WO2013108344A1

WO2013108344A1 - Resin composition, and composition containing polyamide resin and glass fibers

Info

Publication number: WO2013108344A1
Application number: PCT/JP2012/008164
Authority: WO
Inventors: 佳史赤川; 直靖藪; 亮輔佐々木; 斉児玉
Original assignee: 宇部興産株式会社
Priority date: 2012-01-18
Filing date: 2012-12-20
Publication date: 2013-07-25

Abstract

A first invention is a resin composition that contains a polyamide resin (A) and a poly(phenylene ether) resin. The polyamide resin (A) contains a unit derived from a dicarboxylic acid (a) and a unit derived from a diamine (b), the dicarboxylic acid (a) contains an oxalic acid compound, the diamine (b) contains two or more diamines selected from among the group consisting of 1,6-hexanediamine, 1,9-nonanediamine and 2-methyl-1,8-octanediamine, and the content of the poly(phenylene ether) resin is less than 60 mass % relative to the total quantity of the polyamide resin (A) and the poly(phenylene ether) resin. A second invention is a composition for a sliding component, and the composition contains a polyamide resin and glass fibers, and is characterized in that the polyamide resin contains a polyamide resin obtained by using an oxalic acid compound as a raw material.

Description

Resin composition and composition containing polyamide resin and glass fiber

The present invention relates to a resin composition containing a polyamide resin and a polyphenylene ether resin. The present invention relates to a composition comprising a polyamide resin and glass fibers.

Conventionally, polyamide resins typified by nylon 6 and nylon 66 have been widely used as textiles for clothing or industrial materials or general-purpose engineering plastics because of their excellent properties and ease of melt molding.

On the other hand, problems such as insufficient heat resistance, changes in physical properties due to water absorption, deterioration in acid, high-temperature alcohol or hot water, etc. have been pointed out, having higher heat resistance, chemical resistance, hot water resistance, and There is an increasing demand for polyamide resins with lower water absorption.

A polyamide resin using oxalic acid as a dicarboxylic acid component is called a polyoxamide resin, and is known to have a higher melting point and lower water absorption than other polyamide resins having the same amino group concentration (Patent Document 1).

In addition, polyphenylene ether is used in a wide range of applications because of its excellent mechanical properties and heat resistance and excellent dimensional stability.

On the other hand, polyamide resins are widely used in automobile parts, machine parts, and electric / electronic parts because they exhibit excellent properties as engineering plastics. Polyamide resins are particularly useful as molding materials for sliding parts such as gears, cams, and bearings because they are particularly excellent in mechanical properties and frictional wear resistance.

Among them, polyamide 66 reinforced with glass fiber is excellent in mechanical properties and frictional wear resistance properties as disclosed in Patent Document 2, so that it can form sliding parts such as gears, cams, and bearings. A polyamide 66 containing 25 to 35% by mass of glass fiber is generally used.

Japanese Patent No. 4487687 WO / 2006/054774 WO / 2008/072754

Since polyphenylene ether has a high softening point, melt molding is difficult, and there are problems such as decomposition of the resin when the molding temperature is raised. For this reason, it has been attempted to improve melt molding by blending a styrene resin, but the heat resistance and chemical resistance of the resulting molded product are lowered, and the original properties of the polyphenylene ether resin itself are impaired. There is a drawback that it is easy.

In addition to conventional polyamide resins, parts used for electrical and electronic applications are required to have lower water absorption than polyoxamide resin, which has low water absorption. In addition, resins with excellent electrical properties and heat resistance Is required.

The first problem to be solved by the present invention is to provide a resin composition having low water absorption and excellent heat resistance and electrical characteristics.

Generally used polyamide 66 including glass fiber has a large dimensional change, friction coefficient, and wear amount in actual use, and may not be sufficient for use in sliding parts. In particular, gears used in electric power steering require a device for adjusting the backlash (gap) when the dimensional change during actual use is large. In the case of polyamide 66 containing 25-35% by weight of commonly used glass fibers, the equipment is usually required.
The actual use refers to a state of being placed in an atmosphere of a temperature of 23 ° C. ± 2 ° C. and a relative humidity of 50% ± 10% for 500 hours or more.

The second problem to be solved by the present invention is a composition having smaller dimensional change, coefficient of friction and wear amount in actual use than polyamide 66 containing 25 to 35% by mass of commonly used glass fiber. Is to provide.

(First invention)
The present inventors have found that a resin composition containing a specific polyamide resin and a polyphenylene ether resin has low water absorption and is excellent in heat resistance and electrical characteristics, and has completed the present invention. That is, the present invention is a resin composition comprising a polyamide resin (A) and a polyphenylene ether resin,
The polyamide resin (A) includes a unit derived from a dicarboxylic acid (a) and a unit derived from a diamine (b),
The dicarboxylic acid (a) contains an oxalic acid compound,
The diamine (b) includes two or more diamines selected from the group consisting of 1,6-hexanediamine, 1,9-nonanediamine and 2-methyl-1,8-octanediamine;
It is a resin composition whose content of the said polyphenylene ether resin is less than 60 mass% with respect to the total amount of the said polyamide resin (A) and the said polyphenylene ether resin.

(Second invention)
The present inventors have found that a composition containing a polyamide resin and glass fiber using a specific raw material can achieve the above-mentioned problem.
That is, the present invention is a composition comprising a polyamide resin and glass,
The said polyamide resin is a composition for sliding components characterized by including the polyamide resin which uses an oxalic acid compound as a raw material.

The resin composition of the first invention has low water absorption and is excellent in electrical characteristics and heat resistance.
In addition, according to the second invention, it is possible to provide a composition having a smaller dimensional change, coefficient of friction, and wear amount during actual use than polyamide 66 containing 25 to 35% by mass of glass fiber.

A test piece for obtaining dimensional stability is shown.

(First invention)
The present invention is a resin composition comprising a polyamide resin (A) and a polyphenylene ether resin,
The polyamide resin (A) includes a unit derived from a dicarboxylic acid (a) and a unit derived from a diamine (b),
The dicarboxylic acid (a) contains an oxalic acid compound,
The diamine (b) includes two or more diamines selected from the group consisting of 1,6-hexanediamine, 1,9-nonanediamine and 2-methyl-1,8-octanediamine;
It is a resin composition whose content of the said polyphenylene ether resin is less than 60 mass% with respect to the total amount of the said polyamide resin (A) and the said polyphenylene ether resin.

[Polyamide resin (A)]
The polyamide resin (A) used in the present invention contains a unit derived from a dicarboxylic acid (a) and a unit derived from a diamine (b), the dicarboxylic acid (a) contains an oxalic acid compound, and the diamine (b) Two or more diamines selected from the group consisting of 1,6-hexanediamine, 1,9-nonanediamine and 2-methyl-1,8-octanediamine are included.

(1) Dicarboxylic acid (a)
The dicarboxylic acid (a) used in the present invention is a dicarboxylic acid compound having reactivity with an amino group and providing a unit derived from a dicarboxylic acid as a constituent unit of the polyamide resin of the present invention. A oxalic acid compound that provides a unit derived from oxalic acid, which is one type, is included. Examples of the dicarboxylic acid compound include compounds derived from dicarboxylic acid, and examples of the compound derived from dicarboxylic acid include esters derived from dicarboxylic acid.

The oxalic acid compound used in the present invention is a compound that provides a unit derived from oxalic acid, and is a compound derived from oxalic acid such as oxalic acid and / or oxalic acid diester. The oxalic acid compound only needs to have reactivity with an amino group. When producing polyamides at a high polymerization temperature, succinic acid may be thermally decomposed when oxalic acid itself is used as a raw material. Therefore, the oxalic acid compound produced at a high polymerization temperature was derived from oxalic acid. Compounds are preferred.

As the compound derived from oxalic acid, oxalic acid diester is preferable from the viewpoint of suppressing side reactions in the polycondensation reaction.

Examples of oxalic acid diesters include oxalic acid diesters of aliphatic monohydric alcohols, oxalic acid diesters of alicyclic alcohols, and oxalic acid diesters of aromatic alcohols.

Examples of oxalic acid diesters of aliphatic monohydric alcohols include dimethyl oxalate, diethyl oxalate, di-n- (or i-) propyl oxalate, di-n- (or i-, or t-) butyl oxalate, and the number of carbon atoms is More than 3 oxalic acid diesters of aliphatic monohydric alcohols are preferred, di-n-butyl oxalate, di-butyl oxalate and / or di-t-butyl oxalate are more preferred, and di-n-butyl oxalate is more preferred.

Examples of oxalic acid diesters of alicyclic alcohols include dicyclohexyl oxalate.

Examples of oxalic acid diesters of aromatic alcohols include diphenyl oxalate.

