excellent appearance.

(B) The glass fiber may have a round shape or a flat shape in cross section.
(B) The flat shape of the cross section of the glass fiber includes, for example, a rectangle, an oval close to a rectangle, an ellipse, a saddle shape with a narrowed central portion in the longitudinal direction, and the like.
The flatness is represented by D2 / D1 when the major axis of the fiber cross section is D2 and the minor axis of the fiber cross section is D1 (a perfect circle has a flatness ratio of about 1).
When flat glass fibers are used, the flatness is preferably 1.5 to 10.
(B) Among glass fibers, from the viewpoint that excellent mechanical strength characteristics can be imparted to the polyamide resin composition, the number average fiber diameter is 3 to 30 μm, the weight average fiber length is 100 to 750 μm, and the weight average The aspect ratio (L / D) between the fiber length (L) and the number average fiber diameter (D) is preferably 10 to 100.
In addition, the number average fiber diameter (D) and the weight average fiber length (L) are, for example, putting the polyamide resin composition into an electric furnace, incinerating the contained organic matter, and, for example, 100 or more glass fibers from the residue. Can be selected arbitrarily, the number average fiber diameter can be measured by observing with SEM and measuring the fiber diameter, and the weight average fiber length is obtained by measuring the fiber length using an SEM photograph at a magnification of 1000 times Can do.

Content of the said (B) glass fiber is 1-300 mass parts with respect to 100 mass parts of said (A) polyamide copolymers, Preferably it is 10-150 mass parts, More preferably, it is 20-120. It is a mass part, More preferably, it is 30-100 mass parts, More preferably, it is 40-90 mass parts.
By setting the content of the (B) glass fiber to 1 part by mass or more, the effect of improving the strength of the polyamide resin composition is sufficiently expressed, and by setting the content to 200 parts by mass or less, extrudability, A polyamide resin composition having excellent moldability and surface appearance is obtained.

<Treatment with surface treatment agent>
The (B) glass fiber may be treated with a surface treatment agent such as a silane coupling agent.
Although it does not restrict | limit especially as a silane coupling agent, For example, aminosilanes, such as (gamma) -aminopropyltriethoxysilane, (gamma) -aminopropyltrimethoxysilane, and N- (beta)-(aminoethyl) -gamma-aminopropylmethyldimethoxysilane Mercaptosilanes such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane; epoxysilanes; vinylsilanes. These may be used individually by 1 type, or may be used in combination of 2 or more type, and aminosilanes are more preferable.

<Treatment with sizing agent>
The (B) glass fiber may be treated with a sizing agent as necessary.
Examples of the sizing agent include a copolymer containing a carboxylic acid anhydride-containing unsaturated vinyl monomer and an unsaturated vinyl monomer excluding the carboxylic acid anhydride-containing unsaturated vinyl monomer as constituent units, and an epoxy. Resins, polyurethane resins, homopolymers of acrylic acid, copolymers of acrylic acid and other copolymerizable monomers, and salts thereof with primary, secondary, and tertiary amines, carboxylic acid anhydride-containing Examples thereof include a copolymer containing a saturated vinyl monomer and an unsaturated vinyl monomer excluding the carboxylic anhydride-containing unsaturated vinyl monomer.
These may be used individually by 1 type and may be used in combination of 2 or more type. In particular, from the viewpoint of the mechanical strength of the polyamide resin composition, the carboxylic acid anhydride-containing unsaturated vinyl monomer and the unsaturated vinyl monomer excluding the carboxylic acid anhydride-containing unsaturated vinyl monomer are structural units. Copolymer, epoxy compound and polyurethane resin, and combinations thereof are preferably used, and unsaturated vinyl monomer containing carboxylic acid anhydride-containing unsaturated vinyl monomer and unsaturated vinyl monomer containing carboxylic acid anhydride More preferred are copolymers and polyurethane resins containing a polymer as a structural unit, and combinations thereof.

The carboxylic acid anhydride constituting the copolymer comprising the carboxylic acid anhydride-containing unsaturated vinyl monomer and the unsaturated vinyl monomer excluding the carboxylic acid anhydride-containing unsaturated vinyl monomer as constituent units. The contained unsaturated vinyl monomer is not particularly limited, and examples thereof include maleic anhydride, itaconic anhydride, and citraconic anhydride, and maleic anhydride is particularly preferable.
On the other hand, the unsaturated vinyl monomer excluding the carboxylic anhydride-containing unsaturated vinyl monomer means an unsaturated vinyl monomer different from the carboxylic anhydride-containing unsaturated vinyl monomer. The unsaturated vinyl monomer excluding the carboxylic acid anhydride-containing unsaturated vinyl monomer is not limited to the following, but examples thereof include styrene, α-methylstyrene, ethylene, propylene, and butadiene. , Isoprene, chloroprene, 2,3-dichlorobutadiene, 1,3-pentadiene, cyclooctadiene, methyl methacrylate, methyl acrylate, ethyl acrylate, and ethyl methacrylate. In particular, styrene and butadiene are preferable. Among these combinations, selected from the group consisting of a copolymer of maleic anhydride and butadiene, a copolymer of maleic anhydride and ethylene, a copolymer of maleic anhydride and styrene, and a mixture thereof. It is more preferable that it is 1 type or more.

  Further, the copolymer containing the carboxylic acid anhydride-containing unsaturated vinyl monomer and the unsaturated vinyl monomer excluding the carboxylic acid anhydride-containing unsaturated vinyl monomer as constituent units has a weight average molecular weight. It is preferably 2,000 or more. Moreover, from a viewpoint of the fluidity | liquidity improvement of the polyamide resin composition of this embodiment, More preferably, it is 2,000-1,000,000, More preferably, it is 2,000-1,000,000. The weight average molecular weight can be measured by gel permeation chromatography (GPC).

  Examples of the epoxy resin include, but are not limited to, ethylene oxide, propylene oxide, butene oxide, pentene oxide, hexene oxide, heptene oxide, octene oxide, nonene oxide, decene oxide undecene oxide, dodecene. Aliphatic epoxy compounds such as oxide, pentadecene oxide and eicosene oxide; glycidol, epoxypentanol, 1-chloro-3,4-epoxybutane, 1-chloro-2-methyl-3,4-epoxybutane, 1, 4-dichloro-2,3-epoxybutane, cyclopentene oxide, cyclohexene oxide, cycloheptene oxide, cyclooctene oxide, methylcyclohexene oxide, vinylcyclohex Alicyclic epoxy compounds such as oxides and epoxidized cyclohexene methyl alcohol; terpene epoxy compounds such as pinene oxide; aromatic epoxy compounds such as styrene oxide, p-chlorostyrene oxide and m-chlorostyrene oxide; epoxidized soybean oil And epoxidized linseed oil.

The polyurethane resin is not particularly limited as long as it is generally used as a sizing agent.
For example, synthesized from isocyanates such as m-xylylene diisocyanate (XDI), 4,4′-methylenebis (cyclohexyl isocyanate) (HMDI) and isophorone diisocyanate (IPDI), and polyester or polyether diols. Can be suitably used.

The acrylic acid homopolymer (polyacrylic acid) preferably has a weight average molecular weight of 1,000 to 90,000, more preferably 1,000 to 25,000.
The polyacrylic acid may be in a salt form. Examples of the salt of polyacrylic acid include primary, secondary and tertiary amines. For example, triethylamine, triethanolamine, glycine and the like can be mentioned. The degree of neutralization is preferably 20 to 90% and preferably 40 to 60% from the viewpoint of improving the stability of the mixed solution with other concomitant drugs (such as a silane coupling agent) and from the viewpoint of reducing amine odor. It is more preferable. The weight average molecular weight of the polyacrylic acid salt is not particularly limited, but is preferably in the range of 3,000 to 50,000. (B) 3,000 or more is preferable from the viewpoint of improving the convergence of the glass fiber, and 50,000 or less is preferable from the viewpoint of improving strength and rigidity.

The monomer that forms a copolymer of the acrylic acid and other copolymerizable monomers is not limited to the following examples. For example, acrylic acid, maleic acid, methacrylic acid, vinyl acetic acid, crotonic acid, isocrotonic acid, fumaric acid And at least one selected from monomers having a hydroxyl group and / or a carboxyl group, such as itaconic acid, citraconic acid and mesaconic acid (except for acrylic acid only).
In addition, it is preferable to have 1 or more types of ester type monomers among the monomers mentioned above.

  The copolymer of acrylic acid and other copolymerizable monomer may be in the form of a salt. Salts of copolymers of acrylic acid and other copolymerizable monomers are not limited to the following examples, but include primary, secondary, and tertiary amines. For example, triethylamine, triethanolamine and glycine can be mentioned. The degree of neutralization is preferably 20 to 90%, preferably 40 to 60% from the viewpoint of improving the stability of the mixed solution with other concomitant drugs (such as a silane coupling agent) and reducing the amine odor. Is more preferable.

The weight average molecular weight of the copolymer salt of acrylic acid and other copolymerizable monomers is not particularly limited, but is preferably in the range of 3,000 to 50,000.
(B) 3,000 or more is preferable from the viewpoint of improving the convergence of the glass fiber, and 50,000 or less is preferable from the viewpoint of improving strength and rigidity.

(B) The glass fiber is obtained by drying the fiber strand produced by applying the sizing agent to the glass fiber using a known method such as a roller type applicator in the known glass fiber production process. .
The fiber strand may be used as a roving as it is, or may be used as a chopped glass strand by further obtaining a cutting step. Such a sizing agent preferably imparts (adds) 0.2 to 3% by mass or more, more preferably 0.3 to 2% by mass (added) as a solid content with respect to 100% by mass of the glass fiber. . (B) From the viewpoint of maintaining the bundling of the glass fiber, it is preferable that the addition amount of the bundling agent is 0.2% by mass or more as a solid content with respect to 100% by mass of the glass fiber. On the other hand, from the viewpoint of improving the thermal stability of the polyamide resin composition, it is preferably 3% by mass or less. Moreover, drying of a strand may be performed after a cutting process, and you may cut | disconnect, after drying a strand.

