JP2015129244A - Slide part - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a slide part that is excellent in low water absorption, tensile strength, slidability and surface appearance.SOLUTION: A slide part comprises: (A) polyamide comprising (a) one dicarboxylic acid and (b) a unit comprising one diamine and satisfying the following conditions (1), (2): (1) Tg is 70°C or more and (2) Mn (number average molecular weight) is 15000 or more; and (B) inorganic filler.

Description

  The present invention relates to sliding parts such as gears and fastener sliders.

Polyamides typified by polyamide 6 and polyamide 66 (hereinafter sometimes abbreviated as “PA6” and “PA66” respectively) and the like are excellent in molding processability, mechanical properties, and chemical resistance. Polyamide is widely used as various parts materials for automobiles, electric and electronic, industrial materials, industrial materials, daily use and household goods.
Above all, conventional sliding parts such as gears, bearings, bearing retainers, bushes, spacers, rollers, and cams are used without problems under relatively low load, low speed friction and wear conditions. As the friction and wear conditions become higher, the friction and wear become easier, and the temperature rises due to frictional heat. I can't continue.
As various parts such as daily necessities and household items, slide fasteners can be used to open and close items used not only in daily necessities such as clothing, bags, shoes and sundries, but also in industrial items such as water tanks, fishing nets and space suits. It is a tool.
Among the components of the slide fastener, the element rod, slider, top and bottom stops, and hearing tool are generally molded parts manufactured by injection molding, and it is known that polyamide can be used as a material.
For example, in Patent Document 1, a polyamide reinforced with glass fiber is used as a material for the purpose of improving durability of a slider used for a slide fastener for bedding, durability against an iron, and wear resistance against sliding of the slider. A method for injection molding a slider is described. Further, it is described that polyamide 66 is used as the polyamide. Patent Document 2 is a composition comprising a polyamide having a specific weight molecular weight and reinforcing fibers, and 50% by mass or more of the polyamide is an aliphatic polyamide. Molded parts for slide fasteners made of these materials have been proposed.

DE 3444813 International Publication No. 2013/098978 Pamphlet

The molded parts for slide fasteners are required to have high strength that can withstand practical use. Particularly in a polyamide having high water absorption, there is a problem that strength is reduced due to water absorption and cracking occurs due to long-term use.
In addition, high heat resistance against washing and iron and sliding characteristics with respect to sliding of the slider are required. Friction / wear tends to wear as high-speed friction / wear conditions are reached, and due to the temperature rise due to frictional heat, melting occurs when a certain limit is exceeded, and at the same time, significant wear occurs, and steady frictional motion continues. There are problems such as disappearance.
On the other hand, when manufacturing molded parts for slide fasteners, such as sliders, using polyamide resin as a material, the design properties are lacking as they are. Therefore, the design of the slide fastener itself is dyed and the surface is painted or metal-plated. It is often required to increase Therefore, in order to improve the designability, a molded product having an excellent surface appearance is required.

In response to the above requirements, the polyamide compositions disclosed in Patent Document 1 and Patent Document 2 are not sufficiently satisfied with respect to heat resistance, low water absorption, tensile strength, slidability, and surfaces outside the surface. Patent Document 2 also discloses PA in which an aromatic monomer is introduced at a high ratio in polyamide for the purpose of imparting heat resistance and low water absorption. When the molecular weight is increased for the purpose of improving long-term characteristics such as slidability, a polyamide having a high weight average molecular weight (Mw) can be obtained. However, when a polyamide having a high ratio of aromatic monomers is made to have a high molecular weight, the number average molecular weight (Mn) is not increased, and the ratio of polyamide molecules having a high Mw / Mn ratio (that is, polyamide molecules having a three-dimensional structure) is extremely high. Therefore, it is difficult to increase the molecular weight while maintaining good fluidity. Therefore, sufficient performance cannot be exhibited in terms of long-term characteristics such as slidability and surface appearance.
Moreover, in order to suppress the three-dimensional structure, the polyamide as described above needs to increase the end-capping rate with the end-capping agent, which causes a decrease in affinity with the inorganic filler. If the affinity between the polyamide and the sliding material or other inorganic filler is low, the inorganic filler may fall off on the sliding surface and cause wear. In addition, when producing pellets using a twin screw extruder, the strand stability (productivity) is reduced, and fillers that cannot be dispersed well in the polyamide resin are generated as fluffs, reducing the quality of the pellets. Problems may occur.

Moreover, in practical use, since the polyamide having the three-dimensional structure remains continuously produced, the polyamide having the three-dimensional structure is gelled, causing black spots, and the quality is significantly reduced. have.
Furthermore, when polyamide pellets with a high proportion of polyamide molecules having a three-dimensional structure obtained by polymerization are processed at a high temperature with an extruder or molding machine, the three-dimensional structure of the polyamide molecules further advances and the flow characteristics are not stable. have.
The problem to be solved by the present invention is to provide a sliding component excellent in heat resistance, low water absorption, tensile strength, slidability and surface appearance.

  As a result of intensive studies to solve the above problems, the inventors of the present invention contain a unit composed of a dicarboxylic acid and a diamine, and satisfy the specific requirements in terms of Tg and Mn (number average molecular weight). The present inventors have found that a sliding component containing a filler can solve the above-mentioned problems and have completed the present invention.

That is, the present invention is as follows.
[1]
(A) (a) a unit comprising one kind of dicarboxylic acid, and (b) a unit comprising one kind of diamine, and a polyamide satisfying the following conditions (1) and (2):
(1) Tg is 70 ° C. or higher (2) Mn (number average molecular weight) is 15000 or higher (B) an inorganic filler;
A sliding part containing
[2]
The sliding component according to [1], wherein the (B) inorganic filler is at least one selected from the group consisting of glass fiber, carbon fiber, and aramid fiber.
[3]
The sliding component according to the above [1] or [2], which contains 50 to 70% by mass of the (B) inorganic filler.
[4]
The sliding component according to any one of [1] to [3], wherein the polyamide (A) satisfies the following conditions (1) and (2).
(1) Sulfuric acid relative viscosity ηr at 25 ° C. is 2.3 or more (2) Mw (weight average molecular weight) / Mn (number average molecular weight) is 4.0 or less [5]
(A) (a) including one kind of dicarboxylic acid, (b) a polyamide containing a unit composed of one kind of diamine, and (B) an inorganic filler, and the following conditions (1) and (2) And a sliding part that satisfies (3).
(1) Tg is 90 ° C. or more (2) Number average molecular weight is 15000 or more (3) Mw (weight average molecular weight) / Mn (number average molecular weight) is 4.0 or less [6]
(A) The sliding component according to any one of [1] to [5], wherein the one kind of dicarboxylic acid is 1,4-cyclohexanedicarboxylic acid.
[7]
The polyamide (A) has a ratio (η * 1 / η * 100) of a shear viscosity (η * 1) at an angular velocity of 1 rad / s to a shear viscosity (η * 100) at an angular velocity of 100 rad / s is 3 or less. The sliding component according to any one of [1] to [6].
[8]
[1] to [1], wherein (A) the polyamide further contains (c) a unit composed of at least one copolymer component selected from the group consisting of the following (c-1) to (c-3): [7] The sliding part according to any one of [7].
(C-1) Dicarboxylic acid other than (a) dicarboxylic acid (c-2) Diamine other than (b) whose carbon number is less than or equal to that of (b) diamine (c-3) Lactam and / or Aminocarboxylic acid [9]
In the 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 ) The sliding component according to any one of [1] to [8], wherein is 140 ° C. or higher.
[10]
The sliding component according to any one of [1] to [9], wherein (b) the diamine is a diamine having 8 or more carbon atoms.
[11]
The sliding component according to any one of [1] to [10], wherein the (b) diamine is decamethylenediamine.
[12]
[C-2] The diamine other than (b) having a carbon number equal to or less than that of the diamine of (b) is at least one selected from the group consisting of diamines having an even number of carbon atoms [8 ] To [11] The sliding component according to any one of [11].
[13]
(C-2) The diamine other than (b) having a carbon number equal to or less than that of the diamine (b) is at least selected from the group consisting of 1,6-hexamethylenediamine and 2-methylpentamethylenediamine. The sliding component according to any one of [8] to [12], which is a kind.
[14]
The sliding component according to any one of [1] to [13], wherein the sealing amount of the polyamide (A) is 50% or less.
[15]
The sliding component according to any one of [1] to [14], wherein the (B) inorganic filler has a number average fiber diameter of 3 to 9 μm.
[16]
The sliding component according to any one of [1] to [15], wherein a ratio of carbon number to amide group (carbon number / amide group number) is 8 or more.
[17]
In differential scanning calorimetry according to JIS-K7121, after measuring the crystallization peak temperature T _pc-1 obtained by cooling at 20 ° C./min and the crystallization peak temperature T _pc-1 , 50 ° C./min Any one of [1] to [16] above, wherein the difference (T _pc-1 -T _pc-2 ) from the crystallization peak temperature T _pc-2 obtained when cooled again at 10 ° C. is 10 ° C. or less. Sliding parts as described in
[18]
Any of [8] to [17], wherein the content of the copolymer component (c) is 7.5 mol% or more and 20.0 mol% or less with respect to 100 mol% of the total component amount of the polyamide. The sliding part according to one item.
[19]
The sliding component according to any one of [1] to [18], wherein the polyamide is a polyamide obtained through a solid phase polymerization step in at least a part of the polymerization step.
[20]
The sliding component according to any one of [1] to [19], wherein the biomass plasticity is 25% or more.
[21]
Furthermore, the sliding material, the nucleating agent, the lubricant, the stabilizer, and at least one component selected from the group consisting of polymers other than the polyamide described in any one of the above [1] to [20] Sliding parts.
[22]
The sliding component according to any one of [1] to [21], wherein at least a part of the surface is dyed, painted, or metal-plated.

  According to the present invention, it is possible to provide a sliding component having excellent heat resistance, low water absorption, tensile strength, slidability, and surface appearance.

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.
The sliding component of this embodiment is
(A) (a) a polyamide containing one unit of a dicarboxylic acid and (b) one type of diamine, and satisfying the following conditions (1) and (2):
(1) Tg is 70 ° C. or higher (2) Mn (number average molecular weight) is 15000 or higher (B) Inorganic filler.
(A), (B), (C), which will be described later, and additional components such as a sliding material, a nucleating agent, a lubricant, a stabilizer, and a polymer other than the polyamide, which constitute the sliding component of this embodiment. The composition containing the composition may be referred to as a polyamide composition (hereinafter also simply referred to as “composition”).

[(A) Polyamide]
The polyamide of this embodiment is
(A) a unit composed of one kind of dicarboxylic acid;
(B) a unit composed of one kind of diamine;
And satisfies the following conditions (1) and (2).
(1) Tg is 70 ° C. or higher (2) Mn (number average molecular weight) is 15000 or higher

In the present embodiment, polyamide means a polymer having an amide (—NHCO—) bond in the main chain.
In the present embodiment, the dicarboxylic acid is not limited to the dicarboxylic acid itself, 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 has a dicarboxylic acid structure derived from dicarboxylic acid and can be a dicarboxylic acid structure. Examples include dicarboxylic acid anhydrides and halides.
Hereinafter, the components (a) and (b) will be described in detail.

((A) dicarboxylic acid)
The polyamide of this embodiment contains (a) a unit composed of one kind of dicarboxylic acid.
(A) One kind of dicarboxylic acid used in the present embodiment is not limited to the following, and examples thereof include alicyclic dicarboxylic acids (also referred to as alicyclic dicarboxylic acids) and aliphatic dicarboxylic acids. And aromatic dicarboxylic acid. The dicarboxylic acid used in the present embodiment is preferably an alicyclic dicarboxylic acid or an aromatic dicarboxylic acid in terms of heat resistance, fluidity, toughness, low water absorption, strength, rigidity, slidability, surface appearance, and the like. Yes, more preferably alicyclic dicarboxylic acid.
Examples of the aliphatic dicarboxylic acid include, but are not limited to, for example, alicyclic dicarboxylic acids having 3 to 10 carbon atoms in the alicyclic structure, preferably 5 to 10 carbon atoms in the alicyclic structure. The alicyclic dicarboxylic acid which is is mentioned. Examples of the alicyclic dicarboxylic acid include, but are not limited to, 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,3-cyclopentanedicarboxylic acid, and the like.

The alicyclic dicarboxylic acid used in the present embodiment may be unsubstituted or may have a substituent.
Examples of the substituent include, but are not limited to, for example, a carbon number of 1 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. -4 alkyl groups and the like.
As the alicyclic dicarboxylic acid used in the present embodiment, 1,4-cyclohexanedicarboxylic acid is preferable from the viewpoints of heat resistance, low water absorption, tensile strength, surface appearance, slidability, and the like of the polyamide of the present embodiment.

An alicyclic dicarboxylic acid has a trans isomer and a cis geometric 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.
The alicyclic dicarboxylic acid is isomerized at a high temperature to have a certain ratio, and the cis isomer has higher water solubility of the equivalent salt with the diamine than the trans isomer. In the alicyclic dicarboxylic acid, the trans isomer / cis isomer ratio is preferably 50/50 to 0/100, more preferably 40/60 to 10/90, and still more preferably 35 / 65-15 / 85.

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 can be determined by ¹ H-NMR.
Examples of the aliphatic dicarboxylic acid include, but are not limited to, malonic acid, dimethylmalonic acid, succinic acid, 2,2-dimethylsuccinic acid, 2,3-dimethylglutaric acid, 2,2- Diethylsuccinic 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, dodecanedi Examples thereof include linear or branched aliphatic dicarboxylic acids having 3 to 20 carbon atoms such as acid, tetradecanedioic acid, hexadecanedioic acid, octadecanedioic acid, eicosanedioic acid, and diglycolic acid.

The aliphatic dicarboxylic acid used in the present embodiment is preferably an aliphatic dicarboxylic acid having 6 or more carbon atoms, more preferably carbon, from the viewpoint of heat resistance, fluidity, toughness, low water absorption, strength, rigidity, and the like. It is an aliphatic dicarboxylic acid of several tens or more.
Examples of the aliphatic dicarboxylic acid having 10 or more carbon atoms include, but are not limited to, for example, sebacic acid, dodecanedioic acid, tetradecanedioic acid, hexadecanedioic acid, octadecanedioic acid, and eicosanedioic acid. Can be mentioned. Among these, as the aliphatic dicarboxylic acid having 10 or more carbon atoms, sebacic acid and / or dodecanedioic acid are preferable from the viewpoint of heat resistance and the like.
Examples of the aromatic dicarboxylic acid include, but are not limited to, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, 5-methylisophthalic acid, and 5 -An aromatic dicarboxylic acid having 8 to 20 carbon atoms which is unsubstituted or substituted with various substituents such as sodium sulfoisophthalic acid.