The oxalic acid diester is preferably at least one selected from the group consisting of an oxalic acid diester of an aliphatic monohydric alcohol having more than 3 carbon atoms, an oxalic acid diester of an alicyclic alcohol, and an oxalic acid diester of an aromatic alcohol. N-butyl, di-butyl oxalate and / or di-t-butyl oxalate are more preferred, and di-n-butyl oxalate is more preferred.

These oxalic acid compounds can be added alone or in combination of two or more when the polyamide resin (A) is produced.

Examples of dicarboxylic acid compounds other than oxalic acid compounds include aliphatic dicarboxylic acids, alicyclic dicarboxylic acids, aromatic dicarboxylic acids, and compounds derived therefrom.

Aliphatic dicarboxylic acids include malonic acid, dimethylmalonic acid, succinic acid, glutaric acid, adipic acid, 2-methyladipic acid, trimethyladipic acid, pimelic acid, 2,2-dimethylglutaric acid, 3,3-diethylsuccinic acid. Examples include acids, azelaic acid, sebacic acid, and suberic acid.

Examples of the alicyclic dicarboxylic acid include 1,3-cyclopentanedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid.

Aromatic dicarboxylic acids include terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,4-phenylenedioxydiacetic acid, 1,3 -Phenylenedioxydiacetic acid, dibenzoic acid, 4,4'-oxydibenzoic acid, diphenylmethane-4,4'-dicarboxylic acid, diphenylsulfone-4,4'-dicarboxylic acid, 4,4'-biphenyldicarboxylic acid Can be mentioned.

These dicarboxylic acid compounds other than these oxalic acid compounds can be added singly or in combination of two or more when the polyamide resin (A) is produced.

Furthermore, polycarboxylic acids such as trimellitic acid, trimesic acid and pyromellitic acid can be used within the range where melt molding is possible regardless of the presence or absence of dicarboxylic acids other than oxalic acid compounds.

The content of units derived from dicarboxylic acids and / or polycarboxylic acids other than oxalic acid compounds contained in the polyamide resin (A) is the same as the units derived from all dicarboxylic acids and all polyvalent carboxylic acids contained in the polyamide resin (A). The total amount is preferably less than 50 mol%, more preferably 20 mol% or less, further preferably 10 mol% or less, further preferably 5 mol% or less, and further preferably 1 mol% or less.

(2) Diamine (b)
The diamine (b) used in the present invention contains two or more diamines selected from the group consisting of 1,6-hexanediamine, 1,9-nonanediamine and 2-methyl-1,8-octanediamine.

From the viewpoint of increasing the molecular weight of the polyamide resin (A), the diamine (b) includes 1,9-nonanediamine and 2-methyl-1,8-octanediamine (also referred to as C9 diamine), which are diamines having 9 carbon atoms. It is preferable to contain. The content of units derived from 1,9-nonanediamine and 2-methyl-1,8-octanediamine contained in the polyamide resin (A), that is, the content of units derived from C9 diamine is contained in the polyamide resin (A). In the total amount of all diamine-derived units, it is preferably 1 mol% or more, more preferably 20 mol% or more, further preferably 40 mol% or more, and 60 mol% or more. Is more preferably 80 mol% or more, and more preferably 90 mol% or more.

The diamine (b) preferably contains 1,6-hexanediamine, 1,9-nonanediamine and 2-methyl-1,8-octanediamine, and the melting point and thermal decomposition temperature (in nitrogen) of the polyamide resin (A). From the viewpoint of the balance between the 1% weight loss temperature of the polymer and other properties), 1,6-hexanediamine, 1,9-nonanediamine and 2-methyl-1,8- contained in the polyamide resin (A) The total content of octanediamine-derived units is preferably 10 mol% or more, more preferably 20 mol% or more, in the total amount of all diamine-derived units contained in the polyamide resin (A). , 40 mol% or more, more preferably 60 mol% or more, further preferably 80 mol% or more, 90 mol% More preferably a top.

The molar ratio of the sum of 1,9-nonanediamine and 2-methyl-1,8-octanediamine to 1,6-hexanediamine, ie, the molar ratio of C9 diamine to 1,6-hexanediamine is 1,9 -Maintaining the excellent properties of polyamide (hereinafter, sometimes referred to as polyamide 92) formed by polymerizing nonanediamine, 2-methyl-1,8-octanediamine and oxalic acid compound, and in particular, melt moldability and low water absorption. From the viewpoint of increasing the melting point of the polyamide resin (A) without impairing it, and particularly improving the mechanical properties, it is preferably 1:99 to 99: 1. The molar ratio of C9 diamine to 1,6-hexanediamine is more preferably 5.1: 94.9 to 99: 1, still more preferably 10:90 to 99: 1, and the melting point of the polyamide resin (A) From the viewpoint of facilitating polymerization and molding process (melt moldability), more preferably 20:80 to 99: 1, still more preferably 30:70 to 98: 2, and polyamide resin ( From the viewpoint of making the melting point of A) 280 ° C. or less and facilitating melt moldability, it is more preferably 30:70 to 90:10, further preferably 30:70 to 70:30.

The molar ratio of 1,9-nonanediamine and 2-methyl-1,8-octanediamine of C9 diamine, which is a diamine having 9 carbon atoms, is 1:99 to from the viewpoint of increasing the molecular weight of the polyamide resin (A). 99: 1 is preferable, 5:95 to 95: 5 is more preferable, 5:95 to 40:60 or 60:40 to 95: 5 is further preferable, and 5:95 to 30 is preferable. : 70 or 70:30 to 90:10 is more preferable. By including the above units with units derived from 1,9-nonanediamine, 2-methyl-1,8-octanediamine and 1,6-hexanediamine, it becomes possible to slow down the crystallization rate, A polyamide resin (A) excellent in extrusion molding or the like is obtained.

Other diamines can be contained as long as the effects of the present invention are not impaired. Specifically, as other diamines other than 1,6-hexanediamine, 1,9-nonanediamine and 2-methyl-1,8-octanediamine, ethylenediamine, propylenediamine, 1,4-butanediamine, 1, 8-octanediamine, 1,10-decanediamine, 1,12-dodecanediamine, 3-methyl-1,5-pentanediamine, 2,2,4-trimethyl-1,6-hexanediamine, 2,4,4 -Aliphatic diamines such as trimethyl-1,6-hexanediamine and 5-methyl-1,9-nonanediamine, cycloaliphatic diamines such as cyclohexanediamine, methylcyclohexanediamine and isophoronediamine, p-phenylenediamine and m-phenylenediamine , P-xylenediamine, m-xylenediamine, 4,4'-diaminodi Enirumetan, 4,4'-diaminodiphenylsulfone, 4,4'-aromatic diamines diaminodiphenyl ether, etc., and the like, these alone, or in two or more may be added during manufacturing.

The content of other diamine-derived units is not particularly limited as long as it does not impair the effects of the present invention, but is preferably less than 50 mol% in all diamine-derived units of the polyamide resin (A). More preferably, it is 20 mol% or less, More preferably, it is 10 mol% or less, More preferably, it is 5 mol% or less, More preferably, it is 1 mol% or less.

(3) Production of Polyamide Resin (A) The polyamide resin (A) used in the present invention can be produced using any method known as a method for producing polyamide. From the viewpoint of properties, preferably, the diamine (b) and the dicarboxylic acid (a) are produced by polycondensation reaction batchwise or continuously, and more preferably, the diamine (b) and the dicarboxylic acid (a ) Is produced by a two-stage polymerization method comprising a pre-polycondensation step and a post-polycondensation step, or a pressure polymerization method described in WO2008-072754.

Specific examples of the two-stage polymerization method and the pressure polymerization method include the following operations.

(3-1) Two-stage polymerization method (i) Pre-polycondensation step: First, the inside of the reactor is purged with nitrogen, and then the diamine (b) and the dicarboxylic acid (a) are mixed. When mixing, a solvent in which both the diamine (b) and the dicarboxylic acid (a) are soluble may be used. As a solvent in which both the diamine and the oxalic acid compound are soluble, toluene, xylene, trichlorobenzene, phenol, trifluoroethanol and the like can be used, and particularly, toluene can be preferably used. For example, after heating the toluene solution which melt | dissolved diamine to 50 degreeC, oxalic acid diester is added with respect to this.

The charging ratio of the diamine (b) and the dicarboxylic acid (a) is 0.8 to 1.5 (molar ratio) in terms of high molecular weight in terms of the molar amount of the dicarboxylic acid (a) / the molar amount of the diamine (b). ), Preferably 0.91 to 1.1 (molar ratio), more preferably 0.99 to 1.01 (molar ratio).

