JP2013095801A - Polyamide resin composition for electrophotographing device component and electrophotographing device component obtained by molding the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyamide resin composition for an electrophotographing device component including a polyamide resin whereby, in comparison with a conventional aliphatic polyamide resin, sufficient relative viscosity ηr, a wider moldable temperature range, heat resistance and melt-moldability, and reduction in the number of molding cycles can be achieved and an electrophotographing device component excellent in chemical resistance, hydrolysis resistance, and fuel barrier properties can be molded without deteriorating low water absorbability; and to provide an electrophotographing device component obtained by molding the polyamide resin composition and equipped with excellent heat resistance at high temperatures and excellent chemical resistance to various chemicals.SOLUTION: The polyamide resin composition for an electrophotographing device component includes the polyamide resin (component A) and a conductive filler (component B). The component A is produced by binding a unit derived from a dicarboxylic acid to a unit derived from a diamine, wherein the dicarboxylic acid includes an oxalic acid (compound a), the diamine includes a 1,6-hexanediamine (compound b) and a 2-methyl-1,5-pentanediamine (compound c), and the molar ratio of the compound b to the compound c is 99:1 to 50:50.

Description

  The present invention relates to a polyamide resin composition for an electrophotographic apparatus component and an electrophotographic apparatus component obtained by molding the same.

Hereinafter, the name of the polyamide resin may be based on JIS K 6920-1.
Crystalline polyamides such as nylon 6 (PA6) and nylon 66 (PA66) are widely used as textiles for clothing, industrial materials, or general-purpose engineering plastics because of their excellent properties and ease of melt molding. However, on the other hand, problems such as changes in physical properties due to water absorption, acid, high-temperature alcohol, deterioration in hot water, etc. have been pointed out, and there is an increasing demand for polyamides with better dimensional stability and chemical resistance. ing.

  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). It is expected to be used in fields where the use of conventional polyamides, where changes in physical properties have become a problem, is difficult.

So far, polyoxamide resins using various aliphatic linear diamines as diamine components have been proposed. For example,
Non-Patent Document 1 discloses a polyoxamide resin using 1,6-hexanediamine as a diamine component,
Non-Patent Document 2 discloses a polyoxamide resin (hereinafter also referred to as PA92) in which the diamine component is 1,9-nonanediamine,
Patent Document 2 discloses a polyoxamide resin using various diamine components and dibutyl oxalate as a dicarboxylic acid ester,
Patent Document 3 discloses a polyoxamide resin using two kinds of diamines of 1,9-nonanediamine and 2-methyl-1,8-octanediamine as a diamine component in a specific ratio.

JP 2006-57033 A Japanese National Patent Publication No. 5-506466 WO2008 / 072754

S. W. Shalaby, J. et al. Polym. Sci. , 11, 1 (1973) L. Franco, et al. , Macromolecules, 31, 3912 (1998).

However,
Regarding the polyoxamide resin disclosed in Non-Patent Document 1, the melting point (about 320 ° C.) is close to the thermal decomposition temperature (1% weight loss temperature in nitrogen; about 310 ° C.), so that melt polymerization and melt molding are difficult. It is not something that can withstand practical use,
The polyoxamide resin disclosed in Non-Patent Document 2 discloses a production method and crystal structure when diethyl oxalate is used as the oxalic acid source, and PA92 obtained here has an intrinsic viscosity of 0.97 dL / g. , A polymer having a melting point of 246 ° C., and only a low molecular weight body that cannot be formed into a tough molded body has been obtained,
Regarding the polyoxamide resin disclosed in Patent Document 2, it is shown that PA92 having an intrinsic viscosity of 0.99 dL / g and a melting point of 248 ° C. is produced, but the low molecular weight is such that a tough molded body cannot be molded. There is a problem that only the body is obtained,
Regarding the polyoxamide resin disclosed in Patent Document 3, a polyoxamide resin using two kinds of diamines of 1,9-nonanediamine and 2-methyl-1,8-octanediamine as a diamine component in a specific ratio is shown. However, these polyoxamide resins have a wide moldable temperature range, excellent moldability, and low water absorption, chemical resistance, hydrolysis resistance, fuel barrier properties, etc., but the melting point is around 240 ° C., Heat resistance is slightly inferior for electrical and electronic equipment applications that require molding cycle properties and a high melting point.
In addition, when these conventional polyoxamide resins are used as materials for electrophotographic apparatus parts such as various belts and rolls used in electrophotographic apparatuses such as copying machines, printers and fax machines, the conductivity and surface under high-temperature heat treatment The smoothness and mechanical properties were not sufficiently maintained.

The problem to be solved by the present invention is:
Compared with conventional polyoxamide resin,
Melting point Tm (° C.) measured by differential scanning calorimetry measured at a rate of temperature increase of 10 ° C./min under a nitrogen atmosphere and measurement at a rate of temperature increase of 10 ° C./min under a nitrogen atmosphere Moldable temperature estimated from temperature difference (Td-Tm) (° C.) (hereinafter also referred to as temperature difference (Td-Tm)) from 1% weight loss temperature Td (° C.) (thermal decomposition temperature) in thermogravimetric analysis Wide,
Excellent heat resistance estimated from melting point Tm,
It has an appropriate melt viscosity and excellent melt moldability, and the molding cycle can be reduced.
Electrophotographic device parts with superior heat resistance, chemical resistance, hydrolysis resistance, and fuel barrier properties compared to conventional aliphatic polyamide resins without compromising the low water absorption found in aliphatic linear polyoxamide resins A polyamide resin composition for an electrophotographic apparatus component containing a polyamide resin that can be molded, and an electrophotographic apparatus component that is obtained by molding the composition and has excellent conductivity, surface smoothness, and mechanical properties at high temperatures. Is to provide.

The present invention
(1) A polyamide resin composition for an electrophotographic apparatus component comprising a polyamide resin (component A) and a conductive filler (component B),
The component A is composed of a unit derived from a dicarboxylic acid and a unit derived from a diamine,
The dicarboxylic acid comprises oxalic acid (compound a);
The diamine comprises 1,6-hexanediamine (compound b) and 2-methyl-1,5-pentanediamine (compound c);
A polyamide resin composition for an electrophotographic apparatus component in which the molar ratio of the compound b to the compound c is 99: 1 to 50:50, and (2) the polyamide resin composition for an electrophotographic apparatus component described in (1) above. This is an electrophotographic apparatus part obtained by molding.