Examples of the various substituents include, but are not limited to, for example, an alkyl group having 1 to 4 carbon atoms, an aryl group having 6 to 10 carbon atoms, an arylalkyl group having 7 to 10 carbon atoms, and a chloro group. And a halogen group such as a bromo group, a silyl group having 1 to 6 carbon atoms, and a sulfonic acid group and a salt thereof such as a sodium salt.
The aromatic dicarboxylic acid is preferably terephthalic acid or isophthalic acid, more preferably terephthalic acid, from the viewpoints of heat resistance, fluidity, toughness, low water absorption, strength and rigidity.

((B) Diamine)
The polyamide of this embodiment contains the unit which consists of (b) diamine. (B) Diamine (in this specification, (b) component, (b) diamine, may be described as (b)) in this embodiment is not particularly limited as long as it is a diamine. Even in the substituted linear aliphatic diamine, for example, 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 having a substituent, an alicyclic diamine, or an aromatic diamine.
The number of carbon atoms in the (b) diamine used in this embodiment is preferably 8 or more from the viewpoint of low water absorption (reducing water absorption), and 20 or less, that is, 8 to 20 from the viewpoint of increasing the high temperature strength and melting point. It is preferable that it is, it is more preferable that it is 8-15, and it is further more preferable that it is 8-12.

  The (b) aliphatic diamine used in the present embodiment is not limited to the following, but for example, ethylene diamine, propylene diamine, tetramethylene diamine, pentamethylene diamine, hexamethylene diamine, heptamethylene diamine, octamethylene diamine. Linear aliphatic diamines such as nonamethylenediamine, decamethylenediamine, undecamethylenediamine, dodecamethylenediamine, and tridecamethylenediamine, 2-methylpentamethylenediamine, 2,2,4-trimethylhexamethylenediamine, Examples thereof include branched aliphatic diamines such as 2,4,4-trimethylhexamethylenediamine, 2-methyloctamethylenediamine, and 2,4-dimethyloctamethylenediamine.

  As the (b) aliphatic diamine used in the present embodiment, octamethylene diamine, 2-methyloctamethylene diamine, nonamethylene diamine, decamethylene diamine, and undeca are used from the viewpoints of heat resistance, low water absorption, strength, rigidity, and the like. Preferred are methylene diamine and dodecamethylene diamine, more preferred are 2-methyloctamethylene diamine, nonamethylene diamine, decamethylene diamine, undecamethylene diamine, and dodecamethylene diamine, and still more preferred are decamethylene diamine and dodecamethylene diamine. And even more preferably decamethylenediamine.

As the decamethylenediamine, 1,10-decamethylenediamine having a linear decane skeleton having an amino group at the 1,10-position is preferable from the viewpoint of enhancing crystallinity.
1,10-decamethylenediamine is also preferable from the viewpoint of being a biomass-derived raw material.
As 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-C1 such as a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, and tert-butyl group. 4 alkyl groups.

Examples of the alicyclic diamine (also referred to as alicyclic diamine) include, but are not limited to, for example, 1,4-cyclohexanediamine, 1,3-cyclohexanediamine, and 1,3-cyclohexane. And cyclopentanediamine.
The aromatic diamine is a diamine containing an aromatic, and is not limited to the following, and examples thereof include metaxylylenediamine, orthoxylylenediamine, paraxylylenediamine, and the like.
In the present embodiment, when two or more kinds of diamines are combined, the diamine having the largest number of carbon atoms is the component (b), and the other diamines are the component (c-2) described later.

((C) copolymerization component)
In addition to the above-mentioned (a) and (b), the polyamide of this embodiment is a predetermined (c) copolymerization component (in this specification, (c) component, ( c) may also be included)).
The (c) copolymerization component is (c-1) a dicarboxylic acid other than the above (a) (may be referred to as (c-1) component or (c-1) in this specification), (C-2) A diamine other than the above (b) having a carbon number equal to or less than that of the diamine (b) (in this specification, (c-2) component, may be described as (c-2)). ), And (c-3) at least one selected from the group consisting of lactams and / or aminocarboxylic acids (in this specification, (c-3) component, may be described as (c-3)). It is a seed.

(A) The (c) copolymerization component combined with the dicarboxylic acid and the diamine of (b) may be used alone or in combination of two or more.
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).

<(C-1) Dicarboxylic acid other than (a) dicarboxylic acid>
(C-1) The dicarboxylic acid other than the (a) dicarboxylic acid is not limited to the following, and examples thereof include alicyclic dicarboxylic acids, aliphatic dicarboxylic acids, and aromatic dicarboxylic acids.
The alicyclic dicarboxylic acid is not limited to the following. For example, the alicyclic dicarboxylic acid having 3 to 10 carbon atoms in the alicyclic structure, preferably 5 to 5 carbon atoms in the alicyclic structure. Alicyclic dicarboxylic acid which is 10. Examples of the alicyclic dicarboxylic acid include, but are not limited to, 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,3-cyclopentanedicarboxylic acid, and the like.

The alicyclic dicarboxylic acid may be unsubstituted or may have a substituent. Examples of the substituent include, but are not limited to, for example, a carbon number of 1 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. -4 alkyl groups and the like.
Examples of the aliphatic dicarboxylic acid include, but are not limited to, malonic acid, dimethylmalonic acid, succinic acid, 2,2-dimethylsuccinic acid, 2,3-dimethylglutaric acid, 2,2- Diethylsuccinic 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, dodecanedi Examples thereof include linear or branched aliphatic dicarboxylic acids having 3 to 20 carbon atoms such as acid, tetradecanedioic acid, hexadecanedioic acid, octadecanedioic acid, eicosanedioic acid, and diglycolic acid.

Examples of the aromatic dicarboxylic acid include, but are not limited to, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, 5-methylisophthalic acid, and 5 -An aromatic dicarboxylic acid having 8 to 20 carbon atoms which is unsubstituted or substituted with various substituents such as sodium sulfoisophthalic acid.
Examples of the various substituents include, but are not limited to, for example, an alkyl group having 1 to 4 carbon atoms, an aryl group having 6 to 10 carbon atoms, an arylalkyl group having 7 to 10 carbon atoms, and a chloro group. And a halogen group such as a bromo group, a silyl group having 1 to 6 carbon atoms, and a sulfonic acid group and a salt thereof such as a sodium salt.

(C-1) The dicarboxylic acid other than the (a) dicarboxylic acid used in the present embodiment is preferably an aliphatic dicarboxylic acid in terms of heat resistance, fluidity, toughness, low water absorption, strength, rigidity, and the like. Yes, more preferably an aliphatic dicarboxylic acid having 6 or more carbon atoms.
Among these, (c-1) the dicarboxylic acid other than the (a) dicarboxylic acid is preferably an aliphatic dicarboxylic acid having 10 or more carbon atoms from the viewpoint of heat resistance and low water absorption.

Examples of the aliphatic dicarboxylic acid having 10 or more carbon atoms include, but are not limited to, for example, sebacic acid, dodecanedioic acid, tetradecanedioic acid, hexadecanedioic acid, octadecanedioic acid, and eicosanedioic acid. Can be mentioned.
Among these, as the (c-1) dicarboxylic acid other than the (a) dicarboxylic acid, sebacic acid and / or dodecanedioic acid are preferable from the viewpoint of heat resistance and the like.
(C-1) The dicarboxylic acid other than the (a) dicarboxylic acid used in the present embodiment is preferably an aromatic dicarboxylic acid from the viewpoints of heat resistance, fluidity, toughness, low water absorption, strength, rigidity, and the like. Yes, more preferred is an aromatic dicarboxylic acid having 8 carbon atoms.
Among them, (c-1) As the dicarboxylic acid other than the (a) dicarboxylic acid, isophthalic acid is preferable from the viewpoint of heat resistance, fluidity, surface appearance, and the like.

Furthermore, (c-1) a dicarboxylic acid other than the (a) dicarboxylic acid is a trivalent or higher polyvalent carboxylic acid such as trimellitic acid, trimesic acid, and pyromellitic acid as long as the object of the present embodiment is not impaired. An acid may be included.
As said polyvalent carboxylic acid, only 1 type may be used independently and may be used in combination of 2 or more type.

The proportion (mol%) of (a) dicarboxylic acid in (a) dicarboxylic acid and (c-1) dicarboxylic acid other than (a) dicarboxylic acid is not particularly limited, but is 50 to 100 mol%. Is more preferable, it is 60-100 mol%, More preferably, it is 70-100 mol%.
When the proportion of the (a) dicarboxylic acid in the total amount of (a) and (c-1) is 50 to 100 mol%, strength, high-temperature strength, low water absorption, low blocking property, releasability And a polyamide having excellent plasticization time stability is obtained. Moreover, the sliding component containing the said polyamide is excellent in slidability and surface appearance.

<(C-2) Diamines other than the above (b) whose carbon number is equal to or less than the carbon number of the diamine (b)>
(C-2) The diamine other than the above (b) having a carbon number equal to or less than the carbon number of the diamine (b) is not limited to the following, but includes, for example, an aliphatic diamine, an alicyclic diamine, and the like. An aromatic diamine etc. are mentioned.
Examples of the aliphatic diamine include, but are not limited to, ethylenediamine, propylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decamethylene. Linear aliphatic diamines such as diamine, undecamethylenediamine, dodecamemethylenediamine, and tridecamethylenediamine, 2-methylpentamethylenediamine, 2,2,4-trimethylhexamethylenediamine, 2,4,4-trimethyl Examples include branched aliphatic diamines such as hexamethylenediamine, 2-methyloctamethylenediamine, and 2,4-dimethyloctamethylenediamine.

Examples of the alicyclic diamine (also referred to as alicyclic diamine) include, but are not limited to, for example, 1,4-cyclohexanediamine, 1,3-cyclohexanediamine, and 1,3-cyclohexane. And cyclopentanediamine.
The aromatic diamine is a diamine containing an aromatic, and is not limited to the following, and examples thereof include metaxylylenediamine, orthoxylylenediamine, paraxylylenediamine, and the like.

  (C-2) The diamine other than the above (b) having a carbon number equal to or less than the carbon number of the diamine (b) used in the present embodiment is the heat resistance, fluidity, toughness, and low water absorption of the polyamide of the present embodiment. From the viewpoints of properties, strength, rigidity, etc., preferably an aliphatic diamine and an alicyclic diamine, more preferably an aliphatic diamine having 4 to 9 carbon atoms, still more preferably 4, 6 or 6 carbon atoms. 8 aliphatic diamines, and more preferably 1,6-hexamethylenediamine and 2-methylpentamethylenediamine.

Furthermore, (c-2) a diamine other than the above (b) having a carbon number equal to or less than the carbon number of the diamine of the above (b) is a trivalent or higher valence such as bishexamethylenetriamine within a range not impairing the object of the present embodiment. The polyvalent aliphatic amine may be included.
One kind of the polyvalent aliphatic amine may be used alone, or two or more kinds may be used in combination.

  There are no particular restrictions on the proportion (mol%) of (b) diamine in the diamine other than (b) having (b) diamine and (c-2) carbon number equal to or less than that of (b) diamine. , 40-100 mol% is preferable, More preferably, it is 50-100 mol%, More preferably, it is 60-100 mol%. (B) The ratio of diamine is 40 to 100 mol% of the total amount of (b) and (c-2), so that strength, high temperature strength, low water absorption, low blocking property, releasability and plasticization are achieved. The polyamide can be made more excellent in time stability. Moreover, the sliding component containing the polyamide is excellent in heat resistance, low water absorption, tensile strength, surface appearance, and sliding property.

<(C-3) Lactam and / or aminocarboxylic acid>
(C-3) A lactam and / or aminocarboxylic acid means a lactam and / or aminocarboxylic acid that can be combined (condensed).
When the polyamide of the present embodiment is a copolymerized polyamide obtained by copolymerizing (a) dicarboxylic acid, (b) diamine, and (c-3) lactam and / or aminocarboxylic acid, (c- 3) The lactam and / or aminocarboxylic acid is preferably a lactam and / or aminocarboxylic acid having 4 to 14 carbon atoms from the viewpoint of fluidity and toughness, and is a lactam and / or aminocarboxylic acid having 6 to 12 carbon atoms. More preferably.

Examples of the lactam include, but are not limited to, butyrolactam, pivalolactam, ε-caprolactam, caprilactam, enantolactam, undecanolactam, laurolactam (dodecanolactam), and the like.
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.

Examples of the aminocarboxylic acid include, but are not limited to, ω-aminocarboxylic acid and α, ω-amino acid that 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 examples thereof include 6-aminocaproic acid and 11-aminoundecanoic acid. And 12-aminododecanoic acid and the like, and examples of the aminocarboxylic acid include paraaminomethylbenzoic acid and the like.
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.

  (C-3) The addition amount (mol%) of lactam and / or aminocarboxylic acid is not particularly limited, but (a) dicarboxylic acid, (b) diamine, and (c-3) lactam and It is preferably 0.5 mol% or more and 20 mol% or less, more preferably 2 mol% or more and 18 mol% or less, with respect to the molar amount (100 mol%) of the whole monomer of aminocarboxylic acid. (C-3) When the addition amount of lactam and / or aminocarboxylic acid is 0.5 mol% or more and 20 mol% or less, the polyamide is excellent in heat resistance, low water absorption, strength, releasability and the like. be able to.

(Content ratio of components (a) to (c))
In the polyamide of this embodiment, the content ratio of (a) dicarboxylic acid and (b) diamine is preferably the same molar amount. Therefore, it is preferable that the amount of dicarboxylic acid used and the amount of diamine used as raw materials for obtaining the polyamide of the present embodiment is 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) The content of the copolymer component is preferably 5.0 mol% or more and 22.5 mol% or less, more preferably 7.5 mol% or more and 20 mol% or less with respect to 100 mol% of the total component amount of the polyamide. It is 0.0 mol% or less, More preferably, it is 10.0 mol% or more and 18.0 mol% or less. (C) By making the content rate of a copolymerization component into the said range, the polyamide excellent in tensile strength, high temperature strength, low water absorption, low blocking property, mold release property, and plasticization time stability is obtained. Moreover, the sliding component containing this polyamide is excellent in heat resistance, tensile strength, surface appearance, and sliding property.

(End sealant)
When polymerizing the polyamide of this embodiment, in addition to the components (a) to (c), a known end-capping agent can be further added for molecular weight adjustment.
Examples of the end capping agent include, but are not limited to, acid anhydrides such as monocarboxylic acid, monoamine, and phthalic anhydride; monoisocyanates, monoacid halides, monoesters, and monoalcohols. From the viewpoint of thermal stability, monocarboxylic acids and monoamines are preferable.
One type of end capping agent may be used alone, or two or more types 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, lauric acid, tridecylic acid, myristic acid, palmitic acid, stearic acid, pivalic acid, isobutyric acid and other aliphatic monocarboxylic acids; cyclohexanecarboxylic acid and other alicyclic monocarboxylic acids; and benzoic acid, toluyl And aromatic monocarboxylic acids such as acid, α-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, Aliphatic monoamines such as decylamine, stearylamine, dimethylamine, diethylamine, dipropylamine, and dibutylamine; alicyclic monoamines such as cyclohexylamine and dicyclohexylamine; and aromatic monoamines such as aniline, toluidine, diphenylamine, and naphthylamine; Etc.
Monoamines may be used alone or in combination of two or more.
In the polyamide of this embodiment, the end capping amount derived from the end capping agent is preferably 50% or less, more preferably 40% or less, further preferably 30% or less, and even more preferably 20%. Or less, more preferably 10% or less. When the end capping amount derived from the end capping agent is 50% or less, the affinity with the inorganic filler is increased, and a sliding component having excellent tensile strength, slidability and the like can be obtained. If the affinity between the polyamide and the inorganic filler is low, the inorganic filler may drop off on the sliding surface and cause wear. In addition, when producing pellets using a twin screw extruder, the strand stability (productivity) is reduced, and fillers that could not be dispersed well in the polyamide resin are generated as fluff, which reduces the quality of the pellets. There may be a problem of degrading.