((C) Inorganic filler other than glass fiber (B))
The polyamide resin composition of this embodiment comprises (C) an inorganic filler other than glass fiber (B) (in the present specification, (C): (B) an inorganic filler other than glass fiber, (C): (B Inorganic fillers other than ()) and (C) inorganic fillers).
(C): The content of the inorganic filler other than the glass fiber (B) is 1 to 200 parts by mass, preferably 2 to 150 parts by mass with respect to 100 parts by mass of the above-mentioned (A) polyamide copolymer. Yes, more preferably 3 to 120 parts by mass, still more preferably 5 to 100 parts by mass, and even more preferably 10 to 80 parts by mass.
(C): By making content of inorganic fillers other than glass fiber (B) 1 mass part or more, the rigidity improvement effect of a polyamide resin composition is expressed, and content is 200 mass parts or less. Thus, a polyamide resin composition having excellent extrudability and moldability can be obtained.

(C): The inorganic filler other than the glass fiber (B) is not particularly limited. For example, carbon fiber, calcium silicate fiber, potassium titanate fiber, aluminum borate fiber, flaky glass, Talc, kaolin, mica, hydrotalcite, calcium carbonate, magnesium carbonate, clay, zinc carbonate, zinc oxide, calcium monohydrogen phosphate, wollastonite, silica, zeolite, alumina, boehmite, aluminum hydroxide, titanium oxide, oxidation Silicon, magnesium oxide, calcium silicate, sodium aluminosilicate, magnesium silicate, ketjen black, acetylene black, furnace black, carbon nanotube, graphite, brass, copper, silver, aluminum, nickel, iron, calcium fluoride, montmorillo Knight, include swellable fluorine mica and apatite.
In particular, from the viewpoint of strength, rigidity, and surface appearance of the polyamide resin composition of the present embodiment, wollastonite, kaolin, mica, talc, calcium carbonate, magnesium carbonate, potassium titanate fiber, aluminum borate fiber, and clay are used. Wollastonite, kaolin, mica and talc are more preferable, wollastonite and mica are more preferable, and wollastonite is still more preferable. Said (C) inorganic filler may be used individually by 1 type, and may be used in combination of 2 or more type.

(C): The average particle diameter of the inorganic filler other than the glass fiber (B) is preferably 0.01 to 38 μm, preferably 0.03 to 30 μm from the viewpoint of toughness and surface appearance of the polyamide resin composition of the present embodiment. Is more preferable, 0.05 to 25 μm is more preferable, 0.1 to 20 μm is still more preferable, and 0.15 to 15 μm is still more preferable. By setting the average particle size to 38 μm or less, a polyamide resin composition having excellent toughness and surface appearance can be obtained. By making the average particle size 0.01 μm or more, further 0.1 μm or more, cost and powder handling are possible. The balance between surface and physical properties will be good.
In addition, among inorganic fillers, those having a needle-like shape such as wollastonite have an average fiber diameter as an average particle diameter. Furthermore, when the cross section is not a circle, the maximum value of the length is taken as the fiber diameter. Regarding the aspect ratio (L / D) between the weight average fiber length (L) and the number average fiber diameter (D) of the needle-shaped one, the appearance of the molded product and the viewpoint of wear of metallic parts such as injection molding machines Therefore, 1.5 to 10 is preferable, 2.0 to 5 is more preferable, and 2.5 to 4 is still more preferable.
As a specific method for measuring the average particle diameter, using a scanning electron microscope (SEM) (JSM-6700F, manufactured by JEOL Ltd.), (C): an inorganic filler image other than glass fiber (B). Images are taken at a magnification of 1000 to 50000 times, and the particle size is measured from arbitrarily selected 500 inorganic fillers. (C) When the inorganic filler is needle-shaped and the cross section is a circle, the needle diameter is the particle diameter, and when the cross-section is not a circle, the maximum length of the needle-shaped body is the needle diameter. And this is regarded as the particle size.

<Treatment with surface treatment agent>
(C) The inorganic filler other than the glass fiber (B) may be surface-treated with a silane coupling agent or the like.
The silane coupling agent is not limited to the following examples. For example, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) -γ-amino Examples include aminosilanes such as propylmethyldimethoxysilane; mercaptosilanes such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane; epoxysilanes; vinylsilanes.
In particular, at least one selected from the above-listed components is preferable, and aminosilanes are more preferable.
The surface treatment agent can be previously treated on the surface of an inorganic filler other than (C) glass fiber (B), (A) copolymer polyamide, (B) glass fiber, (C) glass fiber (B). You may add when mixing inorganic fillers other than. The amount of the surface treatment agent is preferably in the range of 0.05 to 1.5 parts by mass with respect to 100 parts by mass of the inorganic filler other than (C) glass fiber (B).

  The polyamide resin composition of the present embodiment may contain one or more components selected from the group consisting of a nucleating agent, a lubricant, a stabilizer, and a polymer other than the copolymerized polyamide (A) described above. Good.

(Nucleating agent)
The nucleating agent is not limited to the following. For example, the addition increases the crystallization peak temperature of the polyamide resin composition, or reduces the difference between the extrapolation start temperature and the extrapolation end temperature of the crystallization peak. Or a substance capable of obtaining the effect of miniaturizing the spherulites of the obtained molded product or making the size uniform. The nucleating agent is not particularly limited, and examples thereof include talc, boron nitride, mica, kaolin, calcium carbonate, barium sulfate, silicon nitride, carbon black, potassium titanate, and molybdenum disulfide.

  A nucleating agent may be used by 1 type and may be used in combination of 2 or more types.

  The nucleating agent is preferably talc or boron nitride from the viewpoint of the nucleating agent effect.

  Moreover, since a nucleating agent effect is high, the nucleating agent whose number average particle diameter is 0.01-10 micrometers is preferable.

  The number average particle size of the nucleating agent is measured by dissolving the molded article in a solvent in which polyamide such as formic acid is soluble, and, for example, 100 or more nucleating agents arbitrarily selected from the obtained insoluble components. It can be obtained by observing with an optical microscope or a scanning electron microscope.

  In the polyamide resin composition of the present embodiment, the content of the nucleating agent is preferably 0.001 to 1 part by mass, more preferably 0.001 to 100 parts by mass of the (A) copolymerized polyamide. It is -0.5 mass part, More preferably, it is 0.001-0.09 mass part.

  By setting the content of the nucleating agent to 0.001 part by mass or more with respect to 100 parts by mass of the (A) copolymerized polyamide, the heat resistance of the polyamide resin composition is improved and the nucleation is achieved. By setting the content of the agent to 1 part by mass or less with respect to 100 parts by mass of the copolymerized polyamide, a polyamide resin composition having excellent toughness can be obtained.

(lubricant)
Examples of the lubricant include, but are not limited to, higher fatty acids, higher fatty acid metal salts, higher fatty acid esters, and higher fatty acid amides.

  One type of lubricant may be used, or two or more types may be used in combination.

  Although it does not specifically limit as said higher fatty acid, For example, C8-C40 saturated or unsaturated linear chain, such as stearic acid, palmitic acid, behenic acid, erucic acid, oleic acid, lauric acid, and montanic acid Alternatively, branched aliphatic monocarboxylic acids are exemplified, and stearic acid and montanic acid are preferable.

  As the higher fatty acid, one kind may be used, or two or more kinds may be used in combination.

  The higher fatty acid metal salt is a metal salt of the higher fatty acid.

  The metal element constituting the higher fatty acid metal salt is preferably a group 1, 2, 3 element of the periodic table, zinc, aluminum, or the like, more preferably a first such as calcium, sodium, potassium, magnesium, or the like. , Group 2 elements, aluminum and the like.

  The higher fatty acid metal salt is not particularly limited, and examples thereof include calcium stearate, aluminum stearate, zinc stearate, magnesium stearate, calcium montanate, sodium montanate, calcium palmitate and the like. Metal salts and metal salts of stearic acid are preferred.

  As the higher fatty acid metal salt, one kind may be used, or two or more kinds may be used in combination.

  The higher fatty acid ester is an esterified product of the higher fatty acid and alcohol. The higher fatty acid ester is preferably an ester of an aliphatic carboxylic acid having 8 to 40 carbon atoms and an aliphatic alcohol having 8 to 40 carbon atoms.

  Although it does not specifically limit as said aliphatic alcohol, For example, stearyl alcohol, behenyl alcohol, lauryl alcohol, etc. are mentioned.

  The higher fatty acid ester is not particularly limited, and examples thereof include stearyl stearate and behenyl behenate.

  As the higher fatty acid ester, one kind may be used, or two or more kinds may be used in combination.

  The higher fatty acid amide is an amide compound of the higher fatty acid.

  Examples of the higher fatty acid amide include, but are not limited to, stearic acid amide, oleic acid amide, erucic acid amide, ethylene bisstearyl amide, ethylene bisoleyl amide, N-stearyl stearyl amide, N-stearyl erucamide, and the like. It is done.

  The higher fatty acid amide is preferably stearic acid amide, erucic acid amide, ethylene bisstearyl amide, and N-stearyl erucamide, and more preferably ethylene bisstearyl amide and N-stearyl erucamide.

  As the higher fatty acid amide, one kind may be used, or two or more kinds may be used in combination.

  The lubricant is preferably a higher fatty acid metal salt or a higher fatty acid amide, more preferably a higher fatty acid metal salt, from the viewpoint of the effect of improving the moldability of the polyamide resin composition.

  In the polyamide resin composition of the present embodiment, the content of the lubricant is preferably 0.001 to 1 part by mass, more preferably 0.03 to 0.5 part with respect to 100 parts by mass of the polyamide resin composition. Part by mass.

  When the content of the lubricant is within the above range, the polyamide resin composition having excellent releasability and plasticization time stability and excellent toughness can be obtained, and the molecular chain is broken. The extreme molecular weight reduction of the polyamide can be prevented.