According to the present invention,
Sufficient relative viscosity ηr (high molecular weight) is achieved compared to conventional polyoxamide resin,
The moldable temperature range estimated from the temperature difference (Td−Tm) is wide.
Excellent heat resistance estimated from the melting point Tm,
It has an appropriate melt viscosity and excellent melt moldability, and the molding cycle can be reduced.
Electrophotographic device parts with superior heat resistance, chemical resistance, hydrolysis resistance, and fuel barrier properties compared to conventional aliphatic polyamide resins without compromising the low water absorption found in aliphatic linear polyoxamide resins A polyamide resin composition for an electrophotographic apparatus component containing a polyamide resin that can be molded, and an electrophotographic apparatus component that is excellent in stability at high temperatures of electrical conductivity, surface smoothness, and mechanical properties obtained by molding it. An electrophotographic apparatus component can be provided.

[Component A]
(1) Configuration of Component A Component A, which is a polyamide resin in the present invention,
The dicarboxylic acid component is succinic acid and the diamine component consists of 1,6-hexanediamine and 2-methyl-1,5-pentanediamine,
A polyamide resin formed by bonding a unit derived from a dicarboxylic acid and a unit derived from a diamine,
The dicarboxylic acid comprises oxalic acid (compound a);
The diamine comprises 1,6-hexanediamine (compound b) and 2-methyl-1,5-pentanediamine (compound c);
The molar ratio of the compound b to the compound c is 99: 1 to 50:50,
Preferably, the relative viscosity ηr measured at 25 ° C. using a solution of Component A having a concentration of 1.0 g / dl in 96% sulfuric acid is 1.8 to 6.0.

  Component A uses compounds a, b and c, preferably polycondensation using a mixture thereof, so that it has a high molecular weight, a high melting point, a large difference between the melting point and the thermal decomposition temperature, and excellent melt moldability. Furthermore, it is excellent in chemical resistance, hydrolysis resistance and fuel barrier properties as compared with conventional polyamides without impairing the low water absorption seen in linear polyoxamide resins.

From the viewpoint of ensuring chemical resistance, hydrolysis resistance and fuel barrier properties, component A has a molar ratio of compound b to compound c:
Preferably, 99: 1 to 55:45 mol%,
More preferably, it is 99: 1-60: 40 mol%.
Hereinafter, the molar ratio of the compound b and the compound c also means the molar ratio of the unit derived from the compound b and the unit derived from the compound c in the component A.

When compound a (oxalic acid) is directly used as a raw material in the production of component A, compound a (succinic acid) itself is thermally decomposed, and the melting point of component A exceeds the thermal decomposition temperature. (Hereinafter, also referred to as oxalic acid source) and obtained by polycondensation of oxalic acid derived from the oxalic acid source and diamine. This oxalic acid is derived from an oxalic acid source such as oxalic acid diester, and any oxalic acid may be used as long as it has reactivity with an amino group.
As the oxalic acid source, oxalic acid diester is preferable from the viewpoint of suppressing side reactions in the polycondensation reaction. Dimethyl oxalate, diethyl oxalate, di-n- (or i-) propyl oxalate, di-n- (or i-, or t-) oxalate Examples thereof include oxalic acid diesters of aliphatic monohydric alcohols such as butyl, oxalic acid diesters of alicyclic alcohols such as dicyclohexyl oxalate, and oxalic acid diesters of aromatic alcohols such as diphenyl oxalate.
Among the oxalic acid diesters, oxalic acid diesters of aliphatic monohydric alcohols having more than 3 carbon atoms, oxalic acid diesters of alicyclic alcohols, and oxalic acid diesters of aromatic alcohols are more preferable,
Among them, dibutyl oxalate and diphenyl oxalate are more preferable,
More preferred is dibutyl oxalate.

(2) Relative viscosity of component A
Using oxalic acid as compound a as the carboxylic acid component,
As the diamine component, 1,6-hexanediamine as compound b and 2-methyl-1,5-pentanediamine as compound c are polycondensed so that the melting point is preferably in the range of 200 to 330 ° C. Compared to a polyamide resin obtained by polycondensation of compound a and compound b with a melting point exceeding 330 ° C. (hereinafter also referred to as comparative component A2), in the melt polymerization in the post-polymerization step of component A described later, Since it is not necessary to use an excessively high temperature condition in which a side reaction occurs and inhibits high molecular weight, high molecular weight (increasing relative viscosity) is possible.
Therefore, Component A has an excellent melt moldability because it can increase the relative viscosity as compared with the conventional polyamide resin.
In view of avoiding the tendency of the molded product after melt molding to become brittle and lowering the physical properties, to avoid the tendency to increase the melt viscosity at the time of melt molding and deteriorate the molding processability, the relative viscosity ηr and the melt viscosity are more than a certain level. From the viewpoint of being suitable for uses such as automobile parts and electrical / electronic parts that are preferably high and not excessively high, a 96% concentrated sulfuric acid solution having a concentration of component A of 1.0 g / dl is used. The relative viscosity ηr measured at 25 ° C. is preferably 1.8 to 6.0, more preferably 1.8 to 4.5, more preferably 1.8 to 3.0, still more preferably. May be 1.85 to 2.5, more preferably 1.85 to 2.2.
In the melt polymerization in the post-polymerization step of component A described later, the relative viscosity ηr can be increased by increasing the degree of vacuum.

  From the same viewpoint, the melt viscosity of component A is preferably 100 to 700 Pa · s, more preferably 110 to 600 Pa · s, still more preferably 120 to 500 Pa · s, still more preferably 130 to 400 Pa · s, and further Preferably it is 150-300 Pa.s, More preferably, it is 160-220 Pa.s, More preferably, it is 170-200 Pa.s.

  Furthermore, from the same viewpoint, the number average molecular weight (Mn) of Component A is preferably 10,000 to 50,000, more preferably 11,000 to 40,000, and still more preferably 11,000 to 35,000.