(Characteristics of polyamide)
<Trans isomer ratio>
In the polyamide of this embodiment, the alicyclic dicarboxylic acid structure exists as a geometric isomer of a trans isomer and a cis isomer.
In the polyamide of the present embodiment, the trans isomer ratio in the portion derived from the alicyclic dicarboxylic acid represents the ratio of the trans isomer in the entire alicyclic dicarboxylic acid in the polyamide. 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 alicyclic dicarboxylic acid as a raw material, 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. In the polyamide of the present embodiment, the trans isomer ratio in the portion derived from the alicyclic dicarboxylic acid is preferably within the above range.

When the trans isomer ratio is within the above range, the polyamide of this embodiment has a high melting point, toughness, strength, rigidity, and plasticity time stability. Usually, it has the property of satisfying both the fluidity, which is a property contrary to heat resistance, and high crystallinity at the same time. In addition, the sliding component containing the polyamide is excellent in surface appearance.
Examples of the method for controlling the trans isomer ratio in the portion derived from the alicyclic dicarboxylic acid in the polyamide within the above range include a polyamide polymerization method and a polymerization condition control method. When producing a polyamide by a 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 necessary to produce it under polymerization conditions suitable for the polyamide composition. 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 decreasing the pressure while taking 30 minutes or more until the gauge pressure becomes 0 kg / cm ² .

In the present embodiment, the trans isomer ratio in the polyamide is determined, for example, by dissolving 30 to 40 mg of polyamide in 1.2 g of hexafluoroisopropanol deuteride and measuring the resulting solution by ¹ H-NMR. be able to. 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.

<Biomass plastic degree>
The biomass plasticity degree of the polyamide of this embodiment is preferably 25% or more from the viewpoint of reducing the environmental load. Here, the biomass plasticity means the proportion of units composed of raw materials derived from biomass in polyamide. The bioplastic degree can be calculated by the method described in Examples described later. A more preferable bioplastic degree is 30% or more. Although the upper limit of the biomass plasticity degree of the polyamide of this embodiment is not specifically limited, For example, it is 80% from a heat resistant viewpoint of polyamide.

  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 constituent components of polyamide. For example, synthesizing from sebacic acid, decamethylenediamine, and 11-aminoundecanoic acid, azelaic acid, which can be synthesized from sunflower seed components, cellulose, which can be synthesized from ricinoleic acid triglyceride, which is the main component of castor oil And pentamethylenediamine, γ-aminobutyric acid, etc.

Biomass is accumulated by absorbing carbon dioxide in the atmosphere through photosynthesis. Therefore, even if carbon dioxide is released into the atmosphere by combustion after use of plastics made from these materials, it is originally in the atmosphere. Therefore, the carbon dioxide concentration in the atmosphere does not increase.
Therefore, in polyamide, a high degree of biomass plastics is very effective for reducing the environmental load. Examples of a method for increasing the biomass plasticity degree of polyamide to 25% or more include a method for increasing the blending ratio of the above-described biomass-derived raw materials when producing polyamide.

<25 ° C. sulfuric acid relative viscosity>
The molecular weight of the polyamide of the present embodiment can be determined by using sulfuric acid relative viscosity ηr at 25 ° C. as an index.
The relative viscosity ηr of sulfuric acid at 25 ° C. of the polyamide of the present embodiment is preferably 2.3 to 5.0, more preferably from the viewpoints of moldability, tensile strength, surface appearance, slidability and the like of the polyamide composition. Is 2.4 to 4.0, more preferably 2.5 to 3.5.
As a method for controlling the relative viscosity ηr of sulfuric acid at 25 ° C. within the above range, for example, a known polycondensation catalyst such as phosphoric acid or sodium hypophosphite is added as an additive at the time of hot melt polymerization of polyamide. Control method, method of adjusting the amount of diamine added as an additive during hot melt polymerization of polyamide, method of reducing the amount of end-capping agent added, and polymerization conditions such as heating conditions and reduced pressure conditions And a method of promoting dehydration.
In this embodiment, measurement of sulfuric acid relative viscosity ηr at 25 ° C. of polyamide can be performed according to JIS-K6920 as described in the following examples.

<Mn (number average molecular weight)>
The molecular weight of the polyamide of the present embodiment can be determined using Mn (number average molecular weight) as an index. The Mn (number average molecular weight) of the polyamide of this embodiment is set to 15000 or more from the viewpoints of moldability, tensile strength, surface appearance, slidability and the like of the polyamide composition. Preferably it is 18000-80000, More preferably, it is 20000-80000, More preferably, it is 22000-80000, More preferably, it is 25000-70000.
By setting the Mn (number average molecular weight) of the polyamide to 15000 or more, preferably in the range of 18000 to 80,000, a polyamide composition excellent in moldability, tensile strength, surface appearance, slidability and the like can be obtained.

As a method for controlling the Mn (number average molecular weight) of the polyamide within the above range, for example, a method of adding a known polycondensation catalyst such as phosphoric acid or sodium hypophosphite as an additive at the time of hot melt polymerization of polyamide. , A method for adjusting the amount of diamine added as an additive during the hot melt polymerization of polyamide, a method for reducing the amount of the end-capping agent added, and the polymerization conditions such as heating conditions and reduced pressure conditions. Examples thereof include a method for promoting dehydration.
In this embodiment, the measurement of Mn (number average molecular weight) of polyamide can be performed using GPC (gel permeation chromatography) as described in the following examples.

<Molecular weight distribution>
The molecular weight distribution of the polyamide of this embodiment uses Mw (weight average molecular weight) / Mn (number average molecular weight) as an index.
The Mw (weight average molecular weight) / Mn (number average molecular weight) of the polyamide of the present embodiment is preferably 4.0 or less from the viewpoints of moldability, tensile strength, surface appearance, slidability and the like of the polyamide composition. More preferably, it is 1.5-3.5, More preferably, it is 1.5-3.3, More preferably, it is 1.5-3.0, Most preferably, it is 1.5-2. 5. The lower limit of the molecular weight distribution is 1.0.

By setting the Mw (weight average molecular weight) / Mn (number average molecular weight) of the polyamide of the present embodiment to 4.0 or less, a polyamide having excellent polymerization yield and plasticization time stability in melt polymerization can be obtained. In addition, a polyamide composition containing components represented by a sliding material and an inorganic filler described later is excellent in moldability, tensile strength, surface appearance, slidability, and the like.
The polyamide according to this embodiment has a high molecular weight and a ratio of polyamide molecules having a three-dimensional structure as long as the relative viscosity ηr of sulfuric acid at 25 ° C. is 2.3 or more and Mw / Mn is 4.0 or less. Furthermore, the three-dimensional structure of molecules can be suppressed during high-temperature processing, and excellent fluidity, tensile strength, and surface appearance can be obtained.

As a method for controlling the Mw (weight average molecular weight) / Mn (number average molecular weight) of the polyamide within the above range, for example, known additives such as phosphoric acid and sodium hypophosphite as additives during the hot melt polymerization of the polyamide And a method for controlling polymerization conditions such as heating conditions and reduced pressure conditions.
When the aromatic compound unit is contained in the molecular structure of the polyamide, the molecular weight distribution (Mw / Mn) tends to increase as the molecular weight increases. A high molecular weight distribution indicates a high proportion of polyamide molecules having a three-dimensional structure of the molecule, and the three-dimensional structure of the molecule is further promoted during high-temperature processing, resulting in poor fluidity, tensile strength, and surface appearance. .

The content of the aromatic compound unit in the polyamide of the present embodiment is preferably 50 mol% or less, more preferably 25 mol% or less, and further preferably 20 with respect to 100 mol% of the total component amount of the polyamide. It is not more than mol%, more preferably not more than 15%, most preferably not more than 10%.
In the present embodiment, the measurement of Mw (weight average molecular weight) / Mn (number average molecular weight) of polyamide was carried out using GPC (gel permeation chromatography) as described in the following examples. The average molecular weight) and Mn (number average molecular weight) can be used for calculation.

<Shear viscosity ratio>
In the polyamide of this embodiment, the ratio (η * 1 / η * 100) of the shear viscosity (η * 1) at an angular velocity of 1 rad / s to the shear viscosity (η * 100) at an angular velocity of 100 rad / s is preferably 3 or less. It is.
More preferably, it is 2.5 or less, More preferably, it is 2 or less.
When the ratio (η * 1 / η * 100) is 3 or less, excellent fluidity is obtained in the polyamide of this embodiment.
The ratio (η * 1 / η * 100) is related to the molecular weight distribution (Mw / Mn) of the polyamide. That is, when Mw / Mn is 4 or less, the ratio of three-dimensional structure is small, and further, the three-dimensionalization of molecules during high-temperature processing can be suppressed, and good fluidity can be obtained. 1 / η * 100) ≦ 3 can be realized.
The shear viscosity of the polyamide at a predetermined angular velocity can be measured by the method described in the examples described later.

<Melting peak temperature>
The melting peak temperature (melting point) T _pm-1 described later of the polyamide of the present embodiment is preferably 280 ° C. or higher, more preferably 280 ° C. or higher and 340 ° C. or lower, from the viewpoints of heat resistance and slidability. Preferably they are 280 degreeC or more and 330 degrees C or less, More preferably, they are 280 degreeC or more and 315 degrees C or less.
Polyamide having a melting peak temperature T _pm-1 of 330 ° C. or lower is preferable because thermal decomposition and the like in melt processing such as extrusion and molding can be further suppressed. If the melting peak temperature T _pm-1 is 315 ° C. or lower, the melting processing temperature can be lowered, the dispersibility of the sliding material is improved, and the sliding part has excellent sliding properties. Can do.
As a method for controlling the melting peak temperature (melting point) T _pm-1 of the polyamide within the above range, for example, the constituent components of the polyamide are the above components (a) to (c), and the blending ratio of the components is within the above range. The method of controlling etc. are mentioned.

In the polyamide of this embodiment, the melting peak temperature (melting point), the crystallization peak temperature, and the crystallization enthalpy 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 that appears on the highest temperature side at this time is the melting peak temperature T _pm-1, and the endothermic peak that appears on the lowest temperature side is the 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 .

In the polyamide of this embodiment, the difference (T _pm -T _pm-1 ) between the melting peak temperature T _pm and the melting peak temperature T _pm-1 is preferably 30 ° C. or less, and is preferably 0-20 ° C. The range is more preferable, and the range of 0 to 10 ° C. is more preferable. In polyamide, 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 more thermodynamically stable the portion derived from the alicyclic dicarboxylic acid in the polyamide. It means taking a simple structure. A polyamide 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 within the above range is excellent in plasticization time stability. In addition, the sliding component containing the polyamide is excellent in surface appearance. In the polyamide, as a method for controlling the difference (T _pm -T _pm-1 ) between the melting peak temperature T _pm and the melting peak temperature T _pm-1 within the above range, for example, the above components (a) to (c) And the blending ratio is within the above range, and the ratio of trans isomers derived from the alicyclic dicarboxylic acid in the polyamide is controlled within the range of 65 to 80 mol%.

From the viewpoint of heat resistance, the melting peak temperature T _pm-2 of the polyamide of the present embodiment is preferably 270 ° C. or higher, more preferably 270 to 320 ° C., and 280 to 310 ° C. More preferably.
Examples of the method for controlling the melting peak temperature (melting point) T _pm-2 of the polyamide within the above range include a method for controlling the blending ratio to the above-described range using the components (a) to (c). It is done.

Further, in the polyamide of the present embodiment, the difference between the melting peak temperature T _pm-1 and the melting peak temperature T _pm-2 (T _pm-1 -T _pm-2 ) is preferably 30 ° C. or less, and 10-20 More preferably, it is in the range of ° C. The difference between the melting peak temperature T _pm-1 and the melting peak temperature T _pm-2 (T _pm-1 -T _pm-2 ) in the polyamide is preferably in the above range from the viewpoint of releasability and low blocking property. .
As a method for 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 polyamide within the above range, for example, the above (a) to ( The method of using a component c) and controlling a compounding ratio in the range mentioned above is mentioned.

<Crystallization peak temperature>
The crystallization peak temperature T _pc-1 of the polyamide of the present embodiment is preferably 250 ° C. or higher, more preferably 260 ° C. or higher and 300 ° C. or lower, from the viewpoints of low blocking properties and releasability.
The crystallization peak temperature T _pc-1 can be measured by cooling at 20 ° C./min in differential scanning calorimetry according to JIS-K7121.
Examples of a method for controlling the crystallization peak temperature T _pc-1 of the polyamide within the above range include a method for controlling the blending ratio to the above-described range using the components (a) to (c).

The crystallization peak temperature T _pc-2 of the polyamide of the present embodiment is preferably 240 ° C. or higher, more preferably in the range of 240 to 280 ° C. from the viewpoints of low blocking properties and releasability.
The crystallization peak temperature T _pc-2 is 50 ° C./min after a predetermined operation as described above after the measurement of the crystallization peak temperature T _{pc-1 in} the differential scanning calorimetry according to JIS-K7121. It can be measured by cooling again.
Examples of a method for controlling the crystallization peak temperature T _pc-2 of the polyamide within the above range include a method for controlling the blending ratio to the above range using the components (a) to (c).

Furthermore, in the polyamide of 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 preferably 10 ° C. or less.
In polyamide, the smaller the difference between the crystallization peak temperature T _pc-1 and the crystallization peak temperature T _pc-2 (T _pc-1 -T _pc-2 ), the faster the crystallization speed and the more stable the crystal structure of the polyamide. It means that. 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 polyamide is within the above range, the viewpoint of low blocking property and releasability To preferred.
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 polyamide within the above range, for example, the above (a) The method etc. which control a compounding ratio to the range mentioned above using-(c) component are mentioned. Further, in order to reduce (T _pc-1 -T _pc-2 ) and to make the polyamide have a stable crystal structure, the number of carbon atoms of the components (a) to (c) should be an even number, The ratio of carbon number to amide group number (carbon number / amide group number) is preferably 8 or more and less than 9.

The crystallization enthalpy of the polyamide of this embodiment is preferably 10 J / g or more, more preferably 15 J / g or more, from the viewpoints of heat resistance, vibration fatigue characteristics, slidability, low blocking properties, and releasability. Yes, more preferably 20 J / g or more. Although the upper limit of the crystallization enthalpy of the polyamide of this embodiment is not particularly limited, it is 100 J / g or less.
As a method for controlling the crystallization enthalpy of polyamide within the above range, for example, the ratio of carbon number to amide group number (carbon number / amide group number) in the polyamide is 8 or more, and the above components (a) to (c) And a method of controlling the blending ratio to the above-described range.
The ratio of carbon number to amide group in the polyamide (carbon number / amide group number) can be controlled by the method described later.