((D) heat stabilizer)
The polyamide resin composition of the present embodiment includes a phenol-based heat stabilizer, a phosphorus-based heat stabilizer, an amine-based heat stabilizer, Group Ib, Group IIb, Group IIIa, Group IIIb, Group IVa of the periodic table. It can further contain at least one (D) heat stabilizer selected from the group consisting of metal salts of Group IVb and Group IVb elements, and halides of alkali metals and alkaline earth metals.

(Phenolic heat stabilizer)
Although it does not restrict | limit especially as said phenol type heat stabilizer, For example, a hindered phenol compound is mentioned.
Phenol-based heat stabilizers, particularly hindered phenol compounds, have the property of imparting heat resistance and light resistance to resins such as polyamide and fibers.

The hindered phenol compound is not particularly limited. For example, N, N′-hexane-1,6-diylbis [3- (3,5-di-t-butyl-4-hydroxyphenylpropionamide), Pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], N, N′-hexamethylenebis (3,5-di-t-butyl-4-hydroxy-) Hydrocinnamamide), triethylene glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate], 3,9-bis {2- [3- (3-t-butyl) -4-hydroxy-5-methylphenyl) propynyloxy] -1,1-dimethylethyl} -2,4,8,10-tetraoxapyro [5,5] undecane, 3,5- -T-butyl-4-hydroxybenzylphosphonate-diethyl ester, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, and 1, 3,5-tris (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanuric acid.
A phenol type heat stabilizer may be used individually by 1 type, and may be used in combination of 2 or more type.
In particular, as a phenol-based heat stabilizer, N, N′-hexane-1,6-diylbis [3- (3,5-di-t-butyl-4-hydroxyphenylpropion) is used from the viewpoint of improving heat aging resistance. Amide)] is preferred.

  When using a phenol-based heat stabilizer, the content of the phenol-based heat stabilizer in the polyamide resin composition is preferably 0.01 to 1 part by weight with respect to 100 parts by weight of the copolymerized polyamide (A). More preferably, it is 0.1-1 mass part. When the content of the phenol-based heat stabilizer in the polyamide resin composition is within the above range, the heat aging resistance of the polyamide resin composition can be further improved and the amount of generated gas can be further reduced.

(Phosphorus heat stabilizer)
The phosphorus-based heat stabilizer is not particularly limited. For example, pentaerythritol phosphite compound, trioctyl phosphite, trilauryl phosphite, tridecyl phosphite, octyl diphenyl phosphite, trisisodecyl phosphite, phenyl Diisodecyl phosphite, phenyl di (tridecyl) phosphite, diphenyl isooctyl phosphite, diphenyl isodecyl phosphite, diphenyl (tridecyl) phosphite, triphenyl phosphite, tris (nonylphenyl) phosphite, tris (2,4-di -T-butylphenyl) phosphite, tris (2,4-di-t-butyl-5-methylphenyl) phosphite, tris (butoxyethyl) phosphite, 4,4'-butylidene-bis (3 Methyl-6-tert-butylphenyl-tetra-tridecyl) diphosphite, tetra (C12-C15 mixed alkyl) -4,4′-isopropylidene diphenyldiphosphite, 4,4′-isopropylidenebis (2-tert-butyl) Phenyl) di (nonylphenyl) phosphite, tris (biphenyl) phosphite, tetra (tridecyl) -1,1,3-tris (2-methyl-5-tert-butyl-4-hydroxyphenyl) butanediphosphite, Tetra (tridecyl) -4,4′-butylidenebis (3-methyl-6-tert-butylphenyl) diphosphite, tetra (C1-C15 mixed alkyl) -4,4′-isopropylidene diphenyldiphosphite, tris (mono, Dimixed nonylphenyl) phosphite, 9,10-di-hydro-9-oxa- -Oxa-10-phosphaphenanthrene-10-oxide, tris (3,5-di-t-butyl-4-hydroxyphenyl) phosphite, hydrogenated-4,4'-isopropylidene diphenyl polyphosphite, Bis (octylphenyl) bis (4,4′-butylidenebis (3-methyl-6-tert-butylphenyl)) 1,6-hexanol diphosphite, hexatridecyl-1,1,3-tris (2-methyl -4-hydroxy-5-t-butylphenyl) diphosphite, tris (4,4'-isopropylidenebis (2-t-butylphenyl)) phosphite, tris (1,3-stearoyloxyisopropyl) phosphite, 2 2-methylenebis (4,6-di-t-butylphenyl) octyl phosphite, 2,2-methylenebis (3- Til-4,6-di-t-butylphenyl) 2-ethylhexyl phosphite, tetrakis (2,4-di-t-butyl-5-methylphenyl) -4,4'-biphenylenediphosphite, and tetrakis ( 2,4-di-t-butylphenyl) -4,4′-biphenylene diphosphite.
These may be used alone or in combination of two or more.

Among the phosphorus-based heat stabilizers, among those listed above, from the viewpoint of further improving the heat aging resistance of the polyamide resin composition and reducing the generated gas, a pentaerythritol type phosphite compound, tris (2,4-disulfide) is used. -T-Butylphenyl) phosphite is preferred.
The pentaerythritol type phosphite compound is not particularly limited. For example, (2,6-di-t-butyl-4-methylphenyl) phenylpentaerythritol diphosphite, (2,6-di-t-butyl) -4-methylphenyl) methylpentaerythritol diphosphite, (2,6-di-t-butyl-4-methylphenyl) 2-ethylhexylpentaerythritol diphosphite, (2,6-di-t-butyl-4) -Methylphenyl) isodecylpentaerythritol diphosphite, (2,6-di-t-butyl-4-methylphenyl) laurylpentaerythritol diphosphite, (2,6-di-t-butyl-4-methylphenyl) ) Isotridecyl pentaerythritol diphosphite, (2,6-di-t-butyl-4) Methylphenyl) stearylpentaerythritol diphosphite, (2,6-di-t-butyl-4-methylphenyl) cyclohexylpentaerythritol diphosphite, (2,6-di-t-butyl-4-methylphenyl) benzyl Pentaerythritol diphosphite, (2,6-di-t-butyl-4-methylphenyl) ethyl cellosolve pentaerythritol diphosphite, (2,6-di-t-butyl-4-methylphenyl) butyl carbitol penta Erythritol diphosphite, (2,6-di-t-butyl-4-methylphenyl) octylphenyl pentaerythritol diphosphite, (2,6-di-t-butyl-4-methylphenyl) nonylphenyl pentaerythritol di Phosphite, bis (2,6-di-t-butyl 4-methylphenyl) pentaerythritol diphosphite, bis (2,6-di-t-butyl-4-ethylphenyl) pentaerythritol diphosphite, (2,6-di-t-butyl-4-methyl) Phenyl) (2,6-di-t-butylphenyl) pentaerythritol diphosphite, (2,6-di-t-butyl-4-methylphenyl) (2,4-di-t-butylphenyl) pentaerythritol Diphosphite, (2,6-di-t-butyl-4-methylphenyl) (2,4-di-t-octylphenyl) pentaerythritol diphosphite, (2,6-di-t-butyl-4 -Methylphenyl) (2-cyclohexylphenyl) pentaerythritol diphosphite, (2,6-di-t-amyl-4-methylphenyl) phenylpen Taerythritol diphosphite, bis (2,6-di-t-amyl-4-methylphenyl) pentaerythritol diphosphite, and bis (2,6-di-t-octyl-4-methylphenyl) penta An example is erythritol diphosphite.
These may be used alone or in combination of two or more.

  Among the pentaerythritol type phosphite compounds listed above, bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite, from the viewpoint of reducing the gas generation amount of the polyamide resin composition, Bis (2,6-di-t-butyl-4-ethylphenyl) pentaerythritol diphosphite, bis (2,6-di-t-amyl-4-methylphenyl) pentaerythritol diphosphite, and bis (2 , 6-di-t-octyl-4-methylphenyl) pentaerythritol diphosphite is preferred, and bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite is more preferred.

When the phosphorus heat stabilizer is used, the content of the phosphorus heat stabilizer in the polyamide resin composition is preferably 0.01 to 1 part by mass with respect to 100 parts by mass of the copolymerized polyamide (A). More preferably, it is 0.1-1 mass part.
When the content of the phosphorus-based heat stabilizer in the polyamide resin composition is within the above range, the heat aging resistance of the polyamide resin composition can be further improved, and the amount of gas generated can be reduced.

(Amine heat stabilizer)
The amine heat stabilizer is not particularly limited, and examples thereof include 4-acetoxy-2,2,6,6-tetramethylpiperidine, 4-stearoyloxy-2,2,6,6-tetramethylpiperidine, 4 -Acryloyloxy-2,2,6,6-tetramethylpiperidine, 4- (phenylacetoxy) -2,2,6,6-tetramethylpiperidine, 4-benzoyloxy-2,2,6,6-tetramethyl Piperidine, 4-methoxy-2,2,6,6-tetramethylpiperidine, 4-stearyloxy-2,2,6,6-tetramethylpiperidine, 4-cyclohexyloxy-2,2,6,6-tetramethyl Piperidine, 4-benzyloxy-2,2,6,6-tetramethylpiperidine, 4-phenoxy-2,2,6,6-tetramethylpiperidi 4- (ethylcarbamoyloxy) -2,2,6,6-tetramethylpiperidine, 4- (cyclohexylcarbamoyloxy) -2,2,6,6-tetramethylpiperidine, 4- (phenylcarbamoyloxy) -2 , 2,6,6-tetramethylpiperidine, bis (2,2,6,6-tetramethyl-4-piperidyl) -carbonate, bis (2,2,6,6-tetramethyl-4-piperidyl) -oxalate Bis (2,2,6,6-tetramethyl-4-piperidyl) -malonate, bis (2,2,6,6-tetramethyl-4-piperidyl) -sebacate, bis (2,2,6,6 -Tetramethyl-4-piperidyl) -adipate, bis (2,2,6,6-tetramethyl-4-piperidyl) -terephthalate, 1,2-bis (2,2,6, -Tetramethyl-4-piperidyloxy) -ethane, α, α'-bis (2,2,6,6-tetramethyl-4-piperidyloxy) -p-xylene, bis (2,2,6,6- Tetramethyl-4-piperidyltolylene-2,4-dicarbamate, bis (2,2,6,6-tetramethyl-4-piperidyl) -hexamethylene-1,6-dicarbamate, tris (2,2, 6,6-tetramethyl-4-piperidyl) -benzene-1,3,5-tricarboxylate, tris (2,2,6,6-tetramethyl-4-piperidyl) -benzene-1,3,4 Tricarboxylate, 1- [2- {3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy} butyl] -4- [3- (3,5-di-t-butyl- 4-hydroxyphenyl) propyl Pionyloxy] 2,2,6,6-tetramethylpiperidine, 1,2,3,4-butanetetracarboxylic acid, 1,2,2,6,6-pentamethyl-4-piperidinol and β, β, β ′ , Β′-tetramethyl-3,9- [2,4,8,10-tetraoxaspiro (5,5) undecane] diethanol.
These may be used alone or in combination of two or more.