The temperature inside the reactor charged in this way is increased under normal pressure while stirring and / or nitrogen bubbling. The reaction temperature is preferably controlled so that the final temperature reaches 80 to 150 ° C., preferably 100 to 140 ° C. The reaction time at the final temperature is preferably 3 to 6 hours.

(Ii) Post-polycondensation step: In order to further increase the molecular weight, the polymer produced in the pre-polycondensation step is gradually heated in the reactor under normal pressure. In the temperature raising process, the final reached temperature of the pre-polycondensation step, that is, preferably 80 to 150 ° C., is finally preferably 295 to 350 ° C., more preferably 298 to 345 ° C., and more preferably 298 ° C. A temperature range of 340 ° C. or lower is reached.

It is preferable to carry out the reaction while keeping the temperature rising time preferably 1 to 8 hours, more preferably 2 to 6 hours. Furthermore, in the post-polymerization step, polymerization can be performed under reduced pressure as necessary. The preferable final pressure in the case of carrying out the vacuum polymerization is 13.3 Pa or more and less than 0.1 MPa.

(3-2) Pressurized polymerization method First, the diamine (b) is placed in a pressure-resistant vessel and purged with nitrogen, and then heated to the reaction temperature under a sealing pressure. Thereafter, while maintaining the sealed pressure state at the reaction temperature, the dicarboxylic acid (a) is injected into the pressure resistant vessel to start the polycondensation reaction. The reaction temperature is not particularly limited as long as the polyamide produced by the reaction of diamine (b) and dicarboxylic acid (a) can maintain a slurry or solution state and does not thermally decompose. The charge ratio of the diamine (b) and the dicarboxylic acid (a) is 0.8 to 1.5 (molar ratio), preferably 0.91 in terms of the molar amount of the dicarboxylic acid (a) / the molar amount of the diamine (b). To 1.1 (molar ratio), more preferably 0.99 to 1.01 (molar ratio).

Next, the temperature is raised to a temperature not lower than the melting point of the polyamide resin (A) and not thermally decomposing while keeping the inside of the pressure vessel in a sealed pressure state. For example, in the case of component (a), since the melting point is usually 245 to 300 ° C., the temperature is raised to 250 to 350 ° C., preferably 255 to 340 ° C., more preferably 260 to 335 ° C. To do. The pressure in the pressure-resistant container until reaching the predetermined temperature is adjusted to approximately 0.1 MPaG, preferably 1 MPaG to 0.2 MPaG, from the saturated vapor pressure of the alcohol to be generated. After reaching the predetermined temperature, the pressure is released while distilling off the produced alcohol, and the polycondensation reaction is continued under normal pressure nitrogen flow or reduced pressure as necessary. The preferable final pressure in the case of carrying out the vacuum polymerization is 13.3 Pa or more and less than 0.1 MPa.

(4) Properties of polyamide resin (A) Relative viscosity of polyamide resin (A) used in the present invention measured at 25 ° C. using a solution having a polyamide resin concentration of 1.0 g / dl (solvent: 96 mass% sulfuric acid) Is preferably from 1.8 to 6.0, more preferably from 2.0 to 5.5, and even more preferably from 2.5 to 4.5 from the viewpoints of physical properties and moldability.

[Polyphenylene ether resin]
Specific examples of the polyphenylene ether resin used in the present invention include poly-1,4-phenylene ether, poly-2,6-dimethyl-1,4-phenylene ether, poly-2,6-diethyl-1,4-phenylene. Ether, poly-2,6-dipropyl-1,4-phenylene ether, poly-2-methyl-6-allyl-1,4-phenylene ether, poly-2,6-dimethoxy-1,4-phenylene ether, poly -2-Methyl-6-ethyl-1,4-phenylene ether, poly-2,6-dichloro-1,4-phenylene ether, poly-2,6-dichloromethyl-1,4-phenylene ether, poly-2 , 3,6-trimethyl-1,4-phenylene ether, poly-2,3,5,6-tetrafluoro-1,4 phenylene ether, poly-2,3 Diphenyl-1,4-phenylene ether, poly-2,3-ditolyl-1,4-phenylene ether, copolymer of 2,6-dimethylphenol and other phenols and the like. Of these, poly-2,6-dimethyl-1,4-phenylene ether is preferred.

The polyphenylene ether resin used in the present invention may be a modified polyphenylene ether or a mixture of an unmodified polyphenylene ether and a modified polyphenylene ether. From the viewpoint of affinity with the polyamide resin (A), a modified polyphenylene ether is preferable. The production method of polyphenylene ether may be any known method and is not particularly limited.

The modified polyphenylene ether resin has a carboxylic acid group, a carboxylic acid anhydride group, a carboxylic acid ester group, a carboxylic acid metal base, a carboxylic acid imide group, and a carboxylic acid amide group from the viewpoint of affinity with the polyamide resin (A). And / or an epoxy group, and more preferably at least one functional group selected from the group consisting of a carboxyl group, an acid anhydride group, an amino group, and an epoxy group.

The intrinsic viscosity of the polyphenylene ether resin used in the present invention is not particularly limited, but the intrinsic viscosity measured in chloroform at 30 ° C. is preferably 0.01 to 5 dl / g, preferably 0.1 to 4.5 dl. / G is more preferable.

[Resin composition]
In the resin composition of the present invention, the content of the polyphenylene ether resin is less than 60% by mass, preferably 56% by mass, based on the total amount of the polyamide resin (A) and the polyphenylene ether resin, from the viewpoints of heat resistance and moldability. % Or less, and more preferably 51% by mass or less.

In addition, the total content of the polyamide resin (A) and the polyphenylene ether resin is preferably 50% by mass or more, and 70% by mass in the total amount of the resin composition from the viewpoint of maintaining the effects of the respective resins and the effects of the present invention. % Or more is more preferable, and 90 mass% or more is more preferable.

(1) Other polymer In addition to the polyamide resin (A) and polyphenylene ether resin used in the present invention, the resin composition of the present invention may contain other polymers as long as the effects of the present invention are not impaired. Examples of other polymers include other polyamides such as polyoxamides other than polyamide resin (A), aromatic polyamides, aliphatic polyamides, alicyclic polyamides, and thermoplastic polymers other than polyamides and polyphenylene ethers.

The content of the other polymer is not particularly limited as long as it does not impair the effects of the present invention, but in the resin composition of the present invention, the total is preferably less than 50% by mass, more preferably 30% by mass or less. Preferably, 10 mass% or less is more preferable.

(2) Additive The resin composition of the present invention, the polyamide resin (A) and polyphenylene ether used in the present invention can contain other additives as long as the effects of the present invention are not impaired. As, for example, pigments, dyes, colorants, heat-resistant agents, antioxidants, weathering agents, ultraviolet absorbers, light stabilizers, compatibilizers, lubricants, crystal nucleating materials, crystallization accelerators, mold release agents, Examples thereof include an antistatic agent, a plasticizer, an antistatic agent, a flame retardant, glass fiber, a lubricant, a filler, and a reinforcing fiber. These additives can be contained alone or in combination of two or more. The content is not particularly limited as long as it does not impair the effects of the present invention, but in the resin composition of the present invention, the total content is preferably 50% by mass or less, more preferably 30% by mass or less. A mass% or less is more preferable.

As the heat-resistant agent, a copper-containing compound is preferable, and among them, copper halides such as copper iodide and copper bromide are preferable. The content of the copper-containing compound is preferably 10 to 1000 ppm in the resin composition of the present invention. Usually, an alkyl halogen compound is further added as a secondary antioxidant.

Examples of the antioxidant include phenolic antioxidants, phosphorus antioxidants, and sulfur antioxidants, and one or more of them can be contained in the resin composition of the present invention.

Examples of phenolic antioxidants include triethylene glycol bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol bis [3- (3 , 5-di-t-butyl-4-hydroxyphenyl) propionate], pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3 , 5-di-t-butyl-4-hydroxyphenyl) propionate, 3,5-di-t-butyl-4-hydroxybenzylphosphonate-diethyl ester, N, N′-hexamethylenebis (3,5- Di-t-butyl-4-hydroxy-hydrocinnamamide), 1,3,5-trimethyl-2,4,6-tris (3,5-di-t- Til-4-hydroxybenzyl) benzene, 3,9-bis [2- {3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl] -2, 4,8,10-tetraoxaspiro [5,5] undecane, etc., among which pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate N, N′-hexamethylene bis (3,5-di-t-butyl-4-hydroxy-hydrocinnamamide), or one or more of them contained in the resin composition of the present invention can do.