<Glass transition temperature Tg>
The polyamide glass transition temperature Tg of this embodiment is 70 ° C. or higher, preferably 90 ° C. or higher and 170 ° C. or lower, more preferably 90 ° C. or higher and 160 ° C. or lower, and even more preferably 100 ° C. or higher and 160 ° C. or lower. Yes, more preferably from 115 ° C. to 160 ° C., and most preferably from 120 ° C. to 160 ° C. By setting the glass transition temperature Tg to 70 ° C. or higher, a sliding component having excellent heat resistance, low water absorption, tensile strength, and slidability can be obtained. Further, by setting the glass transition temperature to 170 ° C. or less, it is possible to obtain a sliding component having a good surface appearance.
Examples of the method for controlling the glass transition temperature Tg of the polyamide within the above range include a method of using the above components (a) to (c) and controlling the compounding ratio of the components to the above 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.
As described above, the polyamide of this embodiment has a great feature in that it contains a polyamide having a Tg of 70 ° C. or more and a Mn (number average molecular weight) of 15000 or more. This can solve the problem that melting occurs when a certain limit is exceeded due to, for example, an increase in the surface temperature of the molded product due to frictional heat in sliding parts. In addition, even under long-term friction and wear conditions, there is little deterioration in physical properties and excellent slidability.

In the differential scanning calorimetry, the polyamide of this embodiment has a difference (T _pc-1 −Tg) between the crystallization peak temperature T _pc-1 obtained when cooled at 20 ° C./min and the glass transition temperature Tg. It is preferably 140 ° C or higher, more preferably 145 ° C or higher, and further preferably 150 ° C or higher.
In polyamide, the larger the difference between the crystallization peak temperature T _pc-1 and the glass transition temperature Tg (T _pc-1 -Tg), the wider the temperature range that can be crystallized, and the more stable the crystal structure of the polyamide. means.
A polyamide having a difference (T _pc-1 -Tg) between the crystallization peak temperature T _pc-1 and the glass transition temperature Tg of 140 ° C. or more is excellent in low blocking property and releasability. In addition, a sliding component containing a component represented by a sliding material and an inorganic filler described later is excellent in tensile strength, surface appearance, slidability, and the like. 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, but is preferably 300 ° C. or less from the viewpoint of heat resistance.

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 polyamide, for example, the above components (a) to (c) are used. And the like. Further, in order to increase (T _pc-1 -Tg) and make the polyamide have a stable crystal structure, the components (a) to (c) may have an even number of carbon atoms, or the carbon chain may be linear Preferably, the ratio of the number of carbon atoms to the number of amide groups (number of carbon atoms / number of amide groups) in the polyamide is 8 or more and less than 9.

<Polymer end of polyamide>
The polymer ends of the polyamide in this embodiment are 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 polyamide means the terminal part of a polymer chain obtained by polymerizing dicarboxylic acid and diamine by amide bond. The polymer terminal of the polyamide 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 polymer terminal sealed with carboxylic acid or amine added at the time of superposition | polymerization.
4) The other terminal is a polymer terminal not classified in the above 1) to 4). For example, the terminal generated by deammonia reaction at the amino terminal, the terminal generated by decarboxylation from the carboxyl terminal, etc. Can be mentioned.

  The ratio of the amino terminal amount to the total amount of the amino terminal amount and the carboxyl terminal amount of the polyamide of this embodiment {amino terminal amount / (amino terminal amount + carboxyl terminal amount)} is not particularly limited. It is preferably 3 or more. More preferably, it is 0.5 or more, More preferably, it is 0.7 or more. The upper limit of the ratio of the amino terminal amount to the total amount of the amino terminal amount and the carboxyl terminal amount of the polyamide of the present embodiment {amino terminal amount / (amino terminal amount + carboxyl terminal amount)} is less than 1.0. preferable. By setting the ratio of the amino terminal amount to the total amount of the amino terminal amount and the carboxyl terminal amount of the polyamide to be 0.3 or more, the strength, toughness, thermal stability and hydrolysis resistance of the polyamide can be improved. Moreover, the affinity with the sliding material is increased, and the sliding component containing the polyamide is excellent in surface appearance and sliding property.

As a method for controlling the ratio of the amino terminal amount to the total amount of the amino terminal amount and the carboxyl terminal amount of the polyamide {amino terminal amount / (amino terminal amount + carboxyl terminal amount)}, for example, addition at the time of hot melt polymerization of polyamide Examples thereof include a method of controlling the addition amount of diamine and terminal blocker as a product, and 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 a 90 mass% phenol aqueous solution, and the obtained solution is titrated with 0.025N hydrochloric acid to determine the amino terminal amount. 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 0.1 N NaOH to determine the carboxyl end amount. The end point is determined from the discoloration of the phenolphthalein indicator.

<Carbon number / amide group number>
In the polyamide of this embodiment, the ratio of carbon number to amide group number (carbon number / amide group number) is preferably 8 or more, more preferably 8.2 or more and less than 9 from the viewpoint of low water absorption.
The ratio between the number of carbon atoms and the number of amide groups (carbon number / amide group number) is an index indicating the amino group concentration of polyamide.
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, it was excellent in strength, high temperature strength, low water absorption, low blocking property, releasability and plasticization time stability. Polyamide and a sliding component excellent in slidability and surface appearance can be provided.

As a method for controlling the ratio between the number of carbon atoms and the number of amide groups (number of carbon atoms / number of amide groups) in polyamide, for example, the components (a) to (c) are used, and the compounding ratio of the components is controlled within the above-described range. And the like.
An index indicating the amino group concentration (the number of carbon atoms / the number of amide groups) can be obtained by calculating an average value of the number of carbon atoms per amide group in the polyamide. Specifically, it can be determined by the method described in Examples described later.

[Production method of polyamide]
The method for producing the polyamide according to the present embodiment is not particularly limited, and includes a step of polymerizing the above-described (a) one alicyclic dicarboxylic acid and (b) one diamine. Examples include a method for producing polyamide.
When obtaining the polyamide of this embodiment, it is preferable that the addition amount of dicarboxylic acid and the addition amount of diamine are the same molar amount vicinity. The amount of diamine escaped from the reaction system during the polymerization reaction is also considered in terms of molar ratio, and the molar amount of the diamine is 0.9 to 1.2 with respect to the molar amount 1 of the entire dicarboxylic acid. Is more preferable, 0.95 to 1.1 is more preferable, and 0.98 to 1.05 is still more preferable.

The polyamide production method according to the present embodiment preferably further includes a step of increasing the degree of polymerization of the polyamide.
Examples of the method for producing a polyamide according to this embodiment include various methods as exemplified 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 a polyamide is produced by a 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 necessary to produce it under polymerization conditions suitable for the polyamide composition. 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 polyamide obtained by such a production method can satisfy the characteristics such as the above-mentioned conditions (1) and (2) and the trans isomer ratio.

  In the polyamide production method according to the present embodiment, from the viewpoint of the fluidity of the polyamide, polymerization may be performed while maintaining the trans isomer ratio of the portion derived from the alicyclic dicarboxylic acid in the obtained polyamide at 85% or less. In particular, by maintaining the trans isomer ratio at 80% or less, more preferably 65 to 80%, it is possible to obtain a polyamide having further excellent color tone, tensile elongation and plasticization time stability and having a high melting point. it can. In addition, the sliding component containing the polyamide is excellent in surface appearance.

In the method for producing a polyamide according to this embodiment, in order to increase the degree of polymerization and increase the melting point of the polyamide, the heating temperature may be increased and / or the heating time may be increased. In that case, there is a possibility that the polyamide may be colored by heating or the tensile elongation may be lowered due to thermal degradation. In addition, the rate of increase in molecular weight may be significantly reduced.
In order to prevent such a decrease in tensile elongation and stability in plasticizing time due to coloring or thermal deterioration of the polyamide, and in order to prevent a decrease in the surface appearance of a sliding component containing the polyamide, It is preferable to carry out the polymerization while maintaining the ratio at 80% or less.

As a method for producing the polyamide according to the present embodiment, a method of producing a polyamide 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 polyamide at 80% or less, and the obtained polyamide is excellent in color tone and plasticization time stability. Furthermore, the sliding component containing the polyamide is excellent in surface appearance.
In the method for producing a polyamide according to this 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.
The method for producing the polyamide according to the present embodiment is not particularly limited as long as it is a method capable of obtaining a polyamide satisfying the above-described characteristics (1) and (2). For example, the batch described below Polyamide can be produced by the hot melt polymerization method of the formula.
Examples of the method for producing polyamide by a batch type hot melt polymerization method include the following methods.
When producing a polyamide by a 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 necessary to produce it under polymerization conditions suitable for the polyamide composition.

Using water as a solvent, a solution of about 40 to 60% by mass containing a polyamide component (the above components (a) to (c)) was heated to a temperature of 110 to 180 ° C. and about 0.35 to 6 kg / cm ² (gauge pressure). ) Is concentrated to about 65 to 90% by mass in a concentration tank operated at a pressure of) 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 a molten state, a pressure suitable for the polyamide composition is necessary, and particularly 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. 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 the molten state, it is preferable to reduce the pressure while continuing heating and taking 20 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 polyamide pellets.

[(B) Inorganic filler]
Examples of the inorganic filler include, but are not limited to, glass fiber, carbon fiber, calcium silicate fiber, potassium titanate fiber, aluminum borate fiber, clay, flaky glass, talc, kaolin, mica , Hydrotalcite, calcium carbonate, magnesium carbonate, zinc carbonate, zinc oxide, calcium monohydrogen phosphate, wollastonite, silica, zeolite, alumina, boehmite, aluminum hydroxide, titanium oxide, silicon oxide, magnesium oxide, silicic acid Calcium, sodium aluminosilicate, magnesium silicate, ketjen black, acetylene black, furnace black, carbon nanotube, graphite, brass, copper, silver, aluminum, nickel, iron, calcium fluoride, montmorillonite, swelling Tsu-containing mica and apatite, and the like.

Among them, from the viewpoint of further improving the mechanical strength, from the group consisting of glass fiber, carbon fiber, wollastonite, kaolin, mica, talc, calcium carbonate, magnesium carbonate, potassium titanate fiber, aluminum borate fiber and clay One or more selected are preferred. Among these, one or more selected from the group consisting of glass fiber, carbon fiber, wollastonite, kaolin, mica, talc, calcium carbonate, and clay is more preferable.
The number average fiber diameter of the glass fiber or carbon fiber is preferably 3 to 30 μm, more preferably 3 to 20 μm, further preferably 3 to 12 μm, and more preferably 3 to 9 μm from the viewpoint of improving toughness and the surface appearance of the molded product. Even more preferred is 4-6 μm.
By setting the number average fiber diameter of the glass fiber or carbon fiber to 30 μm or less, a sliding component having excellent toughness and surface appearance can be obtained. On the other hand, when the thickness is 3 μm or more, a sliding component having an excellent balance between cost and powder handling surface and physical properties (fluidity, etc.) can be obtained. Furthermore, by setting it as 3-9 micrometers, it can be set as the sliding component excellent in tensile strength and slidability.

The cross section of the glass fiber or carbon fiber may be a perfect circle or a flat shape. Examples of such a flat cross section include, but are not limited to, a rectangular shape, an oval shape close to a rectangular shape, an elliptical shape, and a saddle shape with a narrowed central portion in the longitudinal direction. Here, the “flattening ratio” in this specification refers to a value represented by D2 / D1, where D2 is the major axis of the fiber cross section and D1 is the minor axis of the fiber cross section (a perfect circle is a flat shape). The rate is about 1.)
Among glass fibers and carbon fibers, the number average fiber diameter is 3 to 30 μm, the weight average fiber length is 100 to 750 μm, and the weight average fiber length from the viewpoint of imparting excellent mechanical strength to the sliding component. Those having an aspect ratio (L / D) of 10 to 100 between (L) and the number average fiber diameter (D) can be suitably used.

  Further, from the viewpoint of reducing warpage of the plate-shaped molded article and improving heat resistance, toughness, low water absorption and heat aging resistance, the flatness is preferably 1.5 or more, more preferably 1.5 to It is 10.0, More preferably, it is 2.5-10.0, More preferably, it is 3.1-6.0. When the flatness is in the above range, it is preferable because crushing can be effectively prevented during the mixing, kneading, molding, and other processing with other components, and a desired effect can be sufficiently obtained for the molded product.

  The thickness of the glass fiber or carbon fiber having an aspect ratio of 1.5 or more is not limited to the following, but the minor axis D1 of the fiber cross section is 0.5 to 25 μm and the major axis D2 of the fiber cross section is 1.25. It is preferable that it is 250 micrometers. Within the above range, the difficulty of spinning fibers can be effectively avoided, and the strength of the molded product can be improved without reducing the contact area with the resin (polyamide). The short diameter D1 is more preferably 3 to 25 μm, still more preferably 3 to 25 μm, and the flatness ratio is preferably larger than 3.

  These glass fibers and carbon fibers having an aspect ratio of 1.5 or more are obtained by using the methods described in, for example, Japanese Patent Publication No. 3-59019, Japanese Patent Publication No. 4-13300, Japanese Patent Publication No. 4-32775, and the like. Can be manufactured. In particular, in an orifice plate having a large number of orifices on the bottom surface, an orifice plate that surrounds a plurality of orifice outlets and has a convex edge extending downward from the bottom surface, or an outer peripheral tip of a nozzle tip having one or more orifice holes A glass fiber having a flatness ratio of 1.5 or more produced by using any one of the nozzle chips for spinning a modified cross-section glass fiber provided with a plurality of convex edges extending downward from the glass fiber is preferred. In these fibrous reinforcing materials, fiber strands may be used as rovings as they are, or a cutting step may be obtained and used as chopped glass strands.

  Here, the number average fiber diameter and the weight average fiber length in the present specification are values obtained by the following method. The polyamide composition is put in an electric furnace and the contained organic substances are incinerated. From the residue after the treatment, 100 or more glass fibers (or carbon fibers) are arbitrarily selected and observed with a scanning electron microscope (SEM) to measure the fiber diameter of these glass fibers (or carbon fibers). To obtain the number average fiber diameter. In addition, the weight average fiber length is obtained by measuring the fiber length using the SEM photograph of the 100 or more glass fibers (or carbon fibers) taken at a magnification of 1,000 times.

  The glass fiber or carbon fiber may be subjected to a surface treatment with a silane coupling agent or the like. Examples of the silane coupling agent include, but are not limited to, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, and N-β- (aminoethyl) -γ-aminopropylmethyl. Examples include aminosilanes such as dimethoxysilane, mercaptosilanes such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane, epoxy silanes, and vinyl silanes. Among these, one or more selected from the group consisting of the above-mentioned components is preferable, and aminosilanes are more preferable.