  When the amine heat stabilizer is used, the content of the amine heat stabilizer in the polyamide resin composition is preferably 0.01 to 1 part by mass with respect to 100 parts by mass of the copolymerized polyamide (A). More preferably, it is 0.1-1 mass part. When the content of the amine heat stabilizer in the polyamide composition is within the above range, the heat aging resistance of the polyamide composition can be further improved, and the amount of generated gas can be further reduced.

(Metal salts of elements of Group Ib, Group IIb, Group IIIa, Group IIIb, Group IVa and Group IVb of the periodic table)
The metal salt of the elements of Group Ib, Group IIb, Group IIIa, Group IIIb, Group IVa, and Group IVb of the periodic table is not particularly limited, but is preferably a copper salt.
Although it does not specifically limit as a copper salt, For example, copper halide (copper iodide, cuprous bromide, cupric bromide, cuprous chloride, etc.), copper acetate, copper propionate, copper benzoate, Examples include copper adipate, copper terephthalate, copper isophthalate, copper salicylate, copper nicotinate and copper stearate, and copper complex salts in which copper is coordinated to a chelating agent such as ethylenediamine and ethylenediaminetetraacetic acid.
These may be used alone or in combination of two or more.

Among the copper salts listed above, at least one selected from the group consisting of copper iodide, cuprous bromide, cupric bromide, cuprous chloride and copper acetate is preferred, and copper iodide and more preferably / Or copper acetate.
When such a preferable copper salt is used, a polyamide resin composition having excellent heat aging resistance and capable of suppressing metal corrosion of the screw or cylinder during extrusion (hereinafter also simply referred to as “metal corrosion”) can be obtained.

When using a copper salt, the content of the copper salt in the polyamide resin composition is preferably 0.01 to 0.2 parts by mass, more preferably 0 to 100 parts by mass of the copolymerized polyamide (A). 0.02 to 0.15 parts by mass.
When the content of the copper salt in the polyamide resin composition is within the above range, the heat aging resistance of the polyamide resin composition is further improved, and copper precipitation and metal corrosion can be suppressed.

  Further, from the viewpoint of improving the heat aging resistance of the polyamide resin composition, the content of copper element is preferably 10 to 500 ppm, more preferably 30 to 500 ppm, and still more preferably, with respect to the total amount of the polyamide resin composition. Is 50-300 ppm.

(Alkali metal and alkaline earth metal halides)
The alkali metal and alkaline earth metal halide is not particularly limited, and examples thereof include potassium iodide, potassium bromide, potassium chloride, sodium iodide and sodium chloride, and mixtures thereof.
In particular, the alkali metal and alkaline earth metal halides are preferably potassium iodide and potassium bromide, and mixtures thereof from the viewpoint of improving the heat aging resistance of the polyamide resin composition and suppressing metal corrosion. More preferably, it is potassium iodide.

  When the alkali metal and alkaline earth metal halide is used, the content of the alkali metal and alkaline earth metal halide in the polyamide resin composition is preferably 100 parts by mass of the copolymerized polyamide (A). Is 0.05-5 parts by mass, more preferably 0.2-2 parts by mass. When it is within the above range, the heat aging resistance is further improved, and copper precipitation and metal corrosion can be suppressed.

  The component (D) heat stabilizer mentioned above may be used individually by 1 type, and may be used in combination of 2 or more type. In particular, the component (D) of the heat stabilizer is preferably a mixture of a copper salt and an alkali metal or alkaline earth metal halide.

  The ratio of the copper salt to the alkali metal and alkaline earth metal halide is included in the polyamide resin composition so that the molar ratio of halogen to copper (halogen / copper) is 2/1 to 40/1. It is preferably 5/1 to 30/1. When the molar ratio of halogen to copper (halogen / copper) is within the above-described range, the heat aging resistance of the polyamide resin composition can be further improved.

When the halogen / copper is 2/1 or more, it is preferable because copper precipitation and metal corrosion can be suppressed.
On the other hand, when the halogen / copper is 40/1 or less, corrosion of the screw of the molding machine and the like can be prevented without substantially impairing mechanical properties such as toughness of the polyamide resin composition.

(Polymers other than copolymerized polyamide (A))
Although it does not specifically limit as polymers other than the said copolyamide (A), A thermoplastic resin, an elastomer component, etc. are mentioned.

  Examples of the thermoplastic resin include polyamides other than the copolymerized polyamide (A).

  The polyamide other than the copolymerized polyamide (A) is not particularly limited. For example, polyamide 66, polyamide 56, polyamide 46, polyamide 610, polyamide 612, polyamide 6T, polyamide 6I, polyamide 6, polyamide 11, polyamide 12, Polyamide MXD6 etc. are mentioned, These homopolymers or copolymers are mentioned.

  Other thermoplastic resins include, for example, polystyrene resins such as atactic polystyrene, isotactic polystyrene, syndiotactic polystyrene, AS resin, ABS resin; polyethylene terephthalate, polybutylene terephthalate, polytrimethylene terephthalate, polyethylene naphthalate, etc. Polyester resins such as liquid crystal polyester, polyarylate, polycarbonate, polyphenylene ether, polysulfone, polyethersulfone, and other polyether resins; polyphenylene sulfide, polyoxymethylene, and other condensation resins, polyacrylic acid, polyacrylate, polymethyl Acrylic resins such as methacrylate, polyolefins such as polyethylene, polypropylene, polybutene, and ethylene-propylene copolymers System resins; polyvinyl chloride, halogen-containing vinyl Compounds resins polyvinylidene chloride, phenol resins, epoxy resins and the like.

  These thermoplastic resins may be used individually by 1 type, and may be used in combination of 2 or more types.

Examples of the elastomer component include, but are not limited to, natural rubber, polybutadiene, polyisoprene, polyisobutylene, neoprene, polysulfide rubber, thiocol rubber, acrylic rubber, urethane rubber, silicone rubber, epichlorohydrin rubber, Styrene-butadiene block copolymer (SBR), hydrogenated styrene-butadiene block copolymer (SEB), styrene-butadiene-styrene block copolymer (SBS), hydrogenated styrene-butadiene-styrene block copolymer (SEBS) ), Styrene-isoprene block copolymer (SIR), hydrogenated styrene-isoprene block copolymer (SEP), styrene-isoprene-styrene block copolymer (SIS), hydrogenated styrene-isoprene Styrene block copolymer (SEPS), styrene-butadiene random copolymer, hydrogenated styrene-butadiene random copolymer, styrene-ethylene-propylene random copolymer, styrene-ethylene-butylene random copolymer, ethylene-propylene Copolymer (EPR), ethylene- (1-butene) copolymer, ethylene- (1-hexene) copolymer, ethylene- (1-octene) copolymer, ethylene-propylene-diene copolymer (EPDM) ), Or butadiene-acrylonitrile-styrene-core shell rubber (ABS), methyl methacrylate-butadiene-styrene-core shell rubber (MBS), methyl methacrylate-butyl acrylate-styrene-core shell rubber (MAS), octyl acrylate-butadiene- Core-shell types such as styrene-core-shell rubber (MABS), alkyl acrylate-butadiene-acrylonitrile-styrene core-shell rubber (AABS), butadiene-styrene-core shell rubber (SBR), siloxane-containing core-shell rubber including methyl methacrylate-butyl acrylate siloxane Etc.
These elastomer components may be used individually by 1 type, and may be used in combination of 2 or more types.

  In the copolymerized polyamide resin composition of the present embodiment, the content of the polymer other than the copolymerized polyamide (A) is preferably 1 to 200 parts by mass, more preferably 100 parts by mass of the copolymerized polyamide (A). Is 5 to 100 parts by mass, more preferably 5 to 50 parts by mass. By setting the content of the polymer other than the copolymerized polyamide (A) within the above range, a polyamide resin composition having excellent heat resistance and releasability can be obtained.

If necessary, colorants such as pigments and dyes (including colored master batches) may be added to the polyamide resin composition of the present embodiment as long as the purpose of the present embodiment is not impaired.
Examples of the colorant include, but are not limited to, dyes such as nigrosine, pigments such as titanium oxide and carbon black, aluminum, colored aluminum, nickel, tin, copper, gold, silver, platinum, iron oxide, stainless steel, and titanium. And at least one colorant selected from the group consisting of metallic pigments such as mica pearl pigment, color graphite, color glass fiber, and color flake glass.

(Other additives)
The polyamide resin composition of the present embodiment can also contain additives conventionally used for polyamide within a range that does not impair the purpose of the present embodiment. The additive is not particularly limited, and examples thereof include flame retardants, fibrillating agents, fluorescent bleaching agents, plasticizers, antioxidants, ultraviolet absorbers, antistatic agents, fluidity improvers, and spreading agents. Can be mentioned.

  When the polyamide resin composition of the present embodiment contains other additives that can be included in the polyamide resin composition described above, the content of the other additives depends on the type and the polyamide resin composition. Since it varies depending on the use and the like, there is no particular limitation as long as the object of the present embodiment is not impaired.