Examples of the phosphorus-based antioxidant include tris (2,4-di-t-butylphenyl) phosphite, 2-[[2,4,8,10-tetrakis (1,1-dimethylether) dibenzo [d, f] [1,3,2] dioxaphosphine 6-yl] oxy] -N, N-bis [2-[[2,4,8,10-tetrakis (1,1-dimethylethyl) dibenzo [ d, f] [1,3,2] dioxaphosphine 6-yl] oxy] -ethyl] ethanamine, bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite, etc. In particular, 2-[[2,4,8,10-tetrakis (1,1-dimethylethyl) dibenzo [d, f] [1,3,2] dioxaphosphine 6-yl ] Oxy] -ethyl] ethanamine, one or more, It can be contained in the resin composition of the invention.

Sulfur-based antioxidants include 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], tetrakis [methylene-3- (dodecylthio) propionate] methane 1 type, or 2 or more types can be contained in the resin composition of the present invention.

Compatibilizers include acrylic acid, methacrylic acid, maleic acid, maleic anhydride, itaconic acid, citric acid, fumaric acid, crotonic acid, methylmaleic acid, methyl fumaric acid, mesaconic acid, citraconic acid, glutaconic acid, cis- 4-cyclohexene-1,2-dicarboxylic acid, endobicyclo [2.2.1] -5-heptene-2,3-dicarboxylic acid and carboxylic acid metal salts thereof, monomethyl maleate, monomethyl itaconate, methyl acrylate, Ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, hydroxyethyl acrylate, aminoethyl methacrylate, dimethyl maleate, dimethyl itaconate, maleic anhydride, itaconic anhydride, citraconic anhydride, endobicyclo- [2.2.1] -5-heptene-2,3-dicarboxylic Acid anhydride, maleimide, N-ethylmaleimide, N-butylmaleimide, N-phenylmaleimide, acrylamide, methacrylamide, glycidyl methacrylate, glycidyl acrylate, glycidyl ethacrylate, glycidyl itaconate, glycidyl citraconic acid, etc. 1 type (s) or 2 or more types can be contained in the resin composition of this invention.

The method for adding the other polymer and the additive is not particularly limited as long as each of them can be dispersed in the polyamide-based resin, and at any point that does not impair the effect, the polyamide resin ( A) can be added. For example, other polymers and additives can be added to the prepolymerization step and / or postpolymerization step of the polyamide resin (A), and can be added to the polyphenylene ether (B). It can also be added before, during and after production of the resin composition of the invention.

(3) Production of Resin Composition The production method of the resin composition of the present invention is not particularly limited as long as it contains the polyamide resin (A) and the polyphenylene ether resin. Examples thereof include a production method by melt kneading such as a single-screw extruder, a twin-screw extruder, a multi-screw extruder, and a kneader. From the viewpoint of dispersibility of the polyamide resin (A) and the polyphenylene ether resin, a production method by melt kneading is preferred, and among them, production using a twin screw extruder from the viewpoint of fluidity during kneading of the resin composition of the present invention. Is more preferable.

The resin composition of the present invention can be molded into various molded products by known molding methods such as injection molding, extrusion molding, blow molding, vacuum molding, and press molding. It is particularly useful in the fields of injection molding and blow molding.

Since the resin composition of the present invention has a wide moldable temperature range and has a low dielectric constant and dielectric loss tangent, it is suitably used for, for example, antennas, ETCs, wireless LANs and mobile phones used in high frequency ranges. it can.

In addition, since the resin composition of the present invention has excellent properties inherently possessed by the polyamide resin and polyphenylene ether in a well-balanced manner and has excellent heat resistance, it can be used for automobile parts, industrial materials, industrial materials, machinery. It can be usefully used for parts, office equipment parts, household goods, sheets, films, fibers and the like.

(Second invention)
The composition of this invention is a composition containing the polyamide resin and glass fiber which used the specific raw material.

[Polyamide resin]
The polyamide resin used for this invention contains the polyamide resin which uses an oxalic acid compound as a raw material. From the viewpoint of dimensional change during actual use of the composition, the amount of wear, and the reduction of the friction coefficient, the polyamide resin made from oxalic acid compound is preferably 10% by mass or more, more preferably 50% by mass or more, based on the total amount of the polyamide resin. 99 mass% or more is more preferable.

(1) Polyamide resin using oxalic acid compound as raw material The oxalic acid compound is a compound that provides a unit derived from oxalic acid, and is a compound derived from oxalic acid such as oxalic acid and / or oxalic acid diester. The oxalic acid compound only needs to have reactivity with an amino group. When producing a polyamide resin at a high polymerization temperature, if oxalic acid itself is used as a raw material, oxalic acid may be thermally decomposed. Derived compounds are preferred.

Examples of oxalic acid diesters of aromatic alcohols include diphenyl oxalate.

These oxalic acid compounds can be added alone or in combination of two or more during the production of a polyamide resin using the oxalic acid compound as a raw material.

Moreover, dicarboxylic acid compounds other than oxalic acid compounds can be used as raw materials for the polyamide resin using oxalic acid compounds as raw materials.

These dicarboxylic acid compounds other than these oxalic acid compounds can be added singly or in combination of two or more when the polyamide resin is produced.

The content of units derived from dicarboxylic acid and / or polyvalent carboxylic acid other than oxalic acid compound contained in polyamide resin using oxalic acid compound as raw material is the total dicarboxylic acid and total polyvalent content contained in polyamide resin using oxalic acid compound as raw material. The total amount of carboxylic acid-derived units is preferably less than 50 mol%, more preferably 20 mol% or less, further preferably 10 mol% or less, further preferably 5 mol% or less, and further preferably 1 mol% or less. preferable.

The diamine used in the polyamide resin made from the oxalic acid compound is not particularly limited, but ethylenediamine, propylenediamine, 1,4-butanediamine, 1,6-hexanediamine, 2-methyl-1,5-pentane. Diamine, 3-methyl-1,5-pentanediamine, 1,8-octanediamine, 1,9-nonanediamine, 2-methyl-1,8-octanediamine, 1,10-decanediamine, 5-methyl-1, Aliphatic diamines such as 9-nonanediamine, 1,12-dodecanediamine, 2,2,4-trimethyl-1,6-hexanediamine, 2,4,4-trimethyl-1,6-hexanediamine, cyclohexanediamine, methyl Cycloaliphatic diamine, isophorone diamine and other alicyclic diamines, p-phenylene diamine, m And aromatic diamines such as phenylenediamine, p-xylenediamine, m-xylenediamine, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylsulfone, and 4,4′-diaminodiphenylether. Alternatively, two or more kinds can be added during production.

Among these, from the relationship between the melting point and thermal decomposition temperature of the obtained polyamide resin, it is composed of 1,6-hexanediamine, 1,9-nonanediamine, 2-methyl-1,8-octanediamine and 1,10-decanediamine. At least one selected from the group is preferred, and 1,9-nonanediamine and 2-methyl-1,8-octanediamine are more preferred.

The molar ratio of 1,9-nonanediamine and 2-methyl-1,8-octanediamine is preferably 1:99 to 99: 1 from the viewpoint of increasing the molecular weight of the polyamide resin using a oxalic acid compound as a raw material, More preferably, it is 5:95 to 95: 5. Furthermore, from the viewpoint of the melting point of the obtained polyamide resin, the molar ratio of 1,9-nonanediamine and 2-methyl-1,8-octanediamine is 5:95 to 40:60 or 60:40 to 95: 5. It is preferably 5:95 to 30:70 or more preferably 70:30 to 90:10.

The content of 1,9-nonanediamine and 2-methyl-1,8-octanediamine is preferably 50 mol% or more, more preferably in the units derived from all diamines of the polyamide resin starting from the oxalic acid compound. Is 80 mol% or more, more preferably 90 mol% or more, further preferably 95 mol% or more, and more preferably 99 mol% or more.

Specific examples of polyamide resins made from oxalic acid compounds include homopolymers such as polyamide 92, polyamide 102, polyamide 122, and polyamide 62, and polyamide 92/62, polyamide 102/62, and polyamide 122/62. A copolymer is mentioned. These can use 1 type (s) or 2 or more types. Among these, at least one selected from the group consisting of polyamide 92, polyamide 102, polyamide 92/62, and polyamide 102/62 is preferable.

Polyamide resin using oxalic acid compound as a raw material has a relative viscosity of 2.3 or more and 6.0 in 96 mass% sulfuric acid in 1 mass% of polyamide resin at a temperature of 25 ° C. according to JIS K-6920. The following is preferable from the viewpoint of fluidity during molding and toughness of the molded product, more preferably 2.5 or more and 5.0 or less, and further preferably 2.7 or more and 4.0 or less.