  In addition, for the above glass fiber and carbon fiber, as a sizing agent, an unsaturated vinyl monomer excluding the carboxylic acid anhydride-containing unsaturated vinyl monomer and the unsaturated vinyl monomer containing the carboxylic acid anhydride-containing unsaturated vinyl monomer; Copolymer, epoxy compound, polyurethane resin, homopolymer of acrylic acid, copolymers of acrylic acid and other copolymerizable monomers, and primary, secondary and tertiary amines thereof And 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. These may be used alone or in combination of two or more.

  Among them, from the viewpoint of the mechanical strength of the resulting sliding part, as the sizing agent, unsaturated vinyl monomers other than the unsaturated vinyl monomer containing carboxylic acid anhydride and the unsaturated vinyl monomer containing carboxylic acid anhydride are used. A copolymer containing a monomer as a constituent unit, an epoxy compound, a polyurethane resin, and a combination thereof are preferable. More preferably, 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 a structural unit, and a polyurethane resin, And combinations thereof.

Glass fiber and carbon fiber are continuously produced by drying the fiber strand produced by applying the sizing agent to the fiber using a known method such as a roller-type applicator in the known fiber production process. Obtained by reaction.
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.
The sizing agent preferably gives (adds) an equivalent of 0.2 to 3% by mass, more preferably an equivalent of 0.3 to 2% by mass, with respect to 100% by mass of glass fiber or carbon fiber. Apply (add). That is, from the viewpoint of maintaining the fiber bundling, the addition amount of the bundling agent is preferably 0.2% by mass or more as a solid content with respect to 100% by mass of the glass fiber or carbon fiber. On the other hand, from the viewpoint of improving the thermal stability of the obtained sliding component, the amount of sizing agent added is preferably 3% by mass or less. The strand may be dried after the cutting step, or may be cut after the strand is dried.

  Inorganic fillers other than glass fibers and carbon fibers are not limited to the following from the viewpoint of improving the strength, rigidity and surface appearance of the molded product, for example, wollastonite, kaolin, mica, talc, Calcium carbonate, magnesium carbonate, potassium titanate fiber, aluminum borate fiber, and clay are preferred. More preferably wollastonite, kaolin, mica, talc, calcium carbonate and clay, more preferably wollastonite, kaolin, mica, talc, even more preferably wollastonite, mica, especially Wollastonite is preferable. These inorganic fillers may be used individually by 1 type, and may be used in combination of 2 or more type.

The average particle diameter of the inorganic filler other than glass fibers and carbon fibers is preferably 0.01 to 38 μm, more preferably 0.03 to 30 μm, from the viewpoint of improving the toughness and the surface appearance of the molded product. ˜25 μm is more preferable, 0.10 to 20 μm is still more preferable, and 0.15 to 15 μm is particularly preferable.
By setting the average particle size of the inorganic filler other than the glass fiber and the carbon fiber to 38 μm or less, a sliding component excellent in toughness and surface appearance can be obtained. On the other hand, when the thickness is 0.1 μm or more, a sliding component having an excellent balance between the cost and the powder handling surface and physical properties (fluidity, etc.) can be obtained.

  Here, among inorganic fillers, those having a needle-like shape such as wollastonite have a number average fiber diameter (hereinafter, also simply referred to as “average fiber diameter”) as an average particle diameter. When the cross section is not a circle, the maximum value of the length is defined as the (number average) fiber diameter.

About the weight average fiber length (hereinafter, also simply referred to as “average fiber length”) of the above-mentioned needle-like shape, the preferred range of the above-mentioned number average fiber diameter, and the following weight average fiber length (L) A numerical range calculated from a preferable range of the aspect ratio (L / D) with the number average fiber diameter (D) is preferable.
Regarding the aspect ratio (L / D) of the weight average fiber length (L) and the number average fiber diameter (D) of the needle-shaped one, the surface appearance of the molded product is improved, and the metal such as an injection molding machine From the viewpoint of preventing wear of the sexual parts, 1.5 to 10 is preferable, 2.0 to 5 is more preferable, and 2.5 to 4 is more preferable.

  In addition, the inorganic filler other than the glass fiber and the carbon fiber may be subjected to a surface treatment using a silane coupling agent, a titanate coupling agent, or the like. Examples of the silane coupling agent include, but are not limited to, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, and N-β- (aminoethyl) -γ-aminopropylmethyldimethoxysilane. Examples include aminosilanes, mercaptosilanes such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane, epoxy silanes, and vinyl silanes. Among these, one or more selected from the components listed above are preferable, and aminosilanes are more preferable. Such a surface treating agent may be previously treated on the surface of the inorganic filler, or may be added when the polyamide and the inorganic filler are mixed. Moreover, the addition amount of the surface treatment agent is preferably 0.05 to 1.5% by mass with respect to 100% by mass of the inorganic filler.

The content of the inorganic filler is preferably 20 to 80% by mass, more preferably 40 to 70% by mass, still more preferably 50 to 70% by mass, particularly preferably relative to the sliding component. Is 55-65 mass%.
By setting the content of the inorganic filler to 20% by mass or more with respect to the sliding component, an effect of improving the strength and rigidity of the resulting sliding component is exhibited. On the other hand, the polyamide composition excellent in extrudability and moldability can be obtained by setting the content of the inorganic filler to 80% by mass with respect to the sliding component.
The sliding component of this embodiment can further contain one or more components selected from the group consisting of a sliding material, a nucleating agent, a lubricant, a stabilizer, and a polymer other than the polyamide.

(Sliding material)
The sliding material used in the present invention is not particularly limited as long as it can improve the slidability such as the limit PV value, wear amount, dynamic friction coefficient, etc. of (A) polyamide by blending with (A) polyamide. Any sliding material can be used.
The sliding material used in the present embodiment is not limited to the following. For example, polytetrafluoroethylene (PTFE), perfluoropolyether, polychlorotrifluoroethylene, polyvinylidene fluoride, polyvinyl fluoride, polytetrafluoro Fluorine resins such as ethylene / perfluoroalkoxyethylene copolymer, polytetrafluoroethylene / polyhexafluoropropylene copolymer; (high molecular weight) (modified) polyethylene, (modified) polyolefin such as polypropylene, polydimethylsiloxane , Polymethylphenylsiloxane, amino-modified polydimethylsiloxane, epoxy-modified polydimethylsiloxane, alcohol-modified polydimethylsiloxane, carboxy-modified polydimethylsiloxane, fluorine-modified polydimethylsiloxane Silicones emissions such as molybdenum disulfide, and the like tungsten disulfide, zinc oxide whiskers, boronic acid whisker, calcium metasilicate whiskers, LCP fibers, organic fibers such as aramid fibers, polymer compounds such as a liquid crystal polyester. Among these, a fluororesin, silicone, modified polyolefin, molybdenum disulfide, and mineral oil are preferable, more preferably a fluororesin, silicone, and molybdenum disulfide, and still more preferably a fluororesin.

These sliding materials may be used individually by 1 type, and may be used in combination of 2 or more type.
Silicone may be liquid or solid at 25 ° C. When the silicone is liquid at 25 ° C., the viscosity at 25 ° C. is preferably 1 to 1 million cs, more preferably 1,000 to 500,000 cs, and more preferably 10,000 to 100,000 cs from the viewpoint of improving sliding properties. Is more preferable. On the other hand, when the silicone is in a solid state at 25 ° C., one that melts during melt processing such as extrusion or molding is preferable.
The average molecular weight of the fluororesin is preferably in the range of 100 to 100,000. When a fluorine oil having an average molecular weight within the above range is used, a sliding component with little bleed-out and excellent slidability can be obtained.
The melting peak temperature (melting point) T _pm-1 of the fluororesin is preferably 280 ° C. or higher, more preferably 280 ° C. or higher and 350 ° C. or lower, more preferably 300 ° C. or higher and 340 ° C. from the viewpoint of affinity with polyamide. Or less, more preferably from 310 ° C to 335 ° C.

The fluororesin preferably has Ra ≦ 20 and 0.50 ≦ Ra when the 50% particle diameter of the particles measured by a Microtrac FRA laser particle size distribution meter is Ra μm and the 90% cumulative diameter of the particles passing through the sieve is Rb μm. /Rb≦1.00.
From the standpoint of achieving good dispersion in the polyamide resin composition and achieving strand stability and suppression of flaking during pellet production, the Ra of the fluororesin is preferably 20 μm or less, more preferably 18 μm or less. Most preferably, it is 15 μm or less. The lower limit of Ra is not particularly limited, but preferably, Ra is 0.5 μm or more. Further, from the viewpoint of achieving good dispersion of the fluororesin in the resin composition and achieving the strand stability at the time of pellet production and the suppression of scuffing, the Ra / Rb is preferably 0.50 or more. More preferably, it is in the range of 55 to 1.00, and most preferably in the range of 0.60 to 1.00.

In the present specification, the 50% particle size of the particles measured with a micro-track FRA laser particle size distribution meter of fluororesin means the particle size and the particle size measured with a micro-track FRA laser particle size distribution meter (manufactured by Nikkiso). Determine the ratio (volume%) of the total volume of the particles to the total volume of all particles, and calculate the particle diameter when the cumulative value obtained by integrating the ratio (volume%) from the low particle diameter side becomes 50 volume% Is the value of Further, the 90% cumulative particle diameter on the sieve passage side of the particles measured with a micro-track FRA laser particle size distribution meter of fluororesin in this specification is the value of the particle diameter when the cumulative value is 90% by volume. .
Furthermore, the fluororesin preferably has a 1% mass reduction temperature by thermogravimetric analysis (TGA) of preferably 380 ° C. or higher, more preferably 390 ° C. or higher, and further preferably 400 ° C. or higher. If the 1% mass reduction temperature by fluorogravimetric analysis (TGA) of the fluororesin is less than 380 ° C., mold contamination will occur during injection molding.

In addition, the 1% mass reduction temperature by thermogravimetric analysis (TGA) of the fluororesin in this specification refers to a temperature increase from 50 ° C. at a heating rate of 10 ° C./min in a nitrogen atmosphere by a thermogravimetric analysis (TGA) meter. Sometimes the temperature when the initial mass of the fluororesin is reduced by 1%.
The fluorine resin may be a fluorine oil having a low molecular weight, and the weight average molecular weight of the fluorine oil is preferably in the range of 100 to 100,000, more preferably in the range of 500 to 10,000, and 2000 to 9000. More preferably. When a fluorine oil having an average molecular weight within the above range is used, a sliding component with little bleed-out and excellent slidability can be obtained. In addition, the weight average molecular weight as used in this specification says the value calculated | required from the PMMA calibration curve by the gel permeation chromatography (GPC) method.

The content of the sliding material is preferably 0.0 with respect to 100 parts by mass of (A) polyamide.
1 to 100 parts by mass, more preferably 0.03 to 60 parts by mass, further preferably 5 to 50 parts by mass, still more preferably 10 to 40 parts by mass, and most preferably 15 to 35 parts by mass. Part by mass.
When the content is 0.01 parts by mass or more, the effect of improving the sliding characteristics is sufficiently exhibited. On the other hand, when the content is 100 parts by mass or less, a sliding member having excellent extrudability, moldability, and surface appearance can be obtained.

(Nucleating agent)
The nucleating agent means that the addition increases the crystallization peak temperature of the polyamide composition, reduces the difference between the extrapolation start temperature and the extrapolation end temperature of the crystallization peak, It means a substance that can achieve the effect of miniaturizing or making the size uniform.
Examples of the nucleating agent include, but are not limited to, talc, boron nitride, mica, kaolin, calcium carbonate, barium sulfate, silicon nitride, carbon black, potassium titanate, and molybdenum disulfide. It is done.
Only one type of nucleating agent may be used alone, or two or more types may be used in combination.

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 determined by dissolving the molded article in a solvent in which polyamide such as formic acid is soluble, and arbitrarily selecting, for example, 100 or more nucleating agents from the obtained insoluble components, It can be determined by observing and measuring with an optical microscope or a scanning electron microscope.
In the sliding component of the present embodiment, the content of the nucleating agent is preferably 0.001 to 1 part by mass, more preferably 0.001 to 0 parts with respect to 100 parts by mass of the polyamide of the present embodiment. 0.5 parts by mass, and more preferably 0.001 to 0.09 parts by mass.
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 polyamide, the heat resistance of the sliding component is improved, and the content of the nucleating agent is set to 100 parts by mass of the polyamide. By making the amount 1 part by mass or less with respect to the part, a sliding component 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 alone, or two or more types may be used in combination.
Examples of higher fatty acids include, for example, stearic acid, palmitic acid, behenic acid, erucic acid, oleic acid, lauric acid, and saturated or unsaturated, linear or branched aliphatic having 8 to 40 carbon atoms Examples thereof include monocarboxylic acids, and stearic acid and montanic acid are preferred.
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 first, such as calcium, sodium, potassium, magnesium or the like. Examples include Group 2 elements, aluminum, and the like.
Examples of the higher fatty acid metal salt include, but are not limited to, calcium stearate, aluminum stearate, zinc stearate, magnesium stearate, calcium montanate, sodium montanate, calcium palmitate, and the like. A metal salt of montanic acid and a metal salt of stearic acid are preferred.
A higher fatty acid metal salt may be used individually by 1 type, and may be used in combination of 2 or more types.

The higher fatty acid ester is an esterified product of the higher fatty acid and alcohol. An ester of an aliphatic carboxylic acid having 8 to 40 carbon atoms and an aliphatic alcohol having 8 to 40 carbon atoms is preferable.
Examples of the aliphatic alcohol include, but are not limited to, stearyl alcohol, behenyl alcohol, and lauryl alcohol.
Examples of the higher fatty acid ester include, but are not limited to, stearyl stearate and behenyl behenate.
As a higher fatty acid ester, one type may be used alone, or two or more types 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 bis oleyl amide, N-stearyl stearyl amide, N-stearyl erucamide. Examples include amides.
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.
Only one type of higher fatty acid amide may be used alone, or two or more types 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 improving moldability.

The content of the lubricant in the sliding component of the present embodiment is preferably 0.001 to 1 part by weight, more preferably 0.03 to 0.5 parts by weight with respect to 100 parts by weight of the polyamide. It is.
When the content of the lubricant is within the above range, it is possible to obtain a sliding part having excellent releasability and plasticizing time stability, and excellent toughness, and a polyamide obtained by cutting the molecular chain. Can be prevented.

(Stabilizer)
Examples of the stabilizer include, but are not limited to, for example, phenol-based heat stabilizers, phosphorus-based heat stabilizers, amine-based heat stabilizers, and groups 3, 4, and 11 to 14 of the periodic table. Metal salts of these elements, and halides of alkali metals and alkaline earth metals.
Examples of the phenol-based heat stabilizer include, but are not limited to, hindered phenol compounds. The hindered phenol compound has a property of imparting excellent heat resistance and light resistance to resins such as polyamide and fibers.