[Production method of polyamide resin composition]
The polyamide resin composition of the present embodiment comprises (A) a polyamide copolymer, (B) glass fibers described above, (C) inorganic fillers other than glass fibers (B), and other deterioration inhibitors as required. It can be prepared by blending various additives such as a moldability improver and a colorant, and other resins.
The production method of the polyamide resin composition of the present embodiment is not particularly limited as long as it is a production method including a step of melt-kneading the raw material component containing the above-mentioned copolymerized polyamide (A). A method in which a raw material component containing polyamide (A) is melt-kneaded with an extruder, and a setting temperature of the extruder is set to a melting peak temperature T _pm-1 + 30 ° C. or less of the above-mentioned copolymerized polyamide (A). preferable.

  The method of melt kneading the raw material component containing the copolymerized polyamide (A) is not particularly limited. For example, the copolymerized polyamide (A) and other raw materials are mixed using a tumbler, a Henschel mixer, etc. Examples thereof include a method of supplying and kneading, and a method of blending other raw materials from the side feeder into the copolymer polyamide (A) that has been melted by a single or twin screw extruder.

  In the method of supplying the components constituting the polyamide resin composition to the melt kneader, all the components may be supplied to the same supply port at once, or the components may be supplied from different supply ports. .

  The melt kneading temperature is preferably 250 to 375 ° C. as the resin temperature.

  The melt kneading time is preferably 0.25 to 5 minutes.

  The apparatus for performing the melt-kneading is not particularly limited, and a known apparatus such as a single- or twin-screw extruder, a Banbury mixer, and a mixing roll can be used.

〔Molding〕
The molded product of this embodiment is a molded product containing the above-mentioned copolymerized polyamide (A) or a polyamide resin composition.
The molded article of this embodiment is obtained by molding the above-mentioned copolymerized polyamide (A) or polyamide resin composition using a known molding method. The molding method is not particularly limited, but is generally known, for example, press molding, injection molding, gas assist injection molding, welding molding, extrusion molding, blow molding, film molding, hollow molding, multilayer molding, and melt spinning. A plastic molding method.

(Use)
Since the molded article of this embodiment is obtained from the above-mentioned copolymerized polyamide (A) or polyamide resin composition, it is excellent in heat resistance, moldability, mechanical strength, low water absorption, vibration fatigue characteristics, and surface appearance. Therefore, the molded product of the present embodiment is suitable as various parts such as automobile parts, electric and electronic parts, home appliance parts, OA equipment parts, portable equipment parts, industrial equipment parts, daily necessities and household goods, and for extrusion applications. Can be used. Among these, the molded product of the present embodiment is suitably used as an automobile part, an electronic part, a home appliance part, an OA equipment part, or a portable equipment part.

  Although it does not specifically limit as an automotive component, For example, an intake system component, a cooling system component, a fuel system component, an interior component, an exterior component, an electrical component, etc. are mentioned.

  Although it does not specifically limit as a motor vehicle intake system component, For example, an air intake manifold, an intercooler inlet, an exhaust pipe cover, an inner bush, a bearing retainer, an engine mount, an engine head cover, a resonator, a throttle body, etc. are mentioned.

  Although it does not specifically limit as a motor vehicle cooling system component, For example, a chain cover, a thermostat housing, an outlet pipe, a radiator tank, an oil noter, a delivery pipe, etc. are mentioned.

  Although it does not specifically limit in a vehicle fuel system component, For example, a fuel delivery pipe, a gasoline tank case, etc. are mentioned.

  Although it does not specifically limit as a vehicle interior component, For example, an instrument panel, a console box, a glove box, a steering wheel, a trim, etc. are mentioned.

  Although it does not specifically limit as a motor vehicle exterior component, For example, a mall, a lamp housing, a front grille, a mud guard, a side bumper, a door mirror stay, a roof rail, etc. are mentioned.

  Although it does not specifically limit as a vehicle electrical component, For example, a connector, a wire harness connector, a motor component, a lamp socket, a sensor vehicle-mounted switch, a combination switch etc. are mentioned.

Although it does not specifically limit as an electrical and electronic component, For example, a connector, the reflector for light-emitting devices, a switch, a relay, a printed wiring board, the housing of an electronic component, an electrical outlet, a noise filter, a coil bobbin, a motor end cap, etc. are mentioned. The reflector for a light emitting device can be widely used in semiconductor packages such as photo diodes, CCDs, and CMOSs as well as optical semiconductors such as LDs in addition to LEDs.
Although it does not specifically limit as portable apparatus components, For example, housing | casings, structures, etc., such as a mobile telephone, a smart phone, a personal computer, a portable game device, a digital camera, etc. are mentioned.

  Although it does not specifically limit as industrial equipment components, For example, a gear, a cam, an insulation block, a valve, an electric tool component, an agricultural equipment component, an engine cover etc. are mentioned.

  Although it does not specifically limit as household goods and household goods, For example, a button, a food container, office furniture, etc. are mentioned.

  Although it does not specifically limit as an extrusion use, For example, it uses for a film, a sheet | seat, a filament, a tube, a stick | rod, a hollow molded article, etc.

Among these various uses, the molded product of the present embodiment has a thin part (for example, a thickness of 0.5 mm), and further undergoes a heat treatment process (for example, an SMT connector, a reflector for a light emitting device). It is particularly suitable for electrical / electronic components such as switches.
Moreover, since the molded product of this embodiment is excellent in surface appearance, it is preferably used as a molded product in which a coating film is formed on the surface of the molded product. The method for forming the coating film is not particularly limited as long as it is a known method, and for example, it can be performed by coating such as a spray method or an electrostatic coating method. The paint used for the coating is not particularly limited as long as it is a known one, and a melamine cross-linked polyester polyol resin paint, an acrylic urethane paint, or the like can be used.

  Hereinafter, the present embodiment will be described more specifically with reference to examples and comparative examples, but the present embodiment is not limited to only these examples.

The raw materials and measurement methods used in Examples and Comparative Examples are shown below. In this example, 1 kg / cm ² means 0.098 MPa.

[Raw material of polyamide resin composition]
(A) Copolymer polyamide, (B) Glass fiber, (C): Inorganic filler other than glass fiber (B), etc. used as raw materials for the polyamide resin composition are shown below.

((A) Copolyamide etc.)
(1) Polyamide (PA-1) obtained by polymerizing 1,4-cyclohexanedicarboxylic acid, decamethylenediamine and sebacic acid as described in Production Example 1
(2) Polyamide (PA-2) obtained by polymerizing 1,4-cyclohexanedicarboxylic acid, decamethylenediamine and isophthalic acid described in Production Example 2
(3) Polyamide obtained by polymerizing 1,4-cyclohexanedicarboxylic acid, octamethylenediamine and isophthalic acid described in Production Example 3 (PA-3)
(4) Polyamide (PA-4) obtained by polymerizing 1,4-cyclohexanedicarboxylic acid, decamethylenediamine and 1,6-diaminohexane described in Production Example 4
(5) Polyamide obtained by polymerizing 1,4-cyclohexanedicarboxylic acid, decamethylenediamine, 1,6-diaminohexane and sebacic acid described in Production Example 5 (PA-5)
(6) Polyamide obtained by polymerizing 1,4-cyclohexanedicarboxylic acid, 1,12-diaminododecane and 1,6-diaminohexane described in Production Example 6 (PA-6)
(7) Polyamide obtained by polymerizing 1,4-cyclohexanedicarboxylic acid, 1,12-diaminododecane and 1,10-diaminodecane described in Production Example 7 (PA-7)
(8) Polyamide obtained by polymerizing 1,4-cyclohexanedicarboxylic acid, decamethylenediamine and ε-caprolactam described in Production Example 8 (PA-8)
(9) Polyamide obtained by polymerizing 1,4-cyclohexanedicarboxylic acid, decamethylenediamine and 11-aminoundecanoic acid described in Production Example 9 (PA-9)
(10) Polyamide 66 (PA-10) obtained by polymerizing hexamethylenediamine and adipic acid as described in Production Example 10
(11) Polyamide obtained by polymerizing 1,4-cyclohexanedicarboxylic acid, hexamethylenediamine, and ε-caprolactam described in Comparative Production Example 1 (PA-11)
(12) Polyamide 9T (PA-12) described in Comparative Production Example 2

  It shows below about the dicarboxylic acid, diamine, caprolactam, etc. which comprise (A) copolymerization polyamide etc. of manufacture examples 1-10 and comparative manufacture examples 1 and 2.

<Dicarboxylic acid>
(1) 1,4-cyclohexanedicarboxylic acid (CHDA)
Product name: 1,4-CHDA HP grade (trans isomer / cis isomer = 25/75)
(Eastman Chemical)
(2) Sebacic acid (C10DC)
Product name: Sebacic acid TA (manufactured by Ito Oil Co., Ltd.)
(3) Isophthalic acid (IPA) (manufactured by Wako Pure Chemical Industries, Ltd.)
(4) Terephthalic acid (TPA) (manufactured by Wako Pure Chemical Industries, Ltd.)
(5) Adipic acid (ADA) (Wako Pure Chemical Industries, Ltd.)

<Diamine>
(1) 1,10-diaminodecane (decamethylenediamine) (C10DA) (manufactured by Tokyo Chemical Industry)
(2) 1,6-diaminohexane (hexamethylenediamine) (C6DA) (manufactured by Tokyo Chemical Industry)
(3) Octamethylenediamine (C8DA) (manufactured by Tokyo Chemical Industry Co., Ltd.)
(4) 1,12-diaminododecane (dodecamethylenediamine) (C12DA) (manufactured by Tokyo Chemical Industry)
(5) 1,9-diaminononane (nonamethylenediamine) (C9DA) (manufactured by Tokyo Chemical Industry)
(6) 2-Methyloctamethylenediamine (2MC8DA) The 2-methyloctamethylenediamine was produced with reference to the production method described in JP-A No. 05-17413.