The number average molecular weight (Mn) is based on the signal intensity obtained from the 1H-NMR spectrum, for example, dibutyl oxalate as the oxalic acid source, 1,6-hexanediamine (compound b) and 2-methyl-1, as the diamine component. In the case of a polyamide produced using 5-pentanediamine (compound c) at a molar ratio of 90:10 [hereinafter abbreviated as PX6-2 (compound b / compound c = 90/10)], it is calculated according to the following formula. did.
Mn = np × 170.21 + n (NH ₂ ) × 115.20 + n (OBu) × 129.13 + n (NHCHO) × 29.14
In addition, the measurement conditions of 1H-NMR are as follows.
・ Model used: Bruker Biospin AVANCE500
-Solvent: Bisulfuric acid-Integration frequency: 1024 times Each term in the above formula is defined as follows.
Np = Np / [(N (NH ₂ ) + N (NHCHO) + N (OBu)) / 2]
・ N (NH ₂ )
= N (NH ₂ ) / [(N (NH ₂ ) + N (NHCHO) + N (OBu)) / 2]
・ N (NHCHO)
= N (NHCHO) / [(N (NH ₂ ) + N (NHCHO) + N (OBu)) / 2]
・ N (OBu)
= N (OBu) / [(N (NH ₂ ) + N (NHCHO) + N (OBu)) / 2]
Np = Sp / sp-N (NHCHO)
N (NH ₂ ) = S (NH ₂ ) / s (NH ₂ )
N (NHCHO) = S (NHCHO) / s (NHCHO)
N (OBu) = S (OBu) / s (OBu)
However, each term has the following meaning.
Np: Total number of repeating units in the molecular chain excluding terminal units of PA62 (compound B / compound C = 90/10).
Np: the number of repeating units in the molecular chain per molecule.
Sp: PX6-2 (compound b / compound c = 90/10) excluding the signal based on the proton of the methylene group adjacent to the oxamide group in the repeating unit in the molecular chain (around 3.1 ppm) Integration value.
Sp: The number of hydrogens (4) counted in the integral value Sp.
· _N (NH 2): The total number of terminal amino groups of PX6-2 (Compound b / Compound c = 90/10).
N (NH ₂ ): number of terminal amino groups per molecule.
S (NH ₂ ): Integral value of a signal (around 2.6 ppm) based on the proton of the methylene group adjacent to the terminal amino group of PX6-2 (compound b / compound c = 90/10).
S (NH ₂ ): The number of hydrogens (2) counted in the integrated value S (NH ₂ ).
N (NHCHO): total number of terminal formamide groups of PX6-2 (compound b / compound c = 90/10).
N (NHCHO): number of terminal formamide groups per molecule.
-S (NHCHO): The integral value of the signal (7.8 ppm) based on the proton of the formamide group of PX6-2 (compound b / compound c = 90/10).
S (NHCHO): The number of hydrogens (one) counted in the integral value S (NHCHO).
N (OBu): the total number of terminal butoxy groups of PX6-2 (compound b / compound c = 90/10).
N (OBu): number of terminal butoxy groups per molecule.
S (OBu): integrated value of a signal (around 4.1 ppm) based on the proton of the methylene group adjacent to the oxygen atom of the terminal butoxy group of PX6-2 (compound b / compound c = 90/10).
S (OBu): The number of hydrogens (two) counted in the integral value S (OBu).

(3) Physical properties of component A Component A further changes the polycondensation ratio of compounds b and c,
The temperature difference (Td−Tm) is large compared to the comparative component A2, and small compared to the polyamide resin obtained by polycondensation of the compound a and the compound c (hereinafter also referred to as the comparative component A1).
The melting point Tm is low compared to the comparative component A2, high compared to the comparative component A1,
1% weight loss temperature Td is higher than the comparative component A1,
The saturated water absorption rate can be smaller than the comparative component A2 and larger than the comparative component A1.

That is, the component A is compared with the conventional polyoxamide resin,
Relative viscosity ηr (high molecular weight),
Moldable temperature range estimated from the temperature difference (Td−Tm),
Heat resistance estimated from melting point Tm,
Both melt moldability estimated from melt viscosity and low water absorption can be sufficiently secured.

  Component A has sufficient chemical resistance, resistance to resistance due to the high polymerization ratio (molar ratio) of compound b after sufficiently ensuring the moldable temperature range, heat resistance, melt moldability and low water absorption. Particularly contributes to hydrolyzability and fuel barrier properties.

From the viewpoint of sufficiently ensuring all of the moldable temperature range, heat resistance, melt moldability and low water absorption,
Tm is preferably 260 to 330 ° C, more preferably 265 to 330 ° C,
Td is preferably 341 to 370 ° C, more preferably 345 to 370 ° C, still more preferably 350 to 365 ° C,
The temperature difference (Td−Tm) is preferably 10 to 95 ° C., more preferably 20 to 95 ° C., still more preferably 25 to 95 ° C.,
The saturated water absorption is preferably 0 to 2.4, more preferably 1 to 2.4, still more preferably 2 to 2.4, and still more preferably 2.3 to 2.4.

(4) Production of Component A Component A can be produced using any method known as a method for producing polyamide, but from the viewpoint of high molecular weight and productivity,
Preferably, it is obtained by polycondensation reaction of diamine and oxalic acid diester batchwise or continuously.
More preferably, the diamine and the oxalic acid diester are obtained 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.
More preferable two-stage polymerization method and pressure polymerization method are specifically shown by the following operations.

(4-1) Two-stage polymerization method (i) Pre-polycondensation step: First, the inside of the reactor is purged with nitrogen, and then diamine (compounds b and c) and oxalic acid diester which is the oxalic acid source of compound a are mixed. When mixing, a solvent in which both the diamine and the oxalic acid diester are soluble may be used. As a solvent in which both the diamine component and the oxalic acid source component are soluble, toluene, xylene, trichlorobenzene, phenol, trifluoroethanol, and the like can be used, and toluene is particularly 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.
At this time, the charging ratio between the oxalic acid diester and the diamine is 0.8 to 1.5 (molar ratio), preferably 0.91 to 1.1 (molar ratio), from the viewpoint of increasing the molecular weight. Ratio), more preferably 0.99 to 1.01 (molar ratio).

  The temperature in 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. From the final ultimate temperature of the pre-polycondensation step in the temperature rising process, that is, preferably from 80 to 150 ° C., finally,
The temperature is preferably 295 ° C. or higher and 350 ° C. or lower, more preferably 298 ° C. or higher and 345 ° C. or lower, more preferably 298 ° C. or higher and 340 ° C. or lower.
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. A preferable final pressure in the case of carrying out the vacuum polymerization is 13.3 Pa to 0.1 MPa.

(4-2) Pressurized polymerization method First, diamine is placed in a pressure vessel and purged with nitrogen, and then heated to the reaction temperature under a sealing pressure. Thereafter, 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 produced by the reaction of the diamine and the oxalic acid compound can maintain a slurry or solution state and does not thermally decompose. For example, in the case of Component a, the reaction temperature is preferably 150 ° C to 250 ° C. Here, the charging ratio of dibutyl oxalate and diamine is 0.8 to 1.5 (molar ratio), preferably 0.91 to 1.1 (molar ratio), in terms of the molar amount of dibutyl oxalate / total molar amount of diamine. More preferably, it is 0.99 to 1.01 (molar ratio).
Next, while maintaining 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 MPa, preferably 1 MPa to 0.2 MPa 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. A preferable final pressure in the case of carrying out the vacuum polymerization is 13.3 Pa to 0.1 MPa.