(2) Manufacture of polyamide resin using oxalic acid compound as raw material The polyamide resin using oxalic acid compound used as a raw material for the present invention can be manufactured using any method known as a method for manufacturing polyamide resin. However, from the viewpoint of increasing the molecular weight and productivity, it is preferable to carry out a batch-wise or continuous polycondensation reaction of a dicarboxylic compound containing a diamine and an oxalic acid compound, more preferably a diamine and an oxalic acid compound. Is produced by a two-stage polymerization method comprising a pre-polycondensation step and a post-polycondensation step, or a pressure polymerization method described in WO2008-072754.

Specific examples of the two-stage polymerization method and the pressure polymerization method are as follows.

(2-1) Two-stage polymerization method (i) Pre-polycondensation step: First, the inside of the reactor is purged with nitrogen, and then a diamine and a dicarboxylic compound containing an oxalic acid compound are mixed. In the case of mixing, a solvent in which both a diamine and a dicarboxylic compound containing an oxalic acid compound are soluble may be used. As a solvent in which both the diamine and the oxalic acid compound are soluble, toluene, xylene, trichlorobenzene, phenol, trifluoroethanol and the like can be used, and particularly, toluene can be preferably used. For example, after heating the toluene solution which melt | dissolved diamine to 50 degreeC, oxalic acid diester is added with respect to this.

The charging ratio of the dicarboxylic compound containing the diamine and the oxalic acid compound is 0.8 to 1.5 (molar ratio) in terms of the high molecular weight in terms of the molar amount of the dicarboxylic acid (a) / the molar amount of the diamine (b). The ratio is preferably 0.91 to 1.1 (molar ratio), more preferably 0.99 to 1.01 (molar ratio).

The temperature inside the reactor charged in this way is increased under normal pressure while stirring and / or nitrogen bubbling. The reaction temperature is preferably controlled so that the final temperature reaches 80 to 150 ° C., preferably 100 to 140 ° C. The reaction time at the final temperature reached is 3-6 hours.

(Ii) Post-polycondensation step: In order to further increase the molecular weight, the polymer produced in the pre-polycondensation step is gradually heated in the reactor under normal pressure. In the temperature raising process, the final ultimate temperature of the pre-polycondensation step, that is, preferably 80 to 150 ° C., is finally preferably 150 to 350 ° C., more preferably 180 to 330 ° C., and further preferably 200 ° C. A temperature range of 320 ° C. or lower is reached.

(2-2) Pressurized polymerization method First, diamine is placed in a pressure-resistant vessel and purged with nitrogen, and then heated to the reaction temperature under a sealing pressure. Thereafter, the dicarboxylic compound containing the oxalic acid compound is injected into the pressure vessel while maintaining the sealed pressure state at the reaction temperature, and the polycondensation reaction is started. The reaction temperature is not particularly limited as long as the polyamide resin produced by the reaction of the dicarboxylic compound containing diamine and oxalic acid compound can maintain a slurry or solution state and does not thermally decompose. The charging ratio of the dicarboxylic compound containing the diamine and the oxalic acid compound is 0.8 to 1.5 (molar ratio), preferably 0.91 to 1.1, in terms of the molar amount of the dicarboxylic compound containing the oxalic acid compound / the molar amount of the diamine. (Molar ratio), more preferably 0.99 to 1.01 (molar ratio).

Next, while keeping the inside of the pressure vessel in a sealed pressure state, the temperature is raised to a temperature not lower than the melting point of the polyamide resin and not pyrolyzed. For example, in the case of Component a, since the melting point is 245 to 300 ° C., the temperature is raised to 250 to 350 ° C., preferably 255 to 340 ° C., more preferably 260 to 335 ° C. The pressure in the pressure-resistant container until reaching the predetermined temperature is adjusted to approximately 0.1 MPaG, preferably 1 MPaG to 0.2 MPaG, from the saturated vapor pressure of the alcohol to be generated. After reaching the predetermined temperature, the pressure is released while distilling off the produced alcohol, and the polycondensation reaction is continued under normal pressure nitrogen flow or reduced pressure as necessary. The preferable final pressure in the case of carrying out the vacuum polymerization is 13.3 Pa or more and less than 0.1 MPa.

(3) Polyamide resin other than polyamide resin using oxalic acid compound as raw material Polyamide resin other than polyamide resin using oxalic acid compound as raw material includes, for example, polycaprolactam (polyamide 6), polyundecanoic acid lactam (polyamide 11), and polylauryl. Lactam (polyamide 12), polyethylene adipamide (polyamide 26), polytetramethylene succinamide (polyamide 44), polytetramethylene glutamide (polyamide 45), polytetramethylene adipamide (polyamide 46), polytetramethylene Azelamide (polyamide 49), polytetramethylene sebamide (polyamide 410), polytetramethylene dodecamide (polyamide 412), polypentamethylene succinamide (polyamide 54), polypentamethylene glutata Amide (polyamide 55), polypentamethylene adipamide (polyamide 56), polypentamethylene azelamide (polyamide 59), polypentamethylene sebacamide (polyamide 510), polypentamethylene dodecamide (polyamide 512), polyhexa Methylene succinamide (polyamide 64), polyhexamethylene glutamide (polyamide 65), polyhexamethylene diaminoadipamide (polyamide 66), polyhexamethylene azelamide (polyamide 69), polyhexamethylene sebacamide (polyamide 610) ), Polyhexamethylene dodecamide (polyamide 612), polynonamethylene adipamide (polyamide 96), polynonamethylene azelamide (polyamide 99), polynonamethylene sebamide (polyamide 910), poly Namethylene Dodecamide (Polyamide 912), Poly Decamethylene Adipamide (Polyamide 106), Poly Decamethylene Azelamide (Polyamide 109), Poly Decamethylene Decamide (Polyamide 1010), Poly Decamethylene Dodecamide (Polyamide 1012), Polydodecamethylene adipamide (polyamide 126), polydodecamethylene azelamide (polyamide 129), polydodecamethylene sebamide (polyamide 1210), polydodecamethylene dodecamide (polyamide 1212), caprolactam / hexamethylenediaminoadipic acid Copolymer (polyamide 6/66), caprolactam / hexamethylene diamino azelaic acid copolymer (polyamide 6/69), caprolactam / hexamethylene diamino sebacic acid copolymer (polymer) Amide 6/610), caprolactam / hexamethylenediaminoundecanoic acid copolymer (polyamide 6/611), caprolactam / hexamethylenediaminododecanoic acid copolymer (polyamide 6/612), caprolactam / aminoundecanoic acid copolymer (polyamide) 6/11), caprolactam / lauryl lactam copolymer (polyamide 6/12), caprolactam / hexamethylenediaminoadipic acid / lauryllactam (polyamide 6/66/12), caprolactam / hexamethylenediaminoadipic acid / hexamethylenediaminosebacin Acid (polyamide 6/66/610) and caprolactam / hexamethylenediaminoadipic acid / hexamethylenediaminododecanedicarboxylic acid (polyamide 6/66/612). These can use 1 type (s) or 2 or more types.

[Glass fiber]
Although the glass fiber used for this invention is not specifically limited, From a viewpoint of improving the adhesiveness of glass fiber and resin, it is preferable that it is converged with the convergence material.

The converging material is not particularly limited, but is preferably a urethane resin and / or an acrylic resin from the viewpoint of compatibility with the polyamide resin. In the case of other convergent materials, the compatibility with the polyamide resin is not sufficient, and the physical properties and the like may decrease.

The glass fiber used in the present invention is not particularly limited, but when the average fiber diameter is 3 μm or more and 13 μm or less and outside the range of 3 μm or more and 13 μm or less, the dimensional stability and mechanical properties of the molded article of the present invention are deteriorated. . From the viewpoint of further improving the dimensional stability, mechanical properties, and sliding properties of the molded article of the present invention, 5 μm or more and 12 μm or less is preferable, and 6 μm or more and 11 μm or less is more preferable.

The average fiber diameter of the glass fiber can be measured according to JIS R3420.

The glass fiber is preferably surface-treated with a surface treatment agent from the viewpoint of adhesiveness with the polyamide resin. Examples of the surface treatment agent include silane compounds, chromium compounds, titanium compounds, and the like, and surface treatment agents of silane compounds and / or titanium compounds are preferable.

As the surface treatment agent for the silane compound, an aminosilane coupling agent excellent in adhesion to the sizing agent is preferable. For example, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ -Aminopropyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropyltriethoxysilane, γ-aminodithiopropyltrihydroxysilane, γ- (polyethyleneamino) propyltrimethoxysilane, N-β- (aminopropyl) -γ-aminopropylmethyldimethoxysilane, N- (trimethoxysilylpropyl) -ethylenediamine, γ-dibutylaminopropyltrimethoxysilane, etc. It is done. These can use 1 type (s) or 2 or more types.