<Caprolactam, etc.>
(1) ε-caprolactam (CPL) (manufactured by Wako Pure Chemical Industries)
(2) 11-aminoundecanoic acid (11AU) (manufactured by Aldrich)

[(B) Glass fiber]
(B-1) Glass fiber Product name ECS03T275H manufactured by Nippon Electric Glass
Average fiber diameter (average particle diameter) 10 μm (circular shape), cut length 3 mm

[(C): (B) inorganic filler other than glass fiber]
(C-1) Wollastonite Brand name NYAD400 made by NYCO
Average fiber diameter (average particle diameter) 7.0 μm Average fiber length 35 μm
(C-2) Wollastonite Brand name NYAD5000 made by NYCO
Average fiber diameter (average particle diameter) 2.2 μm Average fiber length 7.2 μm
(C-3) Mica Yamaguchi Mica Industrial Co., Ltd. Product name A-21
Average particle size 22μm
(C-4) Talc Fuji Talc Kogyo Co., Ltd. Product name PKP-80
Average particle size 14μm
(C-5) Kaolin Hayashi Kasei Co., Ltd. Trade name TRANSLINK 445 Average particle size 1.5 μm

〔Measuring method〕
(1) Content of each structural unit in copolymerized polyamide The content of each structural unit in the copolymerized polyamide was quantified by ¹ H-NMR measurement as follows. The copolyamide pellets obtained in the production examples and comparative production examples were dissolved by heating in heavy hexafluoroisopropanol to a concentration of about 5% by mass, and JEOL nuclear magnetic resonance analyzer JNM ECA-500 was prepared. (A) a unit composed of an alicyclic dicarboxylic acid constituting the copolymer polyamide by analyzing ¹ H-NMR and calculating an integral ratio, (c-1) the (a) alicyclic dicarboxylic acid A unit composed of a dicarboxylic acid other than (b) a unit composed of a diamine having 8 or more carbon atoms, (c-2) a unit composed of a diamine having fewer carbon atoms than the diamine of (b), (c-3) a lactam and / or Alternatively, the content of units consisting of aminocarboxylic acid was determined.

(2) Trans isomerization rate The trans isomerization rate in the part derived from the alicyclic dicarboxylic acid of the copolymer polyamide obtained in the production example and the comparative production example was determined as follows.
30 to 40 mg of copolymerized polyamide was dissolved in 1.2 g of hexafluoroisopropanol deuteride, and ¹ H-NMR was measured using the resulting solution. In the case of 1,4-cyclohexanedicarboxylic acid, from the ratio of the peak area of 1.98 ppm derived from the trans isomer and the peak areas of 1.77 ppm and 1.86 ppm derived from the cis isomer in ¹ H-NMR measurement. The trans isomer ratio in the portion derived from the alicyclic dicarboxylic acid of the copolymerized polyamide was determined.
The trans isomer ratio is shown in Table 2 below.

(3) Melting peak temperature (melting point), crystallization peak temperature, crystallization enthalpy The melting peak temperature (melting point), crystallization peak temperature and crystallization enthalpy of the copolymerized polyamide obtained in the production examples and comparative production examples, According to JIS-K7121, it measured as follows using Diamond-DSC by PERKIN-ELMER. The measurement was performed under a nitrogen atmosphere.
First, about 10 mg of the sample was heated from 50 ° C. to 350 ° C. at a temperature increase rate of 20 ° C./min.
The endothermic peak appearing at this time was taken as the melting peak, and the peak appearing on the highest temperature side was taken as the melting peak temperature _Tpm .
Subsequently, after being kept at 350 ° C. for 3 minutes, it was cooled from 350 ° C. to 50 ° C. at a cooling rate of 20 ° C./min. The exothermic peak appearing at this time was defined as a crystallization peak, the crystallization peak temperature was _defined as T _pc-1 , and the crystallization peak area was defined as a crystallization enthalpy.
Subsequently, after maintaining at 50 ° C. for 3 minutes, the temperature was increased again from 50 ° C. to 350 ° C. at a temperature increase rate of 20 ° C./min. The peak that appeared on the highest temperature side at this time was defined as the melting peak temperature _Tpm-1, and the peak that appeared on the lowest temperature side was defined as the melting peak temperature _Tpm-2 .
Further, after being kept at 350 ° C. for 3 minutes, it was cooled from 350 ° C. to 50 ° C. at a cooling rate of 50 ° C./min. The crystallization peak temperature appearing at this time was _defined as T _pc-2 .
The melting peak temperature T _pm-1 and the melting peak temperature T _pm-2 are shown in Table 2 below.
The difference between the melting peak temperature _Tpm and the melting peak temperature _Tpm-1 was calculated and shown in Table 2 below.
The difference between the melting peak temperature T _pm-1 and the melting peak temperature T _pm-2 was calculated and shown in Table 2 below.
The crystallization peak temperature when cooled at 20 ° C./min is T _pc-1 , and the crystallization peak temperature T _pc-2 when cooled at 50 ° C./min is shown in Table 2 below.
The difference between the crystallization peak temperature T _pc-1 and the crystallization peak temperature T _pc-2 was calculated and is shown in Table 2 below.
The crystallization enthalpies when cooled at 20 ° C./min are shown in Table 2 below.

(4) Glass transition temperature The glass transition temperature of the copolymer polyamide obtained by the manufacture example and the comparative manufacture example was measured as follows using Diamond-DSC by PERKIN-ELMER according to JIS-K7121.
First, the sample was melted on a hot stage (EP80 manufactured by Mettler). The obtained sample in the molten state was quenched with liquid nitrogen and solidified to obtain a measurement sample. Using 10 mg of the measurement sample, the glass transition temperature Tg was measured by raising the temperature in the range of 30 to 350 ° C. under the condition of a temperature elevation rate of 20 ° C./min.
The glass transition temperature Tg is shown in Table 2 below.
Further, the difference between the crystallization peak temperature obtained in the above (3) between T _pc-1 and the glass transition temperature Tg was calculated and shown in Table 2 below.

(5) Sulfuric acid relative viscosity ηr at 25 ° C
The sulfuric acid relative viscosity ηr at 25 ° C. of the copolymerized polyamide obtained in Production Examples and Comparative Production Examples was measured according to JIS-K6920. Specifically, a 1% concentration solution ((polyamide 1 g) / (98% sulfuric acid 100 mL)) was prepared using 98% sulfuric acid, and a temperature of 25 ° C. was obtained using the obtained solution. The sulfuric acid relative viscosity ηr was measured under the conditions.
The values of sulfuric acid relative viscosity ηr at 25 ° C. are shown in Table 2 below.

(6) Amino terminal amount ([NH ₂ ])
In the copolymerized polyamides obtained in Production Examples and Comparative Production Examples, the amount of amino terminals bonded to the polymer terminals was measured by neutralization titration as follows.
3.0 g of polyamide was dissolved in 100 mL of 90% by weight phenol aqueous solution, and the resulting solution was titrated with 0.025N hydrochloric acid, and the amino terminal amount (μ equivalent / g) was determined based on the titration result. The end point was determined from the indicated value of the pH meter.
(7) Carboxyl end amount ([COOH])
In the copolymerized polyamides obtained in Production Examples and Comparative Production Examples, the amount of carboxyl terminal bound to the polymer terminal was measured by neutralization titration as follows.
4.0 g of polyamide was dissolved in 50 mL of benzyl alcohol, and the obtained solution was titrated with 0.1N NaOH, and the carboxyl end amount (μ equivalent / g) was determined based on the titration result. The end point was determined from the discoloration of the phenolphthalein indicator.
([NH ₂ ] / ([NH ₂ ] + [COOH]) was calculated from the values obtained in the above (6) and (7).

(8) Ratio of carbon number to amide group number (carbon number / amide group number)
In the copolymerized polyamides obtained in Production Examples and Comparative Production Examples, the average number of carbon atoms per amide group (carbon number / amide group number) was determined by calculation. Specifically, the ratio of the number of carbons to the number of amide groups (carbon number / number of amide groups) was determined by dividing the number of carbons contained in the molecular main chain by the number of amide groups contained in the molecular main chain. The ratio of the number of carbon atoms to the number of amide groups (carbon number / amide group number) was used as an index indicating the amino group concentration in the copolymerized polyamide.

(9) Biomass plastic degree In the copolymerized polyamide obtained in the production example and the comparative production example, the mass% of the unit composed of the raw material derived from biomass was calculated as the biomass plastic degree.
Specifically, sebacic acid, 1,10-diaminodecane, and 11-aminoundecanoic acid, which use castor oil as a raw material, were used as biomass-derived raw materials.
And in the copolymer polyamide obtained by the manufacture example and the comparative manufacture example, the ratio of the unit derived from sebacic acid or 1,10- diaminodecane was computed, and the said ratio was made into the biomass plasticity.
In the polymerization of polyamide, 2 moles of water molecules are formed from two hydrogen atoms in the diamine, two oxygen atoms in the dicarboxylic acid, and two hydrogen atoms when forming the amide bond. It was calculated taking this into consideration.

(10) Flexural modulus The pellets of the polyamide resin composition obtained in the examples and comparative examples are 4 mm thick according to ISO 3167 using an injection molding machine [PS-40E: manufactured by Nissei Resin Co., Ltd.]. Molded into ISO specimens.
Specific molding conditions were: injection + holding pressure time 25 seconds, cooling time 15 seconds, mold temperature 80 ° C., molten resin temperature, melting of the high temperature side of the copolyamide used in each example and comparative example The peak temperature (T _pm-1 ) was set to + 20 ° C.
Using the obtained test piece, the flexural modulus (Dry flexural modulus) was measured at 23 ° C. according to ISO178.
Further, the flexural modulus at 100 ° C. was measured in the same manner except that the temperature was 100 ° C.
The bending elastic modulus at 100 ° C. is shown in Table 3 below.
Moreover, the 100 degreeC retention was calculated | required using the following formula.
100 ° C. retention rate (%) = 100 ° C. flexural modulus / before water absorption (Dry) flexural modulus × 100
The 100 ° C. retention is shown in Table 3 below.