(5) Component which can be used as dicarboxylic acid in component A In component A, other dicarboxylic acid components other than compound a can be used within a range not impairing the effects of the present invention.
As other dicarboxylic acid components other than compound a (oxalic acid),
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, azelaic acid, sebacic acid , Aliphatic dicarboxylic acids such as suberic acid,
In addition, alicyclic dicarboxylic acids such as 1,3-cyclopentanedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid,
Further, terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,4-phenylenedioxydiacetic acid, 1,3-phenylenedioxydi Aromatic dicarboxylic acids such as acetic acid, dibenzoic acid, 4,4′-oxydibenzoic acid, diphenylmethane-4,4′-dicarboxylic acid, diphenylsulfone-4,4′-dicarboxylic acid, 4,4′-biphenyldicarboxylic acid These may be added alone, or any mixture thereof may be added during the polycondensation reaction.
Furthermore, polyvalent carboxylic acids such as trimellitic acid, trimesic acid, and pyromellitic acid can be used as long as melt molding is possible.
When other dicarboxylic acid components are used, the proportion thereof is 25 mol% or less, preferably 15 mol% or less, more preferably 10 mol% or less, and more preferably 5 mol% or less with respect to compound a (succinic acid). More preferably, it is more preferably 0 mol% (that is, the dicarboxylic acid component consists only of compound a). The molar ratio of the other dicarboxylic acid component to the compound a (succinic acid) also means the molar ratio of the unit derived from the compound a and the unit derived from the other dicarboxylic acid component in the component A.

In component A, other diamine components other than compounds b and c can be used within the range not impairing the effects of the present invention.
As other diamine components other than 1,6-hexanediamine and 2-methyl-1,5-pentanediamine, ethylenediamine, propylenediamine, 1,4-butanediamine, 1,9-nonanediamine, 2-methyl-1, 8-octanediamine, 1,8-octanediamine, 1,10-decanediamine, 1,11-undecanediamine,
1,12-dodecanediamine, 3-methyl-1,5-pentanediamine, 2,2,4-trimethyl-1,6-hexanediamine, 2,4,4-trimethyl-1,6-hexanediamine, 5- Aliphatic diamines such as methyl-1,9-nonanediamine,
Furthermore, alicyclic diamines such as cyclohexanediamine, methylcyclohexanediamine, and isophoronediamine,
Furthermore, aromatic diamines such as p-phenylenediamine, m-phenylenediamine, p-xylenediamine, m-xylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenylether ,
These may be added alone, or any mixture thereof may be added during the polycondensation reaction.
When other diamine components are used, the proportion thereof is 25 mol% or less, preferably 15 mol% or less, more preferably 10 mol% or less, still more preferably 5 mol% or less, with respect to compounds b and c. More preferably, it is 0 mol% (that is, the diamine component consists only of compounds b and c). In addition, the molar ratio of the other diamine component with respect to the compounds b and c also means the molar ratio of the units derived from the compounds b and c and the units derived from the other diamine components in the component A.

(6) Molding of component A As the molding method of component A, all known molding methods applicable to polyamide such as injection, extrusion, hollow, press, roll, foaming, vacuum / pressure air, and stretching can be used. From the viewpoint of shortening the molding cycle performance, it is particularly suitable for molding of electrophotographic apparatus parts, and can be processed into films, sheets, molded articles, fibers, etc. by these molding methods.

[Component B]
Since the electrophotographic apparatus component operates in an environment where static electricity is likely to be generated, the polyamide resin composition of the present invention is blended with Component B, which is a conductive filler, from the viewpoint of suppressing charging of the electrophotographic apparatus component.

  The conductivity means, for example, an electrical characteristic such that static electricity does not accumulate in an insulator such as a resin when an electrophotographic apparatus component operates in the electronic apparatus. Thereby, it is possible to dissipate static electricity generated when the electrophotographic apparatus component operates in the electronic apparatus.

The conductive filler referred to in the present invention includes all fillers added to impart conductive performance to the resin composition,
Examples include particles, flakes, and fibers.
From the viewpoint of ease of manufacturing pellets by melt kneading,
Particulate or fibrous carbon and / or metal are preferred,
More preferably, one or more conductive fillers selected from the group consisting of carbon black, carbon fiber, metal fiber,
Carbon black and / or carbon fiber are more preferable.

As the particulate filler, carbon black, graphite, or the like can be suitably used. As the flaky filler, aluminum flakes, nickel flakes, nickel-coated mica and the like can be suitably used.
As the fibrous filler, metal fibers such as carbon nanotubes, carbon nanofibers, carbon fibers, carbon-coated ceramic fibers, carbon whiskers, aluminum fibers, copper fibers, brass fibers, and stainless fibers can be suitably used.

The carbon black includes all carbon blacks generally used for imparting conductivity.
Preferred carbon blacks include acetylene black obtained by complete combustion of acetylene gas, ketjen black produced by furnace-type incomplete combustion using crude oil as raw material, oil black, naphthalene black, thermal black, lamp black, channel black. , Roll black, disk black and the like, but are not limited thereto.

Carbon black is produced in various carbon powders having different characteristics such as average particle diameter, specific surface area, DBP oil absorption, and ash content.
There is no particular limitation on the characteristics of the carbon black, but those having a good chain structure and a high aggregation density are preferred.
From the viewpoint of obtaining excellent electrical conductivity with a smaller amount, while ensuring the impact resistance stably, the size of the carbon black,
The average particle size is preferably 500 nm or less, more preferably 5 to 100 nm, still more preferably 10 to 70 nm, and the specific surface area (BET method) is 10 to 1500 m ² / g or more. it is preferred, more preferably 300~1500m ² / g or more, further preferably 500~1500m ² / g, DBP (dibutyl phthalate - g) oil absorption, it is 50~500ml / 100g or more Is preferably 100 to 500 ml / 100 g, more preferably 300 to 500 ml / 100 g or more.
As the average particle size, 100 arbitrary particles were selected by electron microscopy, and the arithmetic average value of these particle sizes was used.
The DBP oil absorption is measured by the method defined in ASTM-D2414.

From the viewpoint of ensuring conductivity stably,
The ash content of carbon black is preferably 0.5% or less, more preferably 0.3% or less,
The volatile content of carbon black is more preferably less than 1.0% by weight.

As the carbon fiber, pitch-based and PAN-based carbon fibers are used without limitation, but PAN-based carbon fibers are more preferable in view of properties such as physical properties and conductivity.

The fiber length before kneading of the carbon fiber may be a long fiber extending up to 1000 mm in addition to that of the short fiber depending on the use, but in the case of melt kneading for the purpose of pellet production,
Preferably it is 0.1-12 mm, more preferably 1-8 mm,
The fiber diameter before kneading of the carbon fibers is preferably 5 to 15 μm, and carbon fibers having a finer fiber diameter can also be used.