  Examples of the hindered phenol compound include, but are not limited to, for example, N, N′-hexane-1,6-diylbis [3- (3,5-di-t-butyl-4-hydroxyphenylpropylene). Onamide), 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-tert-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, , 5-Di-tert-butyl-4-hydroxybenzylphosphonate-diethyl ester, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene And 1,3,5-tris (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanuric acid.

These may be used alone or in combination of two or more.
In particular, N, N′-hexane-1,6-diylbis [3- (3,5-di-t-butyl-4-hydroxyphenylpropionamide)] is preferable from the viewpoint of improving heat aging resistance.
When using a phenol-based heat stabilizer, the content of the phenol-based heat stabilizer in the sliding part is preferably 0.01 to 1% by weight, more preferably 0, relative to 100% by weight of the polyamide composition. 0.1 to 1% by mass. When the content of the phenol-based heat stabilizer is within the above range, the heat aging resistance of the sliding component can be further improved, and further the amount of gas generated can be reduced.

Examples of the phosphorus-based heat stabilizer include, but are not limited to, pentaerythritol phosphite compounds, 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-t-butylphenyl-tetra-tridecyl) diphosphite, tetra (C12-C15 mixed alkyl) -4,4'-isopropylidene diphenyldiphosphite, 4,4'-isopropylidenebis (2 -T-butylphenyl) -di (nonylphenyl) phosphite, tris (biphenyl) phosphite, tetra (tridecyl) -1,1,3-tris (2-methyl-5-t-butyl-4-hydroxyphenyl) Butane diphosphite, tetra (tridecyl) -4,4′-butylidenebis (3-methyl-6-tert-butylphenyl) diphosphite, tetra (C1-C15 mixed alkyl) -4,4′-isopropylidene diphenyl diphosphite , Tris (mono, dimixed nonylphenyl) phosphite, 4,4'-isopropylidene (2-t-butylphenyl) -di (nonylphenyl) phosphite, 9,10-di-hydro-9-oxa-9-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-t-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-methyl-4,6-di-t-butylphenyl) 2-ethylhexyl phosphite, tetrakis (2,4-di-t-butyl-5-methylphenyl) -4,4'-biphenylene diphosphite and tetrakis (2,4-di-t-butylphenyl) -4,4'-biphenylene diphos Fight is mentioned.
These may be used alone or in combination of two or more.

Among those listed above, pentaerythritol-type phosphite compounds and / or tris (2,4-di-t-butylphenyl) from the viewpoint of further improving the heat aging resistance of sliding parts and reducing the amount of gas generated Phosphites are preferred. Examples of the pentaerythritol type phosphite compound include, but are not limited to, 2,6-di-t-butyl-4-methylphenyl-phenyl-pentaerythritol diphosphite, -T-butyl-4-methylphenyl-methyl-pentaerythritol diphosphite, 2,6-di-t-butyl-4-methylphenyl-2-ethylhexyl-pentaerythritol diphosphite, 2,6-di-t -Butyl-4-methylphenyl-isodecyl-pentaerythritol diphosphite, 2,6-di-t-butyl-4-methylphenyl-lauryl-pentaerythritol diphosphite, 2,6-di-t-butyl-4 -Methylphenyl-isotridecyl-pentaerythritol diphosphite, 2,6-di-t- Tyl-4-methylphenyl-stearyl pentaerythritol diphosphite, 2,6-di-t-butyl-4-methylphenyl cyclohexyl-pentaerythritol 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-pentaerythritol diphosphite, 2,6-di-t-butyl-4-methylphenyl-octylphenyl-pentaerythritol diphosphite, 2,6-di-t-butyl-4-methylphenyl-nonyl Phenyl pentaerythritol diphosphite, 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-methylphenyl-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-phenyl pentae Rithritol diphosphite, bis (2,6-di-t-amyl-4-methylphenyl) pentaerythritol diphosphite, and bis (2,6-di-t-octyl-4-methylphenyl) pentaerythritol Diphosphite is mentioned.
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, bis, from the viewpoint of reducing the gas generation amount of the sliding parts. (2,6-di-t-butyl-4-ethylphenyl) pentaerythritol diphosphite, bis (2,6-di-t-amyl-4-methylphenyl) pentaerythritol diphosphite, and bis (2, One or more selected from the group consisting of 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 using a phosphorus-based heat stabilizer, the content of the phosphorus-based heat stabilizer in the sliding component is preferably 0.01 to 1% by weight, more preferably 100% by weight, based on the polyamide composition. 0.1 to 1% by mass. When the content of the phosphorous heat stabilizer is within the above range, the heat aging resistance of the sliding component can be further improved, and the amount of gas generated can be reduced.

  Examples of amine heat stabilizers include, but are not limited to, 4-acetoxy-2,2,6,6-tetramethylpiperidine, 4-stearoyloxy-2,2,6,6-tetra. Methylpiperidine, 4-acryloyloxy-2,2,6,6-tetramethylpiperidine, 4- (phenylacetoxy) -2,2,6,6-tetramethylpiperidine, 4-benzoyloxy-2,2,6 6-tetramethylpiperidine, 4-methoxy-2,2,6,6-tetramethylpiperidine, 4-stearyloxy-2,2,6,6-tetramethylpiperidine, 4-cyclohexyloxy-2,2,6 6-tetramethylpiperidine, 4-benzyloxy-2,2,6,6-tetramethylpiperidine, 4-phenoxy-2,2,6,6-tetramethyl Peridine, 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, , 6,6-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-hydroxyfe L) propionyloxy] 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 sliding component is preferably 0.01 to 1% by mass, more preferably 0 to 100% by mass of the polyamide composition. 0.1 to 1% by mass. When the content of the amine heat stabilizer is within the above range, the heat aging resistance of the sliding component can be further improved, and the amount of gas generated can be reduced.

  The metal salts of the elements of Groups 3, 4, and 11-14 of the Periodic Table of Elements are not limited as long as they are salts of metals belonging to these groups. From the viewpoint of further improving the heat aging resistance of the sliding component, a copper salt is preferable. Examples of the copper salt include, but are not limited to, copper halides (copper iodide, cuprous bromide, cupric bromide, cuprous chloride, etc.), copper acetate, copper propionate, benzoic acid. Examples thereof include copper, copper adipate, copper terephthalate, copper isophthalate, copper salicylate, copper nicotinate and copper stearate, and a copper complex 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, preferably one or more selected from the group consisting of copper iodide, cuprous bromide, cupric bromide, cuprous chloride and copper acetate, more preferably Copper iodide and / or copper acetate. When the above-mentioned more preferable copper salt is used, a polyamide composition having excellent heat aging resistance and capable of effectively suppressing metal corrosion of the screw or cylinder part during extrusion (hereinafter also simply referred to as “metal corrosion”). can get.
When using a copper salt, the content of the copper salt in the sliding component is preferably 0.01 to 0.60 mass%, more preferably 0.02 to 0.40, based on 100 mass% of the polyamide. % By mass. When the content of the copper salt is within the above range, the heat aging resistance of the sliding component can be further improved, and copper precipitation and metal corrosion can be effectively suppressed.

In addition, the content of the copper element derived from the copper salt is preferably 10 to 2000 parts by mass, more preferably 10 to 2000 parts by mass, more preferably 10 ⁶ parts by mass, from the viewpoint of improving the heat aging resistance of the sliding component. It is 30-1500 mass parts, More preferably, it is 50-500 mass parts.

Alkali metal and alkaline earth metal halides include, but are not limited to, for example, potassium iodide, potassium bromide, potassium chloride, sodium iodide and sodium chloride, and mixtures thereof. . Among these, potassium iodide and / or potassium bromide is preferable from the viewpoint of improving heat aging resistance and suppressing metal corrosion, and more preferably potassium iodide.
When using alkali metal and alkaline earth metal halides, the content of alkali metal and alkaline earth metal halides in the sliding part is preferably 0.05 to 20 masses per 100 parts by mass of the polyamide. Part, more preferably 0.2 to 10 parts by mass. When the content of the alkali metal and alkaline earth metal halide is within the above range, the heat aging resistance of the sliding component is further improved, and copper precipitation and metal corrosion can be effectively suppressed.

As the heat stabilizer component described above, only one kind may be used alone, or two or more kinds may be used in combination. Among these, from the viewpoint of further improving the heat aging resistance of the sliding component, a mixture of a copper salt and a halide of an alkali metal and an alkaline earth metal is preferable.
The ratio of copper salt to alkali metal and alkaline earth metal halide is preferably 2/1 to 40/1, more preferably 5 /, as the molar ratio of halogen to copper (halogen / copper). 1-30 / 1. In the above-mentioned range, the heat aging resistance of the sliding component can be further improved.
When the above halogen / copper is 2/1 or more, it is preferable because precipitation of copper and metal corrosion can be effectively 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 (toughness and the like).

((A) Polymer other than polyamide)
In the polyamide composition of the present embodiment, when melt-kneading the raw material component containing the above-mentioned (A) polyamide, the polymer other than (A) the polyamide (A) Can be mixed with a raw material component containing, supplied to a melt kneader and kneaded. (A) The polymer other than polyamide is not limited to the following, but, for example, polyamide other than the polyamide of this embodiment, polyester, liquid crystal polyester, polyphenylene sulfide, polyphenylene ether, polycarbonate, polyarylate, phenol resin, An epoxy resin etc. are mentioned.

  Polyamides other than the (A) polyamide according to this embodiment are not limited to the following. For example, polyamide 66, polyamide 56, polyamide 46, polyamide 610, polyamide 612, polyamide 6T, polyamide 6I, polyamide 6 , Polyamide 11, polyamide 12, polyamide MXD6 and the like, and homopolymers or copolymers thereof. The polyamide other than (A) polyamide according to this embodiment is preferably polyamide 66, polyamide 610, polyamide 612, polyamide 6T, polyamide from the viewpoints of heat resistance, toughness, low water absorption, strength, rigidity, surface appearance, and the like. 6I, more preferably polyamide 66, polyamide 610, and polyamide 612, and further preferably polyamide 610 and polyamide 612.

The content of the polymer other than (A) polyamide according to this embodiment is preferably 1 to 100 parts by mass, more preferably 5 to 50 parts by mass, and still more preferably, with respect to 100 parts by mass of (A) polyamide. It is 5-40 mass parts, More preferably, it is 20-35 mass parts. By making the content of the polymer other than polyamide in the polyamide composition of the present embodiment within the above range, a sliding component excellent in heat resistance, toughness, low water absorption, strength, rigidity, surface appearance, and the like can be obtained. it can.
The proportion of the aliphatic polyamide other than (A) polyamide according to this embodiment is preferably from the viewpoint of slidability and surface appearance, such as low water absorption, tensile strength, rigidity, etc. with respect to 100 parts by mass of (A) polyamide. Is 1 to 90 parts by mass.

Examples of the polyester include, but are not limited to, polybutylene terephthalate, polytrimethylene terephthalate, polyethylene terephthalate, and polyethylene naphthalate.
In the sliding component of the present embodiment, additives conventionally used for polyamide, for example, colorants such as pigments and dyes (including colored master batches), are difficult within the range that does not impair the purpose of the present embodiment. A flame retardant, a fibrillating agent, a fluorescent bleaching agent, a plasticizer, an antioxidant, an ultraviolet absorber, an antistatic agent, a fluidity improver, a spreading agent, an elastomer and the like can also be contained.
When the sliding component of the present embodiment contains the other raw materials described above, the content of the other raw materials varies depending on the type and the like, so that the purpose of the present embodiment is not impaired. There is no particular limitation as long as it is present.

(Characteristics of sliding parts)
<Mn (number average molecular weight)>
Mn (number average molecular weight) can be used as an index for the molecular weight of the sliding component of the present embodiment. The Mn (number average molecular weight) of the sliding component of the present embodiment is preferably 15000 or more, more preferably 18000 to 80000, and further preferably 20000, from the viewpoints of tensile strength, surface appearance, slidability, and the like. -80000, more preferably 22000-80000, and most preferably 25000-70000.
By setting the Mn (number average molecular weight) of the sliding component to preferably 15000 or more, the tensile strength, surface appearance, slidability and the like are excellent.

As a method for controlling the Mn (number average molecular weight) of the sliding component within the above range, for example, a known polycondensation catalyst such as phosphoric acid or sodium hypophosphite is used as an additive during hot melt polymerization of polyamide. A method of adding, a method of adjusting the amount of diamine added as an additive during hot melt polymerization of polyamide, a method of reducing the amount of addition of the end-capping agent, and polymerization conditions such as heating conditions and reduced pressure conditions. Examples include a method of controlling and promoting dehydration.
In this embodiment, the measurement of Mn (number average molecular weight) of a sliding component can be performed using GPC (gel permeation chromatography) as described in the following examples.

<Molecular weight distribution>
The molecular weight distribution of the sliding component of this embodiment uses Mw (weight average molecular weight) / Mn (number average molecular weight) as an index.
Mw (weight average molecular weight) / Mn (number average molecular weight) of the sliding component of the present embodiment is preferably 4.0 or less, more preferably 1 from the viewpoint of tensile strength, surface appearance, slidability, and the like. It is 0.5-3.5, More preferably, it is 1.5-3.3, More preferably, it is 1.5-3.0, Most preferably, it is 1.5-2.5. The lower limit of the molecular weight distribution is 1.0.

As a method for controlling the Mw (weight average molecular weight) / Mn (number average molecular weight) of the sliding component within the above range, for example, phosphoric acid or sodium hypophosphite as an additive at the time of hot melt polymerization of polyamide. And a method of adding a known polycondensation catalyst, a method of controlling polymerization conditions such as heating conditions and reduced pressure conditions, and the like.
When an aromatic compound unit is contained in the molecular structure of the polyamide composition, the molecular weight distribution (Mw / Mn) tends to increase with increasing molecular weight. A high molecular weight distribution indicates a high proportion of polyamide molecules having a three-dimensional structure of the molecule, and the three-dimensional structure of the molecule is further promoted during high-temperature processing, resulting in poor fluidity, tensile strength, and surface appearance. .

The content of the aromatic compound unit in the sliding component of the present embodiment is preferably 50 mol% or less, more preferably 25 mol% or less, and still more preferably with respect to 100 mol% of the total component amount of the polyamide. Is 20 mol% or less, more preferably 15% or less, and most preferably 10% or less.
In this embodiment, the measurement of Mw (weight average molecular weight) / Mn (number average molecular weight) of the sliding component was performed using GPC (gel permeation chromatography) as described in the following examples. (Weight average molecular weight) and Mn (number average molecular weight) can be used for calculation.

[Production method of polyamide composition]
The production method of the polyamide composition used for the sliding component 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 polyamide. For example, it is preferable to include a step of melting and kneading the raw material component containing the above-mentioned polyamide with an extruder, and setting the temperature of the extruder to the above-mentioned polyamide melting peak temperature T _pm-1 + 30 ° C. or less.
As a method of melt-kneading raw material components including polyamide, for example, a method in which polyamide and other raw materials are mixed using a tumbler, a Henschel mixer, etc., supplied to a melt-kneader, kneaded, or single-screw or twin-screw extrusion Examples include a method of blending other raw materials from the side feeder into the polyamide melted by a machine.