(11) Flexural modulus after water absorption An ISO test piece having a thickness of 4 mm similar to the test piece used in (10) above was molded, immersed in warm water at 80 ° C. for 24 hours, and then flexural modulus (Wet) according to ISO178. Flexural modulus) was measured.
The wet flexural modulus is shown in Table 3 below.
The wet retention rate was determined using the following formula.
Wet retention (%) = (after water absorption (Wet) flexural modulus / before water absorption (Dry) flexural modulus) × 100
The wet retention rate is shown in Table 3 below.

(12) Evaluation of warpage of molded product The molded product was produced using an injection molding machine.
Using an injection molding machine [PS-40E: made by Nissei Plastics Co., Ltd.], mold temperature is set to Tg + 20 ° C., cylinder temperature = (T _pm-1 +10) ° C. to (T _pm-1 +30) ° C., and cooling is performed. The test piece was fixed at 20 seconds and the injection time was changed (condition 1 (high speed) = 2 seconds, condition 2 (low speed) = 8 seconds) to obtain a test piece of 120 × 80 × 3 mm.
In measuring the warpage of the molded article, the test piece was placed on a horizontal surface, the gate side was fixed to a horizontal plane, and the rising height of the end surface on the opposite side (flow end side) was measured as the amount of warpage. The measurement of the molded product warp was performed on each of the test pieces prepared under the above conditions 1 and 2.
The warp stability was calculated as follows, and the lower the numerical value, the less the molding dependency was evaluated.
Sled stability = [War amount under condition 2 (injection time 8 seconds)]-[War amount under condition 1 (injection time 2 seconds)]
The warpage stability is shown in Tables 3 and 4 below, with values rounded off to one decimal place.

(13) Surface appearance (60 ° gloss)
Flat plate molded pieces were produced from the polyamide resin composition pellets obtained in the examples and comparative examples as follows.
Using an injection molding machine [IS150E: manufactured by Toshiba Machine Co., Ltd.], cooling time is 25 seconds, screw rotation speed is 200 rpm, mold temperature is Tg + 20 ° C., cylinder temperature = (T _pm-1 +10) ° C. to (T _pm-1 +30) ° C., the injection pressure and the injection speed are adjusted as appropriate so that the filling time is in the range of 1.0 ± 0.1 seconds, and the flat plate molded piece (13 cm × 13 cm, 4 mm thick) was produced.
A 60-degree gloss was measured for the central part of the flat plate molded piece thus produced using a gloss meter (IG320 manufactured by HORIBA) in accordance with JIS-K7150.
The larger the measured value, the better the surface appearance.

[Production of copolymerized polyamide]
Hereinafter, production examples of the copolymerized polyamide and comparative production examples will be shown.
In addition, the above measurement items have been implemented and will be described.

(Production Example 1)
The polyamide polymerization reaction was carried out as follows by the “hot melt polymerization method”.
Dicarboxylic acid: CHDA 650 g (3.78 mol), sebacic acid: C10DC85 g (0.42 mol) and diamine: C10DA 720 g (4.18 mol) were dissolved in distilled water 1500 g, and equimolar 50 mass% homogeneous aqueous solution of raw material monomers. Was made.
To this homogeneous aqueous solution, 17 g (0.10 mol) of diamine: C10DA was added.
The aqueous solution thus obtained was charged into an autoclave having an internal volume of 5.4 L (manufactured by Nitto Koatsu) and heated until the liquid temperature (internal temperature) reached 50 ° C., and the interior of the autoclave was purged with nitrogen.
Until the pressure in the autoclave tank (hereinafter also simply referred to as “inside the tank”) is about 2.5 kg / cm ² as gauge pressure (hereinafter, all pressure in the tank is expressed as gauge pressure). The liquid temperature was continuously heated from about 50 ° C. (the liquid temperature in this system was about 145 ° C.). In order to keep the pressure in the tank at about 2.5 kg / cm ² , water was removed from the system while heating was continued until the concentration of the aqueous solution reached about 75% by mass (the liquid temperature in this system was It was about 160 ° C.). The removal of water was stopped, and heating was continued until the pressure in the tank reached about 30 kg / cm ² (the liquid temperature in this system was about 245 ° C.). In order to keep the pressure in the tank at about 30 kg / cm ² , heating was continued until the final temperature (355 ° C. described later) −50 ° C. (here, 305 ° C.) was reached while removing water out of the system. After the liquid temperature rises to the final temperature (355 ° C. described later) −50 ° C. (here, 305 ° C.), the heating continues while the pressure in the tank reaches atmospheric pressure (gauge pressure is 0 kg / cm ² ). The pressure dropped while taking about a minute.

Thereafter, the heater temperature was adjusted so that the final temperature of the resin temperature (liquid temperature) was about 355 ° C. The resin temperature was kept at about 355 ° C., and the inside of the tank was maintained under a reduced pressure of about 53.3 kPa (400 torr) for 30 minutes with a vacuum apparatus to obtain a polyamide copolymer (PA-1). Thereafter, the obtained polyamide copolymer was pressurized with nitrogen to form a strand from the lower nozzle (nozzle), water-cooled, cut, and discharged in a pellet form to obtain a copolymer polyamide pellet. The content of each structural unit in the obtained copolymer polyamide is measured by ¹ H-NMR measurement of the content of diamine and dicarboxylic acid constituting the copolymer polyamide, and it is confirmed that the composition is as prepared. did.
The copolymerized polyamide thus obtained was dried in a nitrogen stream, and the water content was adjusted to about 0.2% by mass. Table 2 below shows the measurement results of the adjusted copolyamide based on the above measurement method.

(Production Examples 2-9, Comparative Production Example 1)
As the dicarboxylic acid, diamine, and caprolactam, the compounds and amounts shown in Table 1 below were used, and the final temperature of the resin temperature was changed to the temperature shown in Table 1 below. Polyamide was polymerized ("hot melt polymerization method").
The content of each structural unit in the obtained copolymer polyamide (PA-2 to PA-9, PA-11) is determined by ¹ H-NMR measurement to determine the content of diamine and dicarboxylic acid constituting the copolymer polyamide. Measurement was made and it was confirmed that the composition was as prepared.
The copolymerized polyamide thus obtained was dried in a nitrogen stream, and the water content was adjusted to about 0.2% by mass. Table 2 below shows the measurement results of the adjusted copolyamide based on the above measurement method.

(Production Example 10)
The polyamide polymerization reaction was carried out as follows by the “hot melt polymerization method”.
Dicarboxylic acid: 620 g (5.33 mol) of ADA and 780 g (5.33 mol) of diamine: C6DA were dissolved in 1500 g of distilled water to prepare an equimolar 50 mass% uniform aqueous solution of raw material monomers.
The aqueous solution thus obtained was charged into an autoclave having an internal volume of 5.4 L (manufactured by Nitto Koatsu) and heated until the liquid temperature (internal temperature) reached 50 ° C., and the interior of the autoclave was purged with nitrogen.
Until the pressure in the autoclave tank (hereinafter also simply referred to as “inside the tank”) is about 2.5 kg / cm ² as gauge pressure (hereinafter, all pressure in the tank is expressed as gauge pressure). The liquid temperature was continuously heated from about 50 ° C. (the liquid temperature in this system was about 145 ° C.). In order to keep the pressure in the tank at about 2.5 kg / cm ² , water was removed from the system while heating was continued until the concentration of the aqueous solution reached about 75% by mass (the liquid temperature in this system was It was about 160 ° C.). The removal of water was stopped, and heating was continued until the pressure in the tank reached about 18 kg / cm ² (the liquid temperature in this system was about 210 ° C.). In order to keep the pressure in the tank at about 18 kg / cm ² , heating was continued until the final temperature (295 ° C. described later) −30 ° C. (265 ° C. here) was reached while water was removed from the system. After the liquid temperature rises to the final temperature (295 ° C. described later) −30 ° C. (265 ° C. in this case), heating continues and the pressure in the tank reaches atmospheric pressure (gauge pressure is 0 kg / cm ² ). The pressure dropped while taking about a minute.
Thereafter, the heater temperature was adjusted so that the final temperature of the resin temperature (liquid temperature) was about 355 ° C. The resin temperature was kept at about 355 ° C., and the inside of the tank was maintained under a reduced pressure of about 53.3 kPa (400 torr) for 30 minutes with a vacuum apparatus to obtain a polyamide copolymer (PA-10). Thereafter, the obtained polyamide copolymer was pressurized with nitrogen to form a strand from the lower nozzle (nozzle), water-cooled, cut, and discharged in a pellet form to obtain a copolymer polyamide pellet. The content of each structural unit in the obtained copolymer polyamide is measured by ¹ H-NMR measurement of the content of diamine and dicarboxylic acid constituting the copolymer polyamide, and it is confirmed that the composition is as prepared. did.
The copolymerized polyamide thus obtained was dried in a nitrogen stream, and the water content was adjusted to about 0.2% by mass. Table 2 below shows the measurement results of the adjusted copolyamide based on the above measurement method.

(Comparative Production Example 2)
Polyamide 9T (hereinafter abbreviated as “PA9T”) was produced with reference to the method described in Example 1 of JP-A-7-228689.
At that time, the terephthalic acid unit was a dicarboxylic acid unit. On the other hand, 1,9-nonamethylenediamine unit and 2-methyloctamethylenediamine unit [1,9-nonamethylenediamine unit: 2-methyloctamethylenediamine unit = 80: 20 (molar ratio)] were used as diamine units.
The raw materials listed in Table 1 below and 1500 g of distilled water were placed in an autoclave (made by Nitto Koatsu Co., Ltd.) having an internal volume of 5.4 L (non-uniform slurry state) and replaced with nitrogen. The mixture was stirred at 100 ° C. for 30 minutes, and the internal temperature was raised to 210 ° C. over 2 hours. At that time, the autoclave was pressurized to 22 kg / cm ² . The reaction was continued for 1 hour, then the temperature was raised to 230 ° C., and then the temperature was kept constant at 230 ° C. for 2 hours. The reaction was carried out while gradually removing water vapor and keeping the pressure at 22 kg / cm ² .
Next, the pressure was reduced to 10 kg / cm ² over 30 minutes, and the reaction was further continued for 1 hour to obtain a prepolymer. This was dried at 100 ° C. under reduced pressure for 12 hours and pulverized to a size of 2 mm or less. This was subjected to solid phase polymerization at 230 ° C. and 0.1 mmHg for 10 hours to obtain PA9T.
The content of each structural unit in the obtained copolymer polyamide (PA-12) is measured by ¹ H-NMR measurement of the content of diamine and dicarboxylic acid constituting the copolymer polyamide, and the composition as prepared. Confirmed that.
The copolymerized polyamide thus obtained was dried in a nitrogen stream, and the water content was adjusted to about 0.2% by mass. Table 2 below shows the measurement results of the adjusted copolyamide based on the above measurement method.