[Component C]
The resin composition of the present invention can produce an electrophotographic apparatus component that is excellent only in components A and B, and has excellent conductivity, surface smoothness, and mechanical properties at high temperatures. In applications where specific physical properties are required, it is preferable that the resin composition of the present invention further contains component C which is a layered silicate.
Moreover, the addition of layered silicate can improve the rigidity and mechanical properties of the electrophotographic apparatus parts produced from the resin composition of the present invention.

  The layered silicate is preferably a flat plate having a side length of 0.002 to 1 μm and a thickness of 6 to 20 mm. In addition, the layered silicate is preferably one in which each layer in the component A is uniformly dispersed with an interlayer distance of about 20 mm or more.

  Here, “interlayer distance” refers to the distance between the centroids of the plate-like layered silicate, and “uniformly dispersed” means that each layer exists mainly in a random state, and the layered silicate 50% by mass or more, preferably 70% by mass or more, is dispersed in a single layer without forming a multilayer.

The amount of the layered silicate is not particularly limited as long as the effect of the layered silicate is exerted, but the rigidity, weather resistance and / or heat resistance of the electrophotographic apparatus component, and the liquid or From the viewpoint of improving the barrier property against steam, and from the viewpoint of ensuring molding processability and impact resistance of the resin composition, with respect to 100 parts by mass of component A,
Preferably it is 0.05-10 mass parts, More preferably, it is 0.05-8 mass parts, More preferably, it is 0.05-5 mass parts.

  As a raw material of the said layered silicate, the layered phyllosilicate mineral comprised from the layer of magnesium silicate or an aluminum silicate, ie, the aluminum silicate phyllosilicate, or the magnesium silicate phyllosilicate can be illustrated. Specific examples include smectite clay minerals such as montmorillonite, saponite, beidellite, nontronite, hectorite, and stevensite, vermiculite, halloysite, and the like. It may be what was done.

  In order to disperse the layered silicate in component A, a swelling agent is usually used. The swelling agent has a role of expanding the interlayer of the clay mineral and a role of giving the clay mineral a force for taking up the interlayer polymer. In the present invention, it is preferable to use 1,6-hexanediamine and 2-methyl-1,5-pentanediamine as the swelling agent.

  The layered silicate is preferably pulverized using a mixer, a ball mill, a vibration mill, a pin mill, a jet mill, a beating machine, or the like to have a desired shape and size in advance.

  The method for adding the layered silicate is not particularly limited as long as the layered silicate can be uniformly dispersed in the component A. For example, when the raw material of the layered silicate is a multilayered clay mineral, as disclosed in JP-A-62-74957, the layered silicate is ionized with hydrochloric acid or the like, and a swelling agent such as, for example, 1,6-hexanediamine and 2-methyl-1,5-pentanediamine are added to widen the space between the layers of the layered silicate in advance. Subsequently, the raw material of component A can be introduce | transduced between the said layers, and also the said raw material can be polymerized between the said layers.

  Alternatively, using an organic compound as a swelling agent, the layers may be preliminarily spread to about 100 mm or more and melt-mixed with component A to disperse each layer in a polyamide resin.

[Polyamide resin composition for electrophotographic apparatus parts]
(Content of component A)
The polyamide resin composition for electrophotographic apparatus parts of the present invention (hereinafter also referred to as resin composition) has a good moldable temperature range, heat resistance, and melt molding for improving the productivity at the time of molding electrophotographic apparatus parts. From the viewpoint of ensuring the properties, and the electrophotographic apparatus parts stably ensure conductivity, surface smoothness and mechanical properties at high temperatures,
The content of Component A in the resin composition is preferably 50 to 100% by mass, more preferably 55 to 100% by mass, and still more preferably 60 to 100% by mass.

(Content of component B)
Since the blending amount of component B, which is a conductive filler, varies depending on the type of conductive filler used, it cannot be specified unconditionally, but from the viewpoint of balance between conductivity, fluidity, mechanical strength, etc.
Preferably it is 2-40 mass parts with respect to 100 mass parts of the whole resin containing a polyamide resin.
In the case of carbon black, from the viewpoint of the balance between conductivity and fluidity, with respect to 100 parts by mass of the entire resin including the polyamide resin,
More preferably, it is 2-30 weight part, More preferably, it is 2-15 weight part.
In the case of carbon fiber, from the viewpoint of the balance of conductivity, impact resistance and the smoothness (slidability) of the surface of the molded product, with respect to 100 parts by mass of the entire resin including the polyamide resin,
More preferably, it is 3-40 mass parts, More preferably, it is 5-35 mass parts, More preferably, it is 7-35 mass parts.

The conductivity required for the material for an electrophotographic apparatus component of the present invention may vary depending on the application, but considering that the surface resistance of the polyamide resin is about 10 ¹⁵ Ω, the conductivity of the resin composition of the present invention is It is preferably about 10 ¹ to 10 ¹² Ω, more preferably about 10 ³ to 10 ¹⁰ Ω, by blending the conductive filler.

(Content of component C)
The amount of the above-mentioned layered silicate ensures the viewpoint of improving the rigidity, weather resistance and / or heat resistance of the parts of the electrophotographic apparatus, and the barrier property against liquid or vapor, and the molding processability and impact resistance of the resin composition. From the viewpoint, with respect to 100 parts by mass of component A,
Preferably it is 0.05-10 mass parts, More preferably, it is 0.05-8 mass parts, More preferably, it is 0.05-5 mass parts.

(Other ingredients)
For electrophotographic apparatus parts, it is preferable to include the following as other components.

(1) Polymer other than Component A In the resin composition of the present invention, if necessary, in order to utilize the characteristics of each polymer,
Other polyamides other than component A, such as at least one polyamide selected from the group consisting of polyoxamides, aromatic polyamides, aliphatic polyamides and alicyclic polyamides, and / or polymers other than polyamides, such as thermoplastic polymers An elastomer can be included.

  The polymer other than component A is not particularly limited as long as it does not impair the effects of the present invention, but is preferably 0 to 50 parts by mass, more preferably 0 to 40 parts by mass, and still more preferably, relative to 100 parts by mass of component A. Is 0-30 parts by mass.

(2) Additive The resin composition of the present invention can contain an additive as long as the effects of the present invention are not impaired. Examples of additives include pigments, dyes, colorants, heat resistance agents, antioxidants, weathering agents, UV absorbers, light stabilizers, lubricants, crystal nucleating agents, crystallization accelerators, mold release agents, and antistatic agents. , Stabilizers such as plasticizers and copper compounds, antistatic agents, flame retardants, glass fibers, lubricants, fillers, reinforcing fibers, reinforcing particles, foaming agents and the like.