Surface treatment agents for titanium compounds include isopropyl triisostearoyl titanate, isopropyl tri (N-aminoethyl) titanate, isopropyl tris (dioctyl pyrophosphate) titanate, tetraisopropyl bis (dioctyl phosphite) titanate, tetraisopropyl titanate, tetraisopropyl titanate, Butyl titanate, tetraoctyl bis (ditridecyl phosphite) titanate, isopropyl trioctanoyl titanate, isopropyl tridodecyl benzene sulfonyl titanate, isopropyl tri (dioctyl phosphate) titanate, bis (dioctyl pyrophosphate) ethylene titanate, isopropyl dimethacrylisostearoyl titanate Tetra (2,2-diallyloxymethyl-1-buty ) Bis (ditridecylphosphite) titanate, isopropyl tricumylphenyl titanate, bis (dioctyl pyrophosphate) oxy acetate titanate, and isopropyl isostearoyl diacryl titanate. These can use 1 type (s) or 2 or more types.

Among these, at least selected from the group consisting of N-β- (aminoethyl) γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) γ-aminopropylmethyldimethoxysilane and γ-aminopropyltriethoxysilane. One is preferred.

[Composition]
The composition of this invention contains the polyamide resin which uses an oxalic acid compound as a raw material, and a specific glass fiber.

From the viewpoint of improving mechanical properties and slidability with respect to the total amount of the composition, the composition of the present invention includes 10% by mass or more and 80% by mass or less of glass fiber, and from the viewpoint of further improving physical properties and slidability, The glass fiber is preferably contained in an amount of 15% by mass or more and 60% by mass or less, and more preferably 20% by mass or more and 50% by mass or less.

The composition of the present invention preferably contains 20% by mass to 90% by mass of the polyamide resin with respect to the total amount of the composition. From the viewpoint of mechanical properties and slidability, the polyamide resin is 40% by mass to 85% by mass. % Or less, more preferably 50% by mass or more and 80% by mass or less.

Furthermore, the composition of the present invention preferably contains cuprous iodide, potassium iodide and melamine, and the total amount of cuprous iodide, potassium iodide and melamine is 0.1% by mass or more. The content is preferably 2.0% by mass or less, more preferably 0.2% by mass or more and 1.0% by mass or less, and further preferably 0.25% by mass or more and 0.38% by mass or less. The mass ratio of cuprous iodide, potassium iodide and melamine (cuprous iodide: potassium iodide: melamine) is preferably 2 to 4:40 to 60: 1 to 3. It is more preferably 5 to 3.5: 45 to 55: 1.5 to 2.5.

The composition of the present invention preferably contains a fatty acid metal from the viewpoint of moldability, and preferably contains 100 ppm or more and 300 ppm or less of the fatty acid metal with respect to the total amount of the composition.

Examples of the fatty acid metal include zinc stearate, calcium stearate, barium stearate, aluminum stearate, magnesium stearate, lithium stearate, calcium laurate, zinc linoleate, calcium ricinoleate, and zinc 2-ethylhexoate. From the viewpoint of properties, at least one selected from the group consisting of lithium stearate, calcium stearate and sodium stearate is preferred.

In the composition of the present invention, various additives, modifiers, reinforcing materials such as heat stabilizers, antioxidants, UV absorption, etc., which are usually blended within the range that does not impair the properties of the composition of the present invention. Agents, weathering agents, fillers, plasticizers, foaming agents, antiblocking agents, tackifiers, sealability improvers, anti-clouding agents, mold release agents, crosslinking agents, foaming agents, flame retardants, colorants (pigments, dyes Etc.), inorganic reinforcing materials such as coupling agents and glass fibers.

The composition of the present invention can contain a thermoplastic resin other than the polyamide resin within a range not impairing the properties of the composition of the present invention. As the thermoplastic resin other than the polyamide resin, a high-density polyethylene (HDPE) can be used. ), Medium density polyethylene (MDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), ultra high molecular weight polyethylene (UHMWPE), polypropylene (PP), ethylene / propylene copolymer (EPR), ethylene / Polyolefin resins such as butene copolymer (EBR), acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, mesaconic acid, citraconic acid, glutaconic acid, cis-4-cyclohexene-1 , 2-dicarboxylic acid, endobicyclo- [2.2.1] -5-heptene Carboxyl groups such as 2,3-dicarboxylic acid and metal salts thereof (Na, Zn, K, Ca, Mg), maleic anhydride, itaconic anhydride, citraconic anhydride, endobicyclo- [2.2.1] -5 -Compounds containing functional groups such as epoxy groups such as acid anhydride groups such as heptene-2,3-dicarboxylic acid anhydride, glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate, glycidyl itaconate, glycidyl citraconic acid Modified by the above-mentioned polyolefin resin, polybutylene terephthalate (PBT), polyethylene terephthalate (PET), polyether resin such as polyphenylene oxide (PPO), polyphenylene sulfide (PPS), polymethacrylonitrile, acrylonitrile / styrene copolymer Polymer (AS), Metallic Ronitoriru / styrene copolymer, acrylonitrile / butadiene / styrene copolymer (ABS).

The production method of the composition of the present invention is not particularly limited, and usually the following production methods can be mentioned. A method using a mixer such as a cylindrical mixer, a method using a twin screw extruder, a single screw extruder, a multi screw extruder, a Banbury mixer, a roll mixer, a kneader or the like, a combination of a mixer and an extruder The manufacturing method etc. can be mention | raise | lifted.

The composition of the present invention is preferably used for slidable parts because it has low dimensional stability, coefficient of friction, and wear during actual use.

[Molding]
Examples of the method for forming the composition of the present invention into a molded product include injection molding and extrusion molding. Among these, the method by injection molding is preferable.

As a molded product formed by molding the polyamide resin composition of the present invention, an injection molded product is preferable. Among the injection molded products, sliding parts are preferable, and among the sliding parts, one type selected from the group consisting of gears, pulleys, cams and bearings is preferable.

(First invention)
Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto.

[Physical property measurement, molding, evaluation method]
Molding and measurement were performed by the following methods.

(1) Relative viscosity (ηr)
The relative viscosity was measured at 25 ° C. with an Oswald viscometer using a solution in which the solvent was 96% by mass sulfuric acid and the polyamide resin concentration was 1.0 g / dl.

(2) Preparation of test piece The obtained resin composition was put into an injection molding machine, and a test piece was prepared at a resin temperature of 300 ° C and a mold temperature of 95 ° C. The dimensions of the test piece were 128 mm × 12.7 mm × 6.2 mm for the test specimen for measuring the deflection temperature under load, 100 mm × 30 mm × 1 mm for the test piece for measuring water absorption, and 80 mm × 80 mm × for the test piece for electrical characteristics. 3 mm.

(3) Deflection temperature under load (thermal deformation temperature)
Based on ASTM D648, the load deflection temperature of the test piece was measured at a load of 1.82 MPa.

(4) Impact strength (with Charpy notch)
The impact strength of the test piece was measured at a temperature of 23 ° C. according to ASTM D6110.

(5) Saturated water absorption rate The test piece was immersed in distilled water at 23 ° C., the mass of the test piece was measured, and the rate of change in the mass of the test piece lasted 3 times every 5 days within a range of 0.2%. In this case, it is determined that the absorption of water in the test piece has reached saturation, and the following equation is obtained from the mass (Zg) of the test piece before immersion in water and the mass (Yg) of the test piece when saturation is reached. The saturated water absorption (%) was calculated from (1).
Saturated water absorption (%) = (Y−Z) / Z × 100 (1)

(6) Electrical characteristics In accordance with IEC60250, the dielectric constant and dielectric loss tangent of a test piece at a frequency of 1 MHz are measured using a dielectric loss measuring device TR-10C manufactured by Ando Electric Co., Ltd. in an environment of 23 ° C. and 50% RH. did.