[Production Example of Polyamide Resin Composition]
Example 1
The copolymerized polyamide (PA-1) obtained in Production Example 1 was dried in a nitrogen stream, and the moisture content was adjusted to about 0.2% by mass.
The production example of the polyamide resin composition includes an upstream supply port in the first barrel from the upstream side of the extruder, a side feed port 1 in the ninth barrel, and a side feed port 2 in the seventh barrel. L / D (extruder cylinder length / extruder cylinder diameter) = 48 (barrel number: 12) twin screw extruder [ZSK-26MC: manufactured by Coperion (Germany)] was used. . In the twin-screw extruder, the range from the upstream supply port to the die was set to the melting peak temperature T _pm-1 + 20 ° C. (348 ° C. in Example 1) of the copolymerized polyamide produced by the above production example or comparative production example. . In the twin-screw extruder, the screw rotation speed was 300 rpm and the discharge rate was 25 kg / h.
(A) Copolymer polyamide is supplied to the twin screw extruder from the upstream supply port so that the ratio shown in Table 3 below is obtained, and the resin supplied from the top feed port is sufficiently melted. The glass fiber (B-1) was supplied from the side feed port 1 in a state of being).
From the side feed port 2 on the downstream side of the extruder (the state where the resin supplied from the top feed port is sufficiently melted), the inorganic fillers other than the above (C) :( B) are shown in Table 3 below. It supplied according to the mass part. The melt-kneaded product extruded from the spinning nozzle was cooled in a strand shape and pelletized to obtain a pellet-like polyamide resin composition.
According to the method described above, the above-described bending elastic moduli (water absorption rigidity (Wet bending elastic modulus) and thermal rigidity (100 ° C. bending elastic modulus)), moldability (molded product warp (warp stability), and surface (Appearance) was evaluated.
The evaluation results are shown in Table 3 below.

(Example 2 , Reference Example 3, Examples 4-14, Comparative Examples 1-3)
A polyamide resin composition pellet was produced in the same manner as in Example 1 except that the ratio of each raw material composition was as shown in Table 3 or 4 below.
Each of the obtained polyamide resin composition pellets was subjected to the above-described methods by using the above-described bending elastic modulus (water absorption rigidity and heat rigidity), moldability (molded product warp (slave stability), and surface appearance).
Was evaluated.
The evaluation results are shown in Table 3 or 4 below.

(Comparative Example 4)
The copolymerized polyamide (PA-4) obtained in Production Example 4 was dried in a nitrogen stream, and the water content was adjusted to about 0.2% by mass.
In the production example of the polyamide resin composition, an L / D (extruder cylinder) has an upstream supply port in the first barrel from the upstream side of the extruder and a side feed port 1 in the ninth barrel. A twin screw extruder [ZSK-26MC: manufactured by Coperion (Germany)] of length / cylinder diameter of extruder = 48 (number of barrels: 12) was used. In the twin-screw extruder, the range from the upstream supply port to the die was set to the melting peak temperature T _pm-1 + 20 ° C. of the copolymerized polyamide produced by the above production example or comparative production example. In the twin-screw extruder, the screw rotation speed was 300 rpm and the discharge rate was 25 kg / h.
(A) Copolymer polyamide is supplied to the twin screw extruder from the upstream supply port so that the ratio shown in Table 3 below is obtained, and the resin supplied from the top feed port is sufficiently melted. (B1) glass fiber was supplied from the side feed port 1 in a state of being).
The melt-kneaded product extruded from the spinning nozzle was cooled in a strand shape and pelletized to obtain a pellet-like polyamide resin composition.
By the above-described methods, the above-described bending elastic moduli (water-absorbing rigidity and thermal rigidity) and moldability (molded product warp (warp stability) and appearance) were evaluated.
The evaluation results are shown in Table 4 below.

  From the results of Table 3, it was confirmed that Examples 1 to 14 all had excellent water absorption rigidity and hot rigidity without impairing the molding appearance, and little dependence on the molding conditions of the molded product warp. .

  According to the present invention, the polyamide has excellent rigidity after water absorption (water absorption rigidity), rigidity under high temperature use (rigidity during heat), good moldability, little dependence on molding conditions such as warping, and excellent appearance. A resin composition is obtained. The polyamide resin composition according to the present invention can be suitably used as a molding material for various parts such as automobiles, electric and electronic, industrial materials, industrial materials, and daily and household products. With the above applicability.

Claims (17)

(A): (a) a unit comprising an alicyclic dicarboxylic acid;
(B) a unit comprising a diamine having 10 or more carbon atoms;
(C) a unit comprising at least one copolymer component selected from the group consisting of the following (c-1) to (c-3);
(C-1) Dicarboxylic acids other than the (a) alicyclic dicarboxylic acid.
(C-2) A diamine having fewer carbon atoms than the diamine (b).
(C-3) Lactam and / or aminocarboxylic acid.
Containing,
And a copolyamide satisfying the following conditions (1) to (3):
(1) In differential scanning calorimetry according to JIS-K7121, the difference between the crystallization peak temperature T _pc-1 obtained when cooled at 20 ° C./min and the glass transition temperature T _g (T _pc-1 − T _g )
However, it is 140 degreeC or more.
(2) The ratio of carbon number to amide group number (carbon number / amide group number) is 8 or more.
(3) In differential scanning calorimetry according to JIS-K7121, the melting peak temperature T _pm obtained when the temperature is raised at 20 ° C./min and the melting peak temperature obtained when the temperature is raised again at 20 ° C./min The difference from T _pm-1 (T _pm -T _pm-1 ) is 30 ° C. or less.
(B): glass fiber;
(C): inorganic filler other than glass fiber (B) (excluding titanium oxide),
Containing,
(B): Glass fiber 1 to 100 parts by weight of (A): polyamide copolymer
Polyamide resin composition (however, containing titanium oxide ) containing 300 parts by weight, (C): 1 to 200 parts by weight of an inorganic filler other than glass fiber (B) (excluding titanium oxide) Except.) (C): An inorganic filler other than glass fiber (B) (excluding titanium oxide),
The polyamide according to claim 1, which is at least one inorganic filler selected from the group consisting of wollastonite, kaolin, mica, talc, calcium carbonate, magnesium carbonate, potassium titanate fiber, aluminum borate fiber, and clay. Resin composition. Said (C): The polyamide resin composition of Claim 1 or 2 whose average particle diameter of inorganic fillers (however, except a titanium oxide) other than glass fiber (B) is 0.01-38 micrometers. The polyamide resin composition according to any one of claims 1 to 3, wherein the (a) alicyclic dicarboxylic acid is 1,4-cyclohexanedicarboxylic acid. The trans isomer ratio in the unit consisting of (a) alicyclic dicarboxylic acid is 65-80.
The polyamide resin composition according to any one of claims 1 to 4, which is mol%. The ratio of the amino terminal amount to the total amount of amino terminal amount and carboxyl terminal amount {amino terminal amount / (amino terminal amount + carboxyl terminal amount)} is 0.0 or more and less than 0.5.
The polyamide resin composition as described in any one of thru | or 5. The polyamide resin composition according to any one of claims 1 to 6, wherein the (b) diamine having 10 or more carbon atoms is decamethylenediamine. The polyamide resin composition according to any one of claims 1 to 7, wherein the (c-1) dicarboxylic acid other than the (a) alicyclic dicarboxylic acid is an aliphatic dicarboxylic acid having 10 or more carbon atoms. . The polyamide resin composition according to claim 1, wherein the (c-1) dicarboxylic acid other than the (a) alicyclic dicarboxylic acid is sebacic acid and / or dodecanedioic acid. The polyamide resin composition according to claim 1, wherein the (c-1) dicarboxylic acid other than the (a) alicyclic dicarboxylic acid is isophthalic acid. The polyamide resin composition according to any one of claims 1 to 10, wherein the (c-2) diamine having a carbon number smaller than that of the diamine (b) is an aliphatic diamine having 4 to 7 carbon atoms. In differential scanning calorimetry according to JIS-K7121, the crystallization peak temperature T _pc-1 obtained when cooled at 20 ° C./min and the crystallization peak temperature T obtained when cooled again at 50 ° C./min. The polyamide resin composition according to any one of claims 1 to 11, wherein a difference from _pc-2 (T _pc-1 -T _pc-2 ) is 10 ° C or less. The total content of all the structural units of the copolymerized polyamide (A) is 100 mol%,
c) The content of the unit consisting of at least one copolymer component selected from the group consisting of (c-1) to (c-3) above is 5.0 mol% or more and 22.5 mol% or less. Claims 1 to 12
Polyamide resin composition as described in any one of these. The polyamide resin composition according to any one of claims 1 to 13, wherein the degree of biomass plasticity of the copolymerized polyamide (A) is 25% or more. 15. The composition according to claim 1, further comprising at least one component selected from the group consisting of an inorganic filler, a nucleating agent, a lubricant, a stabilizer, and a polymer other than the copolymerized polyamide (A). The polyamide resin composition according to item. A molded article comprising the (A) polyamide copolymer or the polyamide resin composition according to any one of claims 1 to 15. The automotive part, the electronic part, the household appliance part, the OA equipment part or the portable equipment part.
Articles described in 1.