The method for adding the polymer and / or additive other than the above component A is not particularly limited as long as each method can be dispersed in component A, and the component can be added at any time that does not impair the effect. A can be added.
For example, polymers and / or additives other than component A
It can also be added during or after the polycondensation reaction of component A.

(3) Reinforcing fiber The resin composition of the present invention may be blended with a reinforcing fiber that does not have electrical conductivity from the viewpoint of ensuring resistance to deformation load received at high temperatures.

Examples of reinforcing fibers include inorganic fibers such as glass fibers and mineral fibers, and organic fibers such as aramid fibers that are tougher than polyamide resins. Glass fibers are preferred from the viewpoint of availability.
By blending the reinforcing fiber, physical properties such as strength and creep resistance of the composition are improved.

As inorganic fiber,
The fiber diameter is preferably 0.01 to 50 μm, more preferably 0.03 to 30 μm,
The fiber length is preferably 1 to 50 mm, more preferably 1 to 30 mm, still more preferably 1 to 20 mm,
Are preferably used.
However, when the polyamide resin composition of the present invention is melt-kneaded to shape the electrophotographic apparatus part, the inorganic fibers are cut and the like, and within the polyamide resin composition of the present invention or the electrophotographic apparatus part,
The fiber diameter of the inorganic fiber is 0.01-20 μm, preferably 0.03-15 μm,
The fiber length of the inorganic fibers may be about 0.5 to 10 mm, preferably about 0.7 to 5 mm.

  The blending ratio of the glass fiber ensures the effect of improving the rigidity and creep resistance of the molded body by the resin composition of the present invention stably, and stably secures the fluidity of the resin composition of the present invention to suppress short shots. From the viewpoint of ensuring a good surface condition, the amount is preferably 2 to 40 parts by weight, more preferably 2 to 38 parts by weight, and still more preferably 3 to 35 parts by weight with respect to 100 parts by weight of the resin composition of the present invention. Part.

  Component A has excellent mechanical strength, chemical resistance, low water absorption, hydrolysis resistance, etc., has a wide moldable temperature range, and excellent melt moldability. In addition, it is basically maintained as it is, and certain characteristics such as mechanical strength and heat resistance are improved by the addition of the reinforcing fiber.

[Electrophotographic equipment parts]
The electrophotographic apparatus component of the present invention is obtained by subjecting the resin composition of the present invention to, for example, injection molding, extrusion molding, blow molding, (press, roll) compression molding, hollow molding, foaming, vacuum / pressure air, stretch foaming, stretching, etc. It can be produced by molding in combination.
When compounding reinforcing fibers and inorganic particles,
Ingredients such as component A and the resin to be blended with the resin composition of the present invention and component B, and if necessary, component B in the resin that is pre-blended with reinforcing fibers or melt-kneaded in the middle of the molding machine For example, reinforcing fibers can be introduced.

  The electrophotographic component can be produced by molding the electrophotographic apparatus component of the present invention by, for example, injection molding, extrusion molding, blow molding, compression molding or the like.

The electrophotographic apparatus component of the present invention is preferably obtained by inflation extrusion from the viewpoint of productivity.
By this method, a molded product having an arbitrary diameter and a thickness of 30 to 1000 μm, more preferably 30 to 500 μm, and still more preferably 30 to 300 μm is obtained.
The parts of the electrophotographic apparatus formed in this way have no seams, and the electrophotographic apparatus such as an electrophotographic copying machine, an intermediate transfer belt used for a printer, a fax machine, a transfer conveying belt, etc. It is useful as a belt for photographic devices.
Similarly, a conductive roll for an electrophotographic apparatus can be obtained by coating an electrophotographic apparatus part formed into a cylindrical shape on a conductive support, and heating and fusing it.
Or it can also be set as an electroconductive roll by carrying out melt coating of the electroconductive polyamide composition continuously on an electroconductive support body with an extruder.
The conductive roll is useful as, for example, a cleaning roll, a charging roll, a developing roll, or a transfer roll.

Furthermore, the electrophotographic apparatus component of the present invention formed into a cylindrical shape with the above-described thickness has an average surface roughness Ra of 1 μm or less, and the ratio between the maximum value and the minimum value of the surface resistivity in the same plane is 10. It is desirable to be less than double.
When the electrophotographic apparatus component of the present invention is used for an intermediate transfer belt, a charging roll, a developing roll, a transfer roll, and the like because Ra is 1 μm or less, the sharpness of the generated image is remarkably improved.
Further, since the ratio of the maximum value and the minimum value of the surface resistivity in the same plane is 10 times or less, the parts of the electrophotographic apparatus of the present invention have a uniform attractive force for attracting toner and paper, and the intermediate transfer belt, transfer conveyance It can be used more suitably as an electrophotographic apparatus component such as a belt, a cleaning roll, a charging roll, a developing roll, and a transfer roll.
In order to set the Ra of the electrophotographic apparatus component to 1 μm or less, it is effective to set the temperature of the annular die at the time of molding slightly higher. Further, in order to suppress the ratio of the maximum value and the minimum value of the volume resistivity in the same plane of the electrophotographic apparatus component to 10 times or less, it is effective to suppress the aggregate size of the conductivity imparting agent to be small. Specifically, a method of forming the aggregate so that the average diameter thereof is 3 μm or less, more preferably 2 μm or less is effective.

[Examples and Comparative Examples]
In Production Examples 1 to 5, Component A was produced.
In Examples 1-1 to 4, 2-1, 3-1 to 5 and 4 to 1-3, the polyamide resin composition for an electrophotographic apparatus component of the present invention was produced.
In Examples 5-1 to 4, 6-1, 7-1 to 5 and 8-1 to 3, the electrophotographic apparatus parts of the present invention were produced.