[Polyamide resin (A)]
・ Polyamide 92
Into a pressure vessel with an internal volume of about 150 L equipped with a raw material inlet, a nitrogen gas inlet, a pressure outlet, a stirrer, a thermometer, a torque meter, a pressure gauge, a pressure regulator, and a polymer outlet directly connected to a pump, a diamine ( b) 1,9-nonanediamine 20.1 kg (127 mol) and 2-methyl-1,8-octanediamine 3.5 kg (22 mol) were charged, and the pressure vessel was pressurized to 0.5 MPaG with nitrogen gas. Then, after repeating the operation of releasing nitrogen gas to normal pressure and replacing with nitrogen, the system was heated while stirring under a sealing pressure. After the internal temperature was raised to 150 ° C. over about 1 hour, 30.2 kg (149 mol) of dibutyl oxalate dicarboxylic acid (a) was supplied into the reaction vessel at a flow rate of 1.49 L / min by a pump and the temperature was raised at the same time. The internal pressure in the pressure vessel immediately after the supply increased to 0.35 MPaG by butanol produced by the polycondensation reaction, and the temperature of the polycondensate increased to about 170 ° C. Thereafter, the temperature was raised to 235 ° C. Meanwhile, the internal pressure was adjusted to 1.0 MPaG while extracting the generated butanol from the pressure release port. Immediately after the temperature of the polycondensate reached 235 ° C., butanol was extracted from the pressure relief port, and the internal pressure was brought to normal pressure. From the normal pressure, the temperature was raised while flowing nitrogen gas at 1.5 L / min, the temperature of the polycondensate was adjusted to 260 ° C., and the reaction was continued at 260 ° C. until the torque value reached a constant value. Thereafter, the stirring is stopped and the inside of the system is pressurized to 1 MPaG with nitrogen and allowed to stand, and then released to an internal pressure of 0.5 MPaG. Polyamide 92 (hereinafter sometimes referred to as PA92) is drawn from the lower outlet of the pressure vessel. Extracted into a shape. The string-like PA92 was immediately cooled with water and pelletized by a pelletizer. The relative viscosity was 3.13. In the obtained PA92, the content of units derived from the succinic acid compound is 100 mol% in the total amount of units derived from all dicarboxylic acids contained in PA92, and 1 in the total amount of units derived from all diamine (b), The total content of units derived from 9-nonanediamine and 2-methyl-1,8-octanediamine is 100 mol%, and the molar ratio of 1,9-nonanediamine and 2-methyl-1,8-octanediamine is 83:17 to 86:14.

・ Polyamide 92/62
Into a pressure vessel with an internal volume of about 150 L equipped with a raw material inlet, a nitrogen gas inlet, a pressure outlet, a stirrer, a thermometer, a torque meter, a pressure gauge, a pressure regulator, and a polymer outlet directly connected to a pump, a diamine ( b) 1,9-nonanediamine 10.5 kg (66.4 mol), 2-methyl-1,8-octanediamine 1.8 kg (11.6 mol) and 1,6-hexamethylenediamine 8.3 kg (71 0.0 mol), the pressure vessel was pressurized to 0.5 MPaG with nitrogen gas, and then the operation of releasing the nitrogen gas to normal pressure was repeated five times to perform nitrogen substitution, and then stirred under a sealing pressure. The temperature inside the system was increased. After the internal temperature was raised to 170 ° C. over about 1 hour, 30.2 kg (149 mol) of dibutyl oxalate of dicarboxylic acid (a) was supplied into the reaction vessel at a flow rate of 1.49 L / min with a pump, and the temperature was raised at the same time. The internal pressure in the pressure vessel immediately after the supply increased to 0.35 MPaG by butanol generated by the polycondensation reaction, and the temperature of the polycondensate increased to about 190 ° C. Thereafter, the temperature was raised to 250 ° C. Meanwhile, the internal pressure was adjusted to 0.5 MPaG while the generated butanol was extracted from the pressure release port. Immediately after the temperature of the polycondensate reached 250 ° C., butanol was extracted from the pressure relief port, and the internal pressure was brought to normal pressure. From the normal pressure, the temperature was raised while flowing nitrogen gas at 1.5 L / min, the temperature of the polycondensate was changed to 270 ° C., and the reaction was continued at 270 ° C. until the torque value became a constant value. Thereafter, the stirring was stopped, the inside of the system was pressurized to 1 MPaG with nitrogen and allowed to stand, then the pressure was released to an internal pressure of 0.5 MPaG, and the polyamide resin (A-2) (hereinafter sometimes referred to as PA92 / 62). A string was extracted from the lower outlet of the pressure vessel. The string-like PA92 / 62 was immediately cooled with water and pelletized by a pelletizer. The relative viscosity was 2.78. In the obtained PA92 / 62, in the total amount of units derived from all dicarboxylic acids contained in PA92 / 62, the content of the unit derived from oxalic acid compound is 100 mol%, and in the total amount of units derived from all diamine (b) In addition, the total content of units derived from 1,9-nonanediamine, 2-methyl-1,8-octanediamine, and 1,6-hexamethylenediamine is 100 mol%, and 1,9-nonanediamine, The weight ratio of -methyl-1,8-octanediamine and 1,6-hexamethylenediamine is 50: 8.8: 41.2 to 52: 9.2: 38.8.

[Polyphenylene ether resin]
-Polyphenylene ether modified with fumaric acid The polyphenylene ether resin is a polyphenylene ether modified with fumaric acid, Zarek (registered trademark) CX-1 (hereinafter also referred to as fumaric acid-modified PPE) manufactured by Idemitsu Kosan Co., Ltd. Was used.

[Example 1]
70 mass% of PA92 and 30 mass% of fumaric acid-modified PPE are fed to a twin screw extruder, melt-kneaded under conditions of a cylinder temperature of 300 ° C., extruded as a strand, cooled and solidified, and then put into a pelletizer. To obtain a pellet-shaped resin composition. The pellet of the obtained resin composition was dried. Test pieces of dried pellets were prepared, and the deflection temperature under load, impact strength, saturated water absorption, dielectric constant, and dielectric loss tangent were measured. The results are shown in Table 1.

[Example 2]
The procedure was the same as Example 1 except that PA92 was changed to 50% by mass and fumaric acid-modified PPE was changed to 50% by mass. The results are shown in Table 1.

[Example 3]
Example 1 was repeated except that PA92 / 62 was used instead of PA92. The results are shown in Table 1.

[Example 4]
Example 2 was repeated except that PA92 / 62 was used instead of PA92. The results are shown in Table 1. The results are shown in Table 1.

[Comparative Example 1]
A specimen of PA92 was prepared, and the deflection temperature under load, impact strength, saturated water absorption, dielectric constant, and dielectric loss tangent were measured. The results are shown in Table 1.

[Comparative Example 2]
A specimen of PA92 / 62 was prepared, and the deflection temperature under load, impact strength, saturated water absorption, dielectric constant and dielectric loss tangent were measured. The results are shown in Table 1.

[Comparative Example 3]
1015B (hereinafter also referred to as PA6), which is polyamide 6 manufactured by Ube Industries, Ltd., was used instead of PA92, and the same procedure as in Example 1 was carried out except that kneading was performed at a cylinder temperature of 280 ° C. The results are shown in Table 1.

[Comparative Example 4]
The same procedure as in Example 1 was carried out except that polyamide 66 manufactured by Ube Industries, Ltd. instead of PA92 and 2020B (hereinafter also referred to as PA66) was used and kneaded at a cylinder temperature of 290 ° C. The results are shown in Table 1.

[Comparative Example 5]
Kneading was performed under the same conditions as in Example 1 at a ratio of 40% by mass of PA92 and 60% by mass of the fumaric acid-modified PPE, but a strand that was a string-like resin composition could not be obtained.

[Comparative Example 6]
Kneading was carried out under the same conditions as in Example 1 at a ratio of 40% by mass of PA92 / 62 and 60% by mass of the fumaric acid-modified PPE, but a strand that was a string-like resin composition could not be obtained.

[Comparative Example 7]
The test piece of fumaric acid-modified PPE had poor molding processability of fumaric acid-modified PPE, and the test piece could not be produced.

(Second invention)
Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples. However, the present invention is not limited to the following examples as long as the gist of the present invention is not exceeded. Various evaluation methods and materials used are shown below.

(1) Dimensional stability Using a SE100D injection molding machine manufactured by Sumitomo Heavy Industries, Ltd., a test piece of 200 mm × 40 mm × 3 mmt in FIG. 1 was prepared, and the test piece was subjected to conditions of 23 ° C. and humidity 50% RH. The weight change due to water absorption was measured at intervals of about 400 hours, and the time when equilibrium was reached was defined as the saturated water absorption. The distance between the marking lines in the test piece was measured with an OLYMPUS microscope, and the dimensional stability was calculated by the following equation. MD indicates dimensional stability in the A direction (flow direction) in FIG. 1, and TD indicates dimensional stability in the B direction (vertical direction) in FIG.
Dimensional stability = (Distance between mold marking lines-Distance between marking lines in test specimen) / Distance between mold marking lines x 100

(2) Limit PV value Using a SE100D injection molding machine manufactured by Sumitomo Heavy Industries, Ltd., creating a test piece of 100 mm × 30 mm × 3 mm and placing it under conditions of 23 ° C. and humidity 50% RH for 500 hours or more In accordance with the JIS K7218A method, a Suzuki friction friction tester was used, using a ring with an outer diameter of 25.6 mm, an inner diameter of 20 mm, and a height of 15 mm, which is S45C carbon steel described in JIS standard G4051. The limit PV value of the specimen is a ring-on-plate method, the test speed is 500 mm / s, the test load is multiplied by 20 kgf (196 N) at the start of the test, and the load is increased by 20 kgf (196 N) every 10 minutes. And measured. The load immediately before the load at which the test piece was melted was defined as the limit PV value.