In the method of supplying the components constituting the polyamide 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 about 250 to 375 ° C. as the resin temperature.
The melt kneading time is preferably about 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, a mixing roll, or the like can be used.

〔Molding〕
The molded article of this embodiment contains the above-mentioned polyamide or polyamide composition.
The molded article of the present embodiment is prepared by using the above-described polyamide or polyamide composition from a known molding method such as press molding, injection molding, gas assist injection molding, welding molding, extrusion molding, blow molding, film molding, hollow molding, It is obtained by molding using generally known plastic molding methods such as multilayer molding and melt spinning.

  Since the molded article of this embodiment is obtained from the above-mentioned polyamide composition, it is excellent in heat resistance, moldability, mechanical strength, low water absorption, vibration fatigue characteristics, slidability and surface appearance. Therefore, the molded product of the present embodiment, as various parts such as various sliding parts, automobile parts, electrical and electronic parts, home appliance parts, OA equipment parts, portable equipment parts, industrial equipment parts, daily necessities and household goods, It can be suitably used for extrusion applications and the like. Especially, the molded article of this embodiment is used suitably as various sliding parts.

The sliding member for automobiles is not limited to the following, but for example, as a material for sliding parts such as gears, actuators, bearing retainers, bearings, chain guides, chain tensioner shoes, switches, pistons, packings, rollers and belts. Can be used.
The sliding member for electric and electronic use, the sliding member for industrial equipment, the sliding member for daily use and household goods is not limited to the following. Used for materials, valve seats, V-rings, rod packings, piston rings, pistons, impellers, vanes and rotors.
The above gear is not limited to the following, for example, spur gear, helical gear, helical gear, internal gear pair, rack-small gear, quick bevel gear, spiral bevel gear, cross-axis face gear, Examples include screw gears, worm gears, and hypoid gears.

  Examples of sliding parts for daily necessities and household goods include slide fastener parts. The molded part for the slide fastener is not particularly limited as long as it is a molded part constituting the slide fastener, but generally includes an element rod, a slider, a puller, an upper stopper and a lower stopper, and a hearing tool. At least one of these slide fastener molded parts can be produced using the resin composition according to the present invention, and in particular, the resin composition according to the present invention can be suitably used as a material for sliders and pullers. . Furthermore, various slide fasteners provided with the molded parts for slide fasteners can be manufactured. The type of the element rod that is the meshing portion of the slide fastener is not particularly limited, and examples thereof include a coil fastener, an extrusion fastener, and an injection fastener.

  Various metal platings can be applied to the molded part for slide fastener according to the present invention. Examples of the metal plating include, but are not limited to, chromium plating, nickel plating, copper plating, gold plating, mana plating, and other alloy plating. There are no particular limitations on the method of metal plating, and dry plating such as vacuum deposition, sputtering, ion plating, etc., as well as electroplating (preferably electroless plating is performed before electroplating) is used as appropriate. Just do it. You may combine these methods. Among these, an electroplating method capable of firmly covering the inside of the slider having a complicated shape is preferable, and it is more preferable to perform electroplating after preliminarily performing electroless plating.

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 materials〕
In the examples and comparative examples, the following compounds were used.

<Dicarboxylic acid>
(1) 1,4-cyclohexanedicarboxylic acid (CHDC)
Product name: 1,4-CHDA HP grade (trans / cis = 25/75) (Eastman Chemical)
(2) Adipic acid (ADA) trade name: adipic acid (manufactured by Wako Pure Chemical Industries) Wako Pure Chemical Industries, Ltd.

<Diamine>
(1) 1,10-diaminodecane (1,10-decamethylenediamine) (C10DA)
Product name: 1,10-decanediamine (manufactured by Ogura Gosei Co., Ltd.)
(2) 1,12-diaminododecane (1,12-dodecamethylenediamine) (C12DA) (manufactured by Tokyo Chemical Industry Co., Ltd.)
(3) 1,6-diaminohexane (1,6-hexamethylenediamine) (C6DA) (manufactured by Tokyo Chemical Industry Co., Ltd.)
(4) 2-methylpentamethylenediamine (2MC5DA) (manufactured by Tokyo Chemical Industry)
(5) 1,9-nonamethylenediamine (C9DA) (manufactured by Aldrich)
(6) 2-Methyloctamethylenediamine (2MOD) The 2-methyloctamethylenediamine was produced with reference to the production method described in JP-A No. 05-17413.

<(B) Inorganic filler>
(1) Glass fiber (GF-1) Product name ECS03T275H Number average fiber diameter (average particle diameter) 10 μm (circular shape), cut length 3 mm
(2) Glass fiber (GF-2) treated with sizing agent containing maleic anhydride copolymer as shown in Production Example A below Number average fiber diameter of GF-2: 7 μm (circular shape)

[Production example of glass fiber]
<Production Example A>
First, the solid content is 2% by mass of polyurethane resin, 4% by mass of maleic anhydride-butadiene copolymer, 0.6% by mass of γ-aminopropyltriethoxysilane, and 0.1% by mass of carnauba wax. Dilution with water gave a glass fiber sizing agent.
The obtained glass fiber sizing agent was adhered to a melt-proofed glass fiber having a number average fiber diameter of 7 μm by an applicator provided in the middle of being wound around a rotating drum.
Then, roving of the glass fiber bundle surface-treated with the said glass fiber sizing agent was obtained by drying the glass fiber to which the glass fiber sizing agent was adhered.
At that time, the glass fiber was made to be a bundle of 1,000 pieces. The adhesion amount of the glass fiber sizing agent to the glass fiber was 0.6% by mass. This was cut into a length of 3 mm to obtain a chopped strand (hereinafter also abbreviated as “GF-2”).
In this example, the average fiber diameter of the glass fibers was measured as follows.
First, the polyamide composition was placed in an electric furnace, and the organic matter contained in the polyamide composition was incinerated. From the residue after the treatment, 100 or more glass fibers arbitrarily selected were observed with a scanning electron microscope (SEM), and the number average fiber diameter was determined by measuring the fiber diameter of these glass fibers. .

〔Measuring method〕
(Content of each structural unit in polyamide)
The content of each structural unit in the polyamide was quantified by ¹ H-NMR measurement as follows.
The polyamide pellets obtained in the examples and comparative examples were dissolved by heating in heavy hexafluoroisopropanol so as to have a concentration of about 5% by mass, and ¹ using a nuclear magnetic resonance analyzer JNM ECA-500 manufactured by JEOL. The following contents were determined by performing an H-NMR analysis and calculating the integration ratio.

(1) Melting peak temperature (melting point), crystallization peak temperature, crystallization enthalpy The melting peak temperature (melting point), crystallization peak temperature and crystallization enthalpy of the polyamides obtained in the production examples and comparative production examples are expressed in JIS- According to K7121, it measured using Diamond-DSC by PERKIN-ELMER.
The measurement was performed in a nitrogen atmosphere.
First, about 10 mg of a sample was set to a temperature rising rate from 50 ° C. to 350 ° C. at a temperature rising 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 .
Difference between melting peak temperature _Tpm and melting peak temperature _Tpm-1 ( _Tpm - _Tpm-1 ), melting peak temperature _Tpm-1
And the difference between the melting peak temperature T _pm-2 (T _pm-1 -T _pm-2 ) and the difference between the crystallization peak temperature T _pc-1 and the crystallization peak temperature T _pc-2 (T _pc-1 -T _pc-2 ), the difference (T _pc-1 -Tg) between the crystallization peak temperature T _pc-1 and the glass transition temperature Tg described later was measured.

(2) Glass transition temperature The glass transition temperature (Tg) of the polyamide obtained in the production example and the comparative example was measured according to JIS-K7121, using a Diamond-DSC manufactured by PERKIN-ELMER.
The measurement conditions were as follows.
A sample in a molten state obtained by melting the sample on a hot stage (EP80 manufactured by Mettler) was rapidly cooled using 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 temperature rising rate of 20 ° C./min.

(3) Sulfuric acid relative viscosity ηr at 25 ° C
The relative viscosity ηr of sulfuric acid at 25 ° C. of the polyamides obtained in the 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.

(4) Mn (number average molecular weight), Mw (weight average molecular weight) / Mn (number average molecular weight)
Mn (number average molecular weight) and Mw (weight average molecular weight) / Mn (number average molecular weight) of the polyamides obtained in the production examples and comparative examples, and the polyamide compositions obtained in the examples and comparative examples are GPC (gel Mw (weight average molecular weight) and number average molecular weight (Mn) measured by permeation chromatography, manufactured by Tosoh Corporation, HLC-8020, hexafluoroisopropanol solvent, PMMA (polymethyl methacrylate) standard sample (manufactured by Polymer Laboratory) ). As a sample, a solution obtained by dissolving 3.0 mg of polyamide and a polyamide composition in 3 mL of hexafluoroisopropanol (added with 0.005N sodium trifluoroacetate) and filtering through a 0.45 μm filter was used for measurement. The measurement conditions were as follows.
Solvent: hexafluoroisopropanol (added 0.005N sodium trifluoroacetate)
Flow rate: 0.5 mL / min Sample injection amount: 0.1 mL
Temperature: 30 ° C

(5) Trans isomerization rate The trans isomerization rate in the polyamides obtained in the production examples and comparative production examples was determined as follows.
30-40 mg of 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 polyamide was determined.

(6) Ratio of shear viscosity at an angular velocity of 1 rad / s to shear viscosity at an angular velocity of 100 rad / s (η * 1 / η * 100)
Test pieces were produced from the polyamide pellets obtained in the production examples and comparative production examples using a compression molding machine.
Specific molding conditions were such that the processing temperature was set to the melting peak temperature (T _pm-1 ) + 20 ° C. on the high temperature side of the polyamide, the preheating time was 2 minutes, the heating time was 2 minutes, and the cooling time was 3 minutes.
Melt viscoelasticity measurement was performed using the obtained molded piece and ARES-G2 (manufactured by TA Instruments Japan Co., Ltd.). Measurement mode: Oscillation Frequency Sweep Test, measurement jig: cone & plate, gap gap: 0.05 mm, stabilization time: 5 minutes, strain: 20%, angular velocity: 0.01 rad / sec to 100 rad / sec, load cell: 2 kg, Environmental state: nitrogen stream, measurement temperature: melting peak temperature (T _pm-1 ) + 20 ° C. on the high temperature side of polyamide.
The ratio of the shear viscosity (η * 1) at an angular velocity of 1 rad / s to the shear viscosity (η * 100) at an angular velocity of 100 rad / s was calculated. When (η * 1 / η * 100) was 3 or less, it was judged that the flow characteristics were good.

(7) Amino terminal amount ([NH ₂ ])
In the polyamides obtained in the 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 a 90 mass% phenol aqueous solution, and the obtained solution was titrated with 0.025N hydrochloric acid to determine the amino terminal amount (μ equivalent / g). The end point was determined from the indicated value of the pH meter.

(8) Amount of carboxyl terminal ([COOH])
In the polyamides obtained in the production examples and comparative production examples, the amount of carboxyl terminals bound to the polymer terminals was measured by neutralization titration as follows.
4.0 g of polyamide was dissolved in 50 mL of benzyl alcohol, and the resulting solution was titrated with 0.1N NaOH to obtain the carboxyl end amount (μ equivalent / g). The end point was determined from the discoloration of the phenolphthalein indicator.
([NH ₂ ] / ([NH ₂ ] + [COOH]) is calculated from the amino terminal amount ([NH ₂ ]) and the carboxyl terminal amount ([COOH]) measured in (7) and (8) above. did.

(9) Ratio of carbon number to amide group number (carbon number / amide group number)
In the polyamides obtained in the production examples and comparative production examples, the average value of the 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 polyamide.

(10) Biomass plastic degree In the polyamides obtained in the production examples and comparative production examples, the mass% of the unit composed of biomass-derived raw materials was calculated as the biomass plastic degree.
Specifically, sebacic acid and 1,10-diaminodecane, which use castor oil as a raw material, were used as biomass-derived raw materials.
And in the polyamide obtained by the Example and the comparative example, the ratio of the unit derived from sebacic acid and 1,10- diaminodecane was computed, and the said ratio was made into the biomass plastic degree.
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.

(11) Tensile strength Multi-purpose specimen A type according to ISO 3167, using pellets of polyamide composition obtained in Examples and Comparative Examples, using an injection molding machine [PS-40E: manufactured by Nissei Plastic Co., Ltd.] The molded piece was molded. Specific molding conditions were injection + holding time 25 seconds, cooling time 15 seconds, mold temperature 80 ° C., and molten resin temperature set to the high temperature melting peak temperature (T _pm-1 ) + 20 ° C. of polyamide. .
Using the obtained multi-purpose test piece A-type molded piece, in accordance with ISO 527, a tensile test was performed at a tensile rate of 5 mm / min under a temperature condition of 23 ° C., and a tensile yield stress was measured to obtain a tensile strength. .

(12) Copper concentration, halogen concentration, and molar ratio of halogen to copper (halogen / Cu)
About the pellet of the polyamide composition obtained by the Example and the comparative example, copper concentration, halogen concentration, and the molar ratio (halogen / Cu) of halogen and copper were measured as follows.
The copper concentration was determined by adding sulfuric acid to the sample, dropping nitric acid while heating to decompose the organic component, measuring the decomposition solution in pure water, and quantifying it by ICP emission analysis (high frequency plasma emission analysis). As an ICP emission analyzer, Vista-Pro manufactured by SEIKO ELECTRONIC INDUSTRY CO., LTD. Was used.
Taking iodine as an example, the halogen concentration is combusted in a flask in which the sample is replaced with high-purity oxygen, and the generated gas is collected in an absorbing solution. The iodine in the collected solution is 1 / 100N silver nitrate solution. Quantification was performed using potentiometric titration.
The molar ratio of halogen to copper (halogen / Cu) was calculated by converting the molecular weight into a mole using the above quantitative values.

(13) Water absorption rate In the dry as mold after forming the multipurpose test piece A-type molded piece as described in (11) above, the mass before the test of the multipurpose test piece A-type molded piece (mass before water absorption) ) Was measured. Next, the multipurpose test piece A-shaped molded piece was immersed in pure water at 80 ° C. for 72 hours. After that, the multi-purpose test piece A-shaped molded piece is taken out from the water, wiped off the water adhering to the surface, left in a constant temperature and humidity (23 ° C, 50RH%) atmosphere for 30 minutes, and then measured mass after test (mass after water absorption) did. The increment of the mass after water absorption with respect to the mass before water absorption was taken as the water absorption amount, the ratio of the water absorption amount with respect to the mass before water absorption was determined by the number of trials n = 3, and the average value was taken as the water absorption rate.

(14) Wear depth (μm)
Using the multipurpose test piece (A type) manufactured in (11) above, a reciprocating friction and wear tester (AFT-15MS: manufactured by Toyo Seimitsu Co., Ltd.) under conditions of a load of 150 g, a linear velocity of 400 mm / sec, and a reciprocating distance of 30 mm The reciprocating test was conducted 100,000 times at an ambient temperature of 23 ° C. As the counterpart material, a SUS ball (SUS304, R = 2.5 mm) was used.
About the part which the multi-purpose test piece after carrying out the reciprocating test was shaved, Rmax was measured using the surface roughness meter (Surfcom: Tokyo Seimitsu Co., Ltd.), and the wear depth was evaluated.