(1) Production Example 1 (Component A: PX6-1)
In a pressure vessel with an internal volume of about 150 liters equipped with a stirrer, thermometer, torque meter, pressure gauge, raw material inlet directly connected with a diaphragm pump, nitrogen gas inlet, pressure outlet, pressure regulator and polymer outlet.
Mixture of compound a (1,6-hexanediamine) 15.407 kg (132.58 mol) and compound b (2-methyl-1,5-pentanediamine) 811.1 g (6.98 mol) (compound a and compound the molar ratio of b is 95: 5),
After pressurizing the interior of the pressure vessel to 0.5 MPa with nitrogen gas having a purity of 99.9999%,
Next, the operation of releasing nitrogen gas to normal pressure was repeated 5 times, and after nitrogen replacement,
The system was heated while stirring under a sealing pressure.
After bringing the temperature of dibutyl oxalate to 80 ° C. over about 30 minutes,
At the same time, 28.230 kg (139.56 mol) of dibutyl oxalate was supplied into the reaction vessel over about 17 minutes at a flow rate of 1.49 liters / minute by means of a diaphragm pump.
The internal pressure in the pressure vessel immediately after the supply increased to 0.35 MPa by butanol generated by the polycondensation reaction, and the temperature of the polycondensate increased to about 170 ° C.
Thereafter, the temperature was raised to 330 ° C. over 2 hours.
Meanwhile, the internal pressure was adjusted to 0.75 MPa while extracting the generated butanol from the pressure relief port. Immediately after the temperature of the polycondensate reached 330 ° C., butanol was extracted from the pressure relief port over about 20 minutes, and the internal pressure was brought to normal pressure.
From the normal pressure, the temperature was raised while flowing nitrogen gas at 1.5 liters / minute, and the reaction was carried out for 4.5 hours.
Thereafter, the stirring was stopped and the system was pressurized to 1 MPa with nitrogen and allowed to stand for about 10 minutes. Then, the pressure was released to an internal pressure of 0.1 MPa, and the polycondensate was extracted in a string form from the lower outlet of the pressure vessel.
The string-like polymer was immediately cooled with water, and the water-cooled string-like resin was pelletized with a pelletizer.
The obtained polyamide was a white tough polymer with ηr = 1.95.

(2) Production Example 2 (Component A: PX6-2)
A mixture of 14.717 kg (126.64 mol) of compound a and 1.635 kg (14.07 mol) of compound b (molar ratio of compound a and compound b is 90:10) is charged.
Except for charging 28.462 kg (140.71 mol) of dibutyl oxalate,
Reaction was carried out in the same manner as in Example 1 to obtain polyamide.
The obtained polyamide was a white tough polymer with ηr = 2.05.

(3) Production Example 3 (Component A: PX6-3)
A mixture of 12.16 kg (104.64 mol) of compound a and 5.212 kg (44.85 mol) of compound b (the molar ratio of compound a to compound b is 70:30) is charged.
At the same time, 30.238 kg (149.49 mol) of dibutyl oxalate was supplied into the reaction vessel by a diaphragm pump at a flow rate of 1.49 liters / minute over about 17 minutes.
The internal pressure in the pressure vessel immediately after the supply increased to 0.35 MPa by butanol generated by the polycondensation reaction, and the temperature of the polycondensate increased to about 170 ° C.
Thereafter, the temperature was raised to 290 ° C. over 1.5 hours.
Meanwhile, the internal pressure was adjusted to 0.5 MPa while extracting the generated butanol from the pressure relief port. Immediately after the temperature of the polycondensate reached 290 ° C., butanol was extracted from the pressure relief port over about 20 minutes, and the internal pressure was brought to normal pressure.
The temperature was raised from normal pressure while flowing nitrogen gas at 1.5 liters / minute, the temperature of the polycondensate was brought to 310 ° C. over about 1 hour, and the reaction was carried out at 310 ° C. for 1.5 hours. .
Thereafter, the stirring was stopped and the system was pressurized to 1 MPa with nitrogen and allowed to stand for about 10 minutes. Then, the pressure was released to an internal pressure of 0.1 MPa, and the polycondensate was extracted in a string form from the lower outlet of the pressure vessel.
The string-like polymer was immediately cooled with water, and the water-cooled string-like resin was pelletized with a pelletizer.
The obtained polyamide was a white tough polymer with ηr = 2.40.

(4) Production Example 4 (Component A: PX6-4)
A mixture of 10.294 kg (88.583 mol) of compound a and 6.863 kg (59.057 mol) of compound b (molar ratio of compound a to compound b is 60:40) is charged.
29.864 kg (147.64 mol) of dibutyl oxalate was supplied into the reaction vessel at a flow rate of 1.49 liter / min by a diaphragm pump over about 17 minutes, and the temperature was raised.
The internal pressure in the pressure vessel immediately after the supply increased to 0.35 MPa by butanol generated by the polycondensation reaction, and the temperature of the polycondensate increased to about 170 ° C.
Thereafter, the temperature was raised to 275 ° C. over 1.5 hours.
Meanwhile, the internal pressure was adjusted to 0.5 MPa while extracting the generated butanol from the pressure relief port.
Immediately after the temperature of the polycondensate reached 270 ° C., butanol was extracted from the pressure release port over about 20 minutes, and the internal pressure was brought to normal pressure.
From the normal pressure, the temperature was raised while flowing nitrogen gas at 1.5 liters / minute, the temperature of the polycondensate was changed to 290 ° C. over about 1 hour, and the reaction was carried out at 290 ° C. for 2 hours.
Thereafter, the stirring was stopped and the system was pressurized to 1 MPa with nitrogen and allowed to stand for about 10 minutes. Then, the pressure was released to an internal pressure of 0.1 MPa, and the polycondensate was extracted in a string form from the lower outlet of the pressure vessel.
The string-like polymer was immediately cooled with water, and the water-cooled string-like resin was pelletized with a pelletizer.
The obtained polyamide was a white tough polymer, and ηr = 2.68.

(5) Production Example 1-5 (Component A: PX6-5)
A mixture of 8.361 kg (71.947 mol) of compound a and 8.361 kg (71.947 mol) of compound b (molar ratio of compound a and compound b is 50:50),
At the same time, 29.107 kg (143.89 mol) of dibutyl oxalate was supplied into the reaction vessel at a flow rate of 1.49 liters / minute over about 17 minutes by a diaphragm pump.
The internal pressure in the pressure vessel immediately after the supply increased to 0.35 MPa by butanol generated by the polycondensation reaction, and the temperature of the polycondensate increased to about 170 ° C.
Thereafter, the temperature was raised to 260 ° C. over 1.5 hours.
Meanwhile, the internal pressure was adjusted to 0.5 MPa while extracting the generated butanol from the pressure relief port.
Immediately after the temperature of the polycondensate reached 260 ° C., butanol was extracted from the pressure release port over about 20 minutes, and the internal pressure was brought to normal pressure.
The temperature was raised from normal pressure while flowing nitrogen gas at 1.5 liters / minute, and the temperature of the polycondensate was changed to 275 ° C. over about 1 hour, and the reaction was carried out at 275 ° C. for 3 hours.
Thereafter, the stirring was stopped and the system was pressurized to 1 MPa with nitrogen and allowed to stand for about 10 minutes. Then, the pressure was released to an internal pressure of 0.1 MPa, and the polycondensate was extracted in a string form from the lower outlet of the pressure vessel.
The string-like polymer was immediately cooled with water, and the water-cooled string-like resin was pelletized with a pelletizer.
The obtained polyamide was a white tough polymer, and ηr = 2.61.