(3) Coefficient of dynamic friction Using the above-mentioned limit PV value measuring device, the sliding speed is applied by applying a constant load of 500 mm / s and 20 kgf (196 N) by the ring-on-plate method in the same manner as the measurement of the limit PV value. Was measured under conditions of 3 km and 5 km. The dynamic friction coefficient was calculated from the following equation.
Coefficient of dynamic friction = (friction resistance) / (load applied to specimen)

(4) Amount of wear Using the above-mentioned limit PV value measuring device, measurement is performed under the same conditions as the measurement of the dynamic friction coefficient, and the amount of wear is determined from the difference between the weight of the test piece before the measurement and the weight of the test piece after the measurement. Was calculated.
Amount of wear = (weight of specimen before measurement) − (weight of specimen after measurement)

[material]
(1) Polyamide resin made from oxalic acid compound (polyamide 92)
Into a pressure vessel with an internal volume of about 150 L equipped with a raw material inlet, a nitrogen gas inlet, a pressure outlet, a stirrer, a thermometer, a torque meter, a pressure gauge, a pressure regulator, and a polymer outlet directly connected to a pump, a diamine ( b) 1,9-nonanediamine 20.1 kg (127 mol) and 2-methyl-1,8-octanediamine 3.5 kg (22 mol) were charged, and the pressure vessel was pressurized to 0.5 MPaG with nitrogen gas. Then, after repeating the operation of releasing nitrogen gas to normal pressure and replacing with nitrogen, the system was heated while stirring under a sealing pressure. After the internal temperature was raised to 150 ° C. over about 1 hour, 30.2 kg (149 mol) of dibutyl oxalate dicarboxylic acid (a) was supplied into the reaction vessel at a flow rate of 1.49 L / min by a pump and the temperature was raised at the same time. The internal pressure in the pressure vessel immediately after the supply increased to 0.35 MPaG by butanol produced by the polycondensation reaction, and the temperature of the polycondensate increased to about 170 ° C. Thereafter, the temperature was raised to 235 ° C. Meanwhile, the internal pressure was adjusted to 1.0 MPaG while extracting the generated butanol from the pressure release port. Immediately after the temperature of the polycondensate reached 235 ° C., butanol was extracted from the pressure relief port, and the internal pressure was brought to normal pressure. From the normal pressure, the temperature was raised while flowing nitrogen gas at 1.5 L / min, the temperature of the polycondensate was adjusted to 260 ° C., and the reaction was continued at 260 ° C. until the torque value reached a constant value. Thereafter, the stirring is stopped and the inside of the system is pressurized to 1 MPaG with nitrogen and allowed to stand, and then released to an internal pressure of 0.5 MPaG. Polyamide 92 (hereinafter sometimes referred to as PA92) is drawn from the lower outlet of the pressure vessel. Extracted into a shape. The string-like PA92 was immediately cooled with water and pelletized by a pelletizer. The relative viscosity was 3.13. In the obtained PA92, the content of units derived from the succinic acid compound is 100 mol% in the total amount of units derived from all dicarboxylic acids contained in PA92, and 1 in the total amount of units derived from all diamine (b), The total content of units derived from 9-nonanediamine and 2-methyl-1,8-octanediamine is 100 mol%, and the molar ratio of 1,9-nonanediamine and 2-methyl-1,8-octanediamine is 83:17 to 86:14.
(2) Polyamide resins other than polyamide resins made from oxalic acid compounds (polyamide 66)
Polyamide 66 (PA66-1) (hereinafter sometimes referred to as (PA66-1))
A polyamide 66 having a relative viscosity of 2.6 to 2.8 measured in 96 mass% sulfuric acid in a polyamide concentration of 1 mass% and a temperature of 25 ° C. according to JIS K-6920.
Polyamide 66 (PA66-2) (hereinafter sometimes referred to as (PA66-2))
Polyamide 66 having a relative viscosity of 3.2 to 3.4 measured in 96 mass% sulfuric acid in a polyamide resin concentration of 1 mass% and a temperature of 25 ° C. according to JIS K-6920.

(3) Glass fiber / glass fiber (GF-1) (hereinafter sometimes referred to as (GF-1))
ECS03T-251DE manufactured by Nippon Electric Glass Co., Ltd., which is a glass fiber having an average fiber diameter of 6.5 μm, was used.
Glass fiber (GF-2) (hereinafter sometimes referred to as (GF-2))
ECS03T-251H manufactured by Nippon Electric Glass Co., Ltd., which is a glass fiber having an average fiber diameter of 10.5 μm, was used.
Glass fiber (GF-3) (hereinafter sometimes referred to as (GF-3))
ECS03T-289DE manufactured by Nippon Electric Glass Co., Ltd., which is a glass fiber having an average fiber diameter of 6.5 μm, was used.
Glass fiber (GF-4) (hereinafter sometimes referred to as (GF-4))
ECS03T-289 manufactured by Nippon Electric Glass Co., Ltd., which is a glass fiber having an average fiber diameter of 13.0 μm, was used.

[Examples 1 and 2, Comparative Examples 1 and 2]
The polyamide resin and glass fiber described in Table 2 were kneaded by a 44 mmφ vented twin-screw extruder set at a barrel temperature of 260 ° C. at the ratio described in Table 2, pelletized by a pelletizer, and the composition pellets were Obtained.
Next, the pellets of the obtained composition were dried at 110 ° C. and 10 Torr (1330 Pa) for 24 hours, and then injection molded at a cylinder temperature of 260 ° C. and a mold temperature of 80 ° C. to obtain various test pieces. The obtained test piece was evaluated by the above evaluation method. The results are shown in Table 2.

From the results shown in Table 2, it is clear that the composition containing polyamide resin and glass fiber made from an oxalic acid compound is excellent in dimensional stability and wear resistance.

The resin composition containing the polyamide resin and the polyphenylene ether resin of the first invention has low water absorption, excellent heat resistance and molding processability, and low dielectric constant and dielectric loss tangent. . The resin composition of the present invention can be used in a wide range of fields such as electric / electronic parts, OA parts, vehicle parts, and machine parts.
The composition of 2nd invention can be used conveniently as various sliding members, such as a motor vehicle, an electric / electronic, an industrial material, an industrial material, daily necessities, and household goods.

Claims

A resin composition comprising a polyamide resin (A) and a polyphenylene ether resin;
The polyamide resin (A) includes a unit derived from a dicarboxylic acid (a) and a unit derived from a diamine (b),
The dicarboxylic acid (a) contains an oxalic acid compound,
The diamine (b) includes two or more diamines selected from the group consisting of 1,6-hexanediamine, 1,9-nonanediamine and 2-methyl-1,8-octanediamine;
The resin composition whose content of the said polyphenylene ether resin is less than 60 mass% with respect to the total amount of the said polyamide resin (A) and the said polyphenylene ether resin.
The resin composition according to claim 1, wherein the diamine (b) contains 1,9-nonanediamine and 2-methyl-1,8-octanediamine.
The resin composition according to claim 1, wherein the diamine (b) contains 1,6-hexanediamine, 1,9-nonanediamine and 2-methyl-1,8-octanediamine.
The molar ratio of the total of the 1,9-nonanediamine and 2-methyl-1,8-octanediamine to the 1,6-hexanediamine is 5.1: 94.9 to 99: 1. The resin composition as described.
The resin composition according to any one of claims 2 to 4, wherein a molar ratio of the 1,9-nonanediamine and the 2-methyl-1,8-octanediamine is 5:95 to 95: 5.
The resin composition according to any one of claims 1 to 5, wherein the dicarboxylic acid (a) is an oxalic acid diester.
A molded article produced using the resin composition according to any one of claims 1 to 6.
A composition comprising a polyamide resin and glass fibers;
The composition for a sliding part, wherein the polyamide resin includes a polyamide resin made of an oxalic acid compound as a raw material.
A composition comprising a polyamide resin and glass fibers;
The polyamide resin includes a polyamide resin using a oxalic acid compound as a raw material,
The composition whose fiber diameter of the said glass fiber is 3 micrometers or more and 13 micrometers or less.
The composition according to claim 8, wherein the fiber diameter of the glass fiber is 3 µm or more and 13 µm or less.
The composition according to any one of claims 8 to 10, comprising 10% by mass to 80% by mass of glass fiber based on the total amount of the composition.
A sliding part comprising the composition according to any one of claims 8 to 11.
The sliding component according to claim 12, wherein the sliding component is a gear.