(15) Surface appearance (60 ° gloss)
Flat plate molded pieces were produced from the polyamide composition pellets obtained in Examples and Comparative Examples as follows.
Using an injection molding machine [FN-3000: manufactured by Nissei Resin Co., Ltd.], cooling time 25 seconds, screw rotation speed 200 rpm, mold temperature Tg + 20 ° C., cylinder temperature = (Tpm-1 + 10) ° C. to (Tpm-1 + 30) The injection pressure and the injection speed were appropriately adjusted so that the filling time was in the range of 1.0 ± 0.1 seconds, and a flat plate molded piece (13 cm × 13 cm, thickness 1 mm) from the polyamide composition pellets. ) Was manufactured.
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.

  Examples of polyamide and comparative examples are shown below. In addition, the above measurement items have been implemented and will be described.

[Production Example 1]
(Production of polyamide)
The polyamide polymerization reaction was carried out as follows by the “hot melt polymerization method”.
(A) 750 g (4.35 mol) of CHDC as the dicarboxylic acid and 750 g (4.35 mol) of C10DA as the diamine were dissolved in 1500 g of distilled water to prepare an equimolar aqueous solution of about 50% by mass of the raw material monomer.

The obtained aqueous solution and 17 g (0.10 mol) of C10DA, which is an additive at the time of melt polymerization, are charged into an autoclave (made by Nitto Koatsu) with an internal volume of 5.4 L, and the liquid temperature (internal temperature) is 50. The temperature was kept at 0 ° C., and the inside of the autoclave was replaced with nitrogen. Until the pressure in the autoclave tank (hereinafter also referred to simply as “inside the tank”) reaches 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 (350 ° C. described later) −60 ° C. (here, 290 ° C.) was reached while removing water out of the system. After the liquid temperature rises to the final temperature (350 ° C. described later) −60 ° C. (here, 290 ° 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) in the tank was about 350 ° C. The resin temperature was kept at about 350 ° C., and the inside of the tank was maintained under a reduced pressure of about 13.3 kPa (about 100 torr) for 10 minutes with a vacuum apparatus to obtain a polymer. Thereafter, the obtained polymer was pressurized with nitrogen to form a strand from the lower nozzle (nozzle), water-cooled, cut, and discharged in a pellet form to obtain polyamide pellets.
Each physical property of the obtained polyamide was measured based on the above method. The measurement results are shown in Table 1.

[Production Examples 2 to 6]
(A) Dicarboxylic acid, (b) diamine, (c) copolymerization component, and additives used in melt polymerization, the compounds and amounts shown in Table 1 were used, and the final resin temperature was shown in Table 1. Except that the temperature was as described in 1., a polyamide polymerization reaction was performed by the method described in Production Example 1 ("hot melt polymerization method") to obtain polyamide pellets.
Each physical property of the obtained polyamide was measured based on the above method.
The measurement results are shown in Table 1.

[Production Example 7]
The polyamide polymerization reaction was carried out as follows by the “hot melt polymerization method”.
(A) CHDC 800 g (4.65 mol) as dicarboxylic acid, (b) C10DA 520 g (3.02 mol) as diamine, (C-2) C6DA 189 g (1.63 mol) as diamine having fewer carbon atoms than diamine of (b) ) Was dissolved in 1500 g of distilled water to prepare an equimolar aqueous solution of about 50% by mass of the raw material monomer.

The obtained aqueous solution was charged into an autoclave (made by Nitto High Pressure Co., Ltd.) having an internal volume of 5.4 L, kept warm until the liquid temperature (internal temperature) reached 50 ° C., and the autoclave was purged with nitrogen. The liquid temperature was continuously heated from about 50 ° C. until the pressure in the autoclave tank reached about 2.5 kg / cm ² as gauge pressure (hereinafter, all pressure in the tank was expressed as gauge pressure). (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 (335 ° C. described later) −50 ° C. (here, 285 ° C.) was reached while removing water out of the system. After the liquid temperature rises to the final temperature (335 ° C. described later) −50 ° C. (here, 285 ° C.), it is 120 until the pressure in the tank reaches atmospheric pressure (gauge pressure is 0 kg / cm ² ) while heating continues. 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 335 ° C. The resin temperature was kept at about 325 ° C., and the inside of the tank was maintained under a reduced pressure of about 13.3 kPa (about 100 torr) for 25 minutes with a vacuum apparatus to obtain a polymer. Thereafter, the obtained polymer was pressurized with nitrogen to form a strand from the lower nozzle (nozzle), water-cooled, cut, and discharged in a pellet form to obtain polyamide pellets.
Each physical property of the obtained polyamide was measured based on the above method.
The measurement results are shown in Table 1.

[Production Example 8]
The polyamide polymerization reaction was carried out as follows by the “hot melt polymerization method”.
(A) CHDC 800 g (4.65 mol) as dicarboxylic acid, (b) C10DA 520 g (3.02 mol) as diamine, (C-2) C6DA 189 g (1.63 mol) as diamine having fewer carbon atoms than diamine of (b) ) Was dissolved in 1500 g of distilled water to prepare an equimolar aqueous solution of about 50% by mass of the raw material monomer.

The obtained aqueous solution was charged into an autoclave (made by Nitto High Pressure Co., Ltd.) having an internal volume of 5.4 L, kept warm until the liquid temperature (internal temperature) reached 50 ° C., and the autoclave was purged with nitrogen. The liquid temperature was continuously heated from about 50 ° C. until the pressure in the autoclave tank reached about 2.5 kg / cm ² as gauge pressure (hereinafter, all pressure in the tank was expressed as gauge pressure). (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 (345 ° C. described later) −50 ° C. (here, 295 ° C.) was reached while removing water out of the system. After the liquid temperature rises to the final temperature (345 ° C. described later) −50 ° C. (here, 295 ° 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 345 ° C. The resin temperature was kept at about 345 ° C., and the inside of the tank was maintained under a reduced pressure of about 80 kPa (about 600 torr) for 3 minutes with a vacuum apparatus to obtain a polymer. Thereafter, the obtained polymer was pressurized with nitrogen to form a strand from the lower nozzle (nozzle), water-cooled, cut, and discharged in a pellet form to obtain polyamide pellets.
Each physical property of the obtained polyamide was measured based on the above method.
The measurement results are shown in Table 1.

[Production Example 9]
The polyamide polymerization reaction was carried out as follows by the “hot melt polymerization method”.
836 g (5.72 mol) of ADA and 664 g (5.72 mol) of HMD were dissolved in 1500 g of distilled water to prepare an equimolar aqueous solution of about 50% by mass of the raw material monomer.
The obtained aqueous solution was charged into an autoclave (made by Nitto High Pressure Co., Ltd.) having an internal volume of 5.4 L, kept warm until the liquid temperature (internal temperature) reached 50 ° C., and the autoclave was purged with nitrogen. The liquid temperature was continuously heated from about 50 ° C. until the pressure in the autoclave tank reached about 2.5 kg / cm ² as gauge pressure (hereinafter, all pressure in the tank was expressed as gauge pressure). (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 245 ° C.). In order to keep the pressure in the tank at about 30 kg / cm ² , heating was continued until the final temperature (290 ° C. described later) −20 ° C. (here, 270 ° C.) was reached while removing water out of the system. After the liquid temperature rises to the final temperature (290 ° C. described later) −20 ° C. (here, 270 ° C.), the 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 290 ° C. The resin temperature was kept at about 290 ° C., and the inside of the tank was maintained under a reduced pressure of about 13.3 kPa (about 100 torr) for 25 minutes with a vacuum apparatus to obtain a polymer. Thereafter, the obtained polymer was pressurized with nitrogen to form a strand from the lower nozzle (nozzle), water-cooled, cut, and discharged in a pellet form to obtain polyamide pellets.
Each physical property of the obtained polyamide was measured based on the above method.
The measurement results are shown in Table 1.
The following polyamides, sliding materials, inorganic fillers, copper compounds and metal halides were used as raw materials for the polyamide composition.

[Production Example 10]
(A) Dicarboxylic acid, (b) diamine, (c) copolymerization component, and additives used in melt polymerization, the compounds and amounts shown in Table 1 were used, and the final resin temperature was shown in Table 1. Except that the temperature was as described in (4), a polyamide polymerization reaction was carried out by the method described in Production Example 9 (“hot melt polymerization method”) to obtain polyamide pellets.
Each physical property of the obtained polyamide was measured based on the above method.
The measurement results are shown in Table 1.

(Production of polyamide composition and evaluation of physical properties)
[Example 1]
A twin screw extruder (TEM35 manufactured by Toshiba Machine Co., Ltd., L / D = 47.6 (D = 37 mmφ), set temperature T _pm-1 + 10 ° C. (in this case, 334 + 10 = 344 ° C.), screw rotation speed 300 rpm) Used to produce a polyamide composition as follows.
The polyamide (100 parts by mass) of Production Example 1 with the moisture content adjusted is supplied from a top feed port provided at the most upstream part of the biaxial extruder, and the downstream side (top feed port) of the biaxial extruder. Glass fiber (GF-1) was supplied as an inorganic filler from the side feed port in a state where the supplied resin is sufficiently melted) and fed from the die head in the ratio (parts by mass) shown in Table 2 below. The melt-kneaded product was cooled in the form of strands and pelletized to obtain polyamide composition pellets.
Each physical property of the obtained polyamide composition was measured based on the above method.
The measurement results are shown in Table 2.

[Examples 2 to 11], [Comparative Examples 1 and 2]
Polyamide composition pellets were produced in the same manner as described in Example 1, except that the polyamides, sliding materials, and inorganic fillers of Production Examples were supplied in the proportions (parts by mass) shown in Table 2.
Each physical property of the obtained polyamide composition was measured based on the above method.
The measurement results are shown in Table 2.

As in Examples 1, 2, 4 to 12, a composition comprising a polyamide obtained by polymerizing (a) one dicarboxylic acid and (b) one diamine and a sliding material has a low content. It was confirmed that the water absorption rate, tensile strength, sliding properties and surface appearance were excellent.
Furthermore, it was found that the polyamide composition of Example 3 using GF having a number average fiber system of 7 μm was more excellent in tensile strength and slidability.
In addition, when the raw material component containing (A) polyamide was melt-kneaded, the polymers other than (A) polyamide were mixed with the raw material component containing (A) polyamide, and supplied to a melt-kneader to knead Examples 4 and 9 It was found that the polyamide compositions of ˜11 were excellent in tensile strength and surface appearance.

  The present invention has industrial applicability, such as being able to be suitably used as a sliding part such as a slider, an upper stopper and a lower stopper.

Claims (22)

A polyamide containing (A) (a) one dicarboxylic acid and (b) one unit of diamine and satisfying the following conditions (1) and (2):
(1) Tg is 70 ° C. or higher (2) Mn (number average molecular weight) is 15000 or higher (B) an inorganic filler;
A sliding part containing   The sliding component according to claim 1, wherein the (B) inorganic filler is at least one selected from the group consisting of glass fiber, carbon fiber, and aramid fiber.   The sliding component according to claim 1 or 2, which contains 50 to 70 mass% of the (B) inorganic filler. The sliding component according to any one of claims 1 to 3, wherein the polyamide (A) satisfies the following conditions (1) and (2).
(1) The sulfuric acid relative viscosity ηr at 25 ° C. is 2.3 or more. (2) Mw (weight average molecular weight) / Mn (number average molecular weight) is 4.0 or less. (A) (a) including one kind of dicarboxylic acid, (b) a polyamide containing a unit composed of one kind of diamine, and (B) an inorganic filler, and the following conditions (1) and (2) And a sliding part that satisfies (3).
(1) Tg is 70 ° C. or higher (2) Number average molecular weight is 15000 or higher (3) Mw (weight average molecular weight) / Mn (number average molecular weight) is 4.0 or lower   The sliding component according to any one of claims 1 to 5, wherein the (a) one kind of dicarboxylic acid is 1,4-cyclohexanedicarboxylic acid.   The polyamide (A) has a ratio (η * 1 / η * 100) of a shear viscosity (η * 1) at an angular velocity of 1 rad / s to a shear viscosity (η * 100) at an angular velocity of 100 rad / s is 3 or less. The sliding part as described in any one of Claims 1 thru | or 6. The said (A) polyamide further contains the unit which consists of at least 1 sort (s) of a copolymerization component chosen from the group which consists of (c) following (c-1)-(c-3). The sliding part as described in any one of Claims.
(C-1) Dicarboxylic acid other than (a) dicarboxylic acid (c-2) Diamine other than (b) whose carbon number is less than or equal to that of (b) diamine (c-3) Lactam and / or Aminocarboxylic acid In the 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 ) The sliding component according to claim 1, wherein is 140 ° C. or higher.   The sliding component according to any one of claims 1 to 9, wherein the (b) diamine is a diamine having 8 or more carbon atoms.   The sliding component according to any one of claims 1 to 10, wherein the (b) diamine is decamethylenediamine.   The (c-2) diamine other than the (b) having a carbon number equal to or less than that of the diamine (b) is at least one selected from the group consisting of diamines having an even number of carbon atoms. The sliding component as described in any one of thru | or 11.   (C-2) The diamine other than (b) having a carbon number equal to or less than that of the diamine (b) is at least selected from the group consisting of 1,6-hexamethylenediamine and 2-methylpentamethylenediamine. The sliding component according to any one of claims 8 to 12, which is a kind.   The sliding component according to any one of claims 1 to 13, wherein a sealing amount of the (A) polyamide is 50% or less.   The sliding component according to any one of claims 1 to 14, wherein the (B) inorganic filler has a number average fiber diameter of 3 to 9 µm.   The sliding component according to any one of claims 1 to 15, wherein a ratio of carbon number to amide group number (carbon number / amide group number) is 8 or more. In differential scanning calorimetry according to JIS-K7121, after measuring the crystallization peak temperature T _pc-1 obtained by cooling at 20 ° C./min and the crystallization peak temperature T _pc-1 , 50 ° C./min The difference (T _pc-1 -T _pc-2 ) from the crystallization peak temperature T _pc-2 obtained when re-cooled in the step is 10 ° C. or less. Sliding parts.   The content of the (c) copolymerization component is 7.5 mol% or more and 20.0 mol% or less with respect to 100 mol% of the total component amount of the polyamide, according to any one of claims 8 to 17. The sliding parts described.   The sliding component according to any one of claims 1 to 18, wherein the polyamide is a polyamide obtained through a solid phase polymerization step in at least a part of the polymerization step.   The sliding component according to any one of claims 1 to 19, wherein the degree of biomass plastic is 25% or more.   The sliding material according to any one of claims 1 to 20, further comprising at least one component selected from the group consisting of a sliding material, a nucleating agent, a lubricant, a stabilizer, and a polymer other than the polyamide. parts.   The sliding component according to any one of claims 1 to 21, wherein at least a part of the surface is dyed, painted, or metal-plated.