(6) Comparative Production Example 1: (Polyamide resin: PX6-6)
(I) Pre-polycondensation step: The inside of a 1 L separable flask equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, and a raw material inlet is replaced with nitrogen gas having a purity of 99.9999%.
500 ml of dehydrated toluene,
1,6-hexanediamine 58.7209 g (0.5053 mol) was charged.
After this separable flask was placed in an oil bath and heated to 50 ° C,
Dibutyl oxalate (102.1956 g, 0.5053 mol) was charged.
Next, the temperature of the oil bath was raised to 130 ° C., and the reaction was carried out for 5 hours under reflux.
Note that all operations from preparation of raw materials to completion of the reaction were performed under a nitrogen stream of 50 ml / min.
(Ii) Post-polycondensation step: The prepolymer obtained by the above operation is charged into a glass reaction tube having a diameter of about 35 mmφ equipped with a stirrer, an air cooling tube, and a nitrogen introduction tube, and the pressure inside the reaction tube is reduced to 13.3 Pa or less. Then, the operation of introducing nitrogen gas to normal pressure was repeated 5 times, and then the mixture was transferred to a salt bath maintained at 290 ° C. under a nitrogen stream of 50 ml / min. After the temperature of the salt bath was set to 340 ° C. over 1 hour, the pressure in the container was reduced to about 66.5 Pa, and the reaction was further continued for 2 hours.
Subsequently, after introducing nitrogen gas to normal pressure, it was removed from the salt bath and cooled to room temperature under a nitrogen stream of 50 ml / min to obtain a polyamide resin.
The obtained polymer was a yellow polymer, and ηr = 1.65.

(7) Comparative resin examples 1-2 and 3
As a polyamide resin of a resin composition for electrophotographic apparatus parts,
Pellets of nylon 6 (Ube Industries, UBE nylon 1015B: PA6) (Comparative Resin Example 1-2) and nylon 66 (Ube Industries, UBE nylon 2020B: PA66) (Comparative Resin Example 1-3) were used.

(8) Examples 1-1 to 4, 2-1, 3-1 to 5, Comparative Examples 1-1 and 2-1, Examples 4-1 to 4, 5-1, 6-1 to 5 and comparison Examples 4-1 and 5-1
(8-1) As the polyamide resin, PA6 and PA66 produced in Examples 1-1 to 5, conductive filler and layered silicate,
Carbon black (EC600JD made by Ketjen Black International),
Carbon fiber (Besfight HTA-C6NR (fiber diameter 7 μm) manufactured by Toho Tenax Co., Ltd.)
Organized montmorillonite (Nanocor, Nanomer 30TC)
Were used to prepare a mixture having the ratio shown in Table 2 (carbon black is described as CB).
Furthermore, each of these mixtures was used using a twin-screw kneader with a cylinder diameter of 40 mm (Tex44 twin-screw extruder manufactured by Nippon Steel).
When PX6-1 to PX3 are used as the polyamide resin, 340 ° C.,
300 ° C when PX6-4-5 is used as the polyamide resin,
In the case of using PA6 as the polyamide resin,
290 ° C when PA66 is used as the polyamide resin
The mixture was melt kneaded and extruded into strands, cooled in a water tank, and then pelletized as a resin composition of the present invention using a pelletizer.
(8-2) Using the pellets produced in (8-1) above, a seamless belt-like film having a thickness of 200 μm was prepared by an inflation extrusion molding method.
The inflation extrusion molding method uses an extruder with a screw diameter of 30 mm (cylinder temperature 250 to 340 ° C.) manufactured by Nippon Steel Co., Ltd., a take-off speed of 40 m / min, a die lip width of 2 mm, and a blow ratio of 1.2. A seamless belt-like film of 150 mm was produced.

Production Examples 1 to 5, Comparative Production Example 1, Comparative Resin Examples 2 to 3,
Examples 1-1 to 4, 2-1, 3-1 to 5, Comparative Examples 1-1 and 2-1,
Examples 4-1 to 4, 5-1, 6-1 to 5 and Comparative Examples 4-1 and 5-1
About polyamide resin in
Relative viscosity, melting point, 1% weight loss temperature, melt viscosity, saturated water absorption, chemical resistance, hydrolysis resistance, physical properties in dry and wet conditions, surface resistance value and tensile strength before and after treatment at 150 ° C. for 12 hours,
Examples 1-1 to 4, 2-1, 3-1 to 5, Comparative Examples 1-1 and 2-1,
The smoothness of the surface was measured for the seamless belt-like films in Examples 4-1 to 4, 5-1, 6-1 to 5 and Comparative Examples 4-1 and 5-1.
The results are shown in Tables 1 and 2.

[Physical property measurement, molding, evaluation conditions]
The following contents were used.

(1) Relative viscosity ηr of polyamide resin
ηr was measured at 25 ° C. using an Ostwald viscometer using 96% sulfuric acid solution (concentration: 1.0 g / dl) of each polyamide resin of Production Examples 1 to 5 and Comparative Production Examples 1 and 2.

(2) Melt Viscosity of Polyamide Resin The melt viscosities of the polyamide resins of Examples 1 to 5 and Comparative Production Examples 1 and 2 were measured using a 25 mm cone / cone measuring instrument ARES manufactured by TA Instruments Japan. Put the plate in nitrogen,
When PX6-1 to PX3 are used as the polyamide resin, 340 ° C.,
300 ° C when PX6-4-5 is used as the polyamide resin,
In the case of using PA6 as the polyamide resin,
The measurement was performed under conditions of a shear rate of 0.1 ^s-1 .

(3) Melting point of polyamide resin (Tm)
Tm of each polyamide resin of Production Examples 1 to 5, Comparative Production Example 1 and Comparative Resin Examples 2 to 3 was measured under a nitrogen atmosphere using PYRIS Diamond DSC manufactured by PerkinELmer.
Tm when PA 6-1 to 2 and 6 are included as the polyamide resin is
The temperature is raised from 30 ° C. to 350 ° C. at a rate of 10 ° C./min (referred to as a temperature rise first run),
After holding at 350 ° C for 3 minutes,
The temperature is decreased to -100 ° C at a rate of 10 ° C / min (referred to as a temperature decrease first run),
Next, the temperature was raised to 350 ° C. at a rate of 10 ° C./min (referred to as a temperature raised second run).
Tm when PA6-3-5, PA6 and PA66 are included as the polyamide resin is
The temperature is increased from 30 ° C. to 310 ° C. at a rate of 10 ° C./min (referred to as a temperature rising first run),
After holding at 310 ° C for 3 minutes,
The temperature is decreased to -100 ° C at a rate of 10 ° C / min (referred to as a temperature decrease first run),
Next, the temperature was raised to 310 ° C. at a rate of 10 ° C./min (referred to as a temperature rise second run).
The endothermic peak temperature of the elevated temperature second run was defined as Tm.

(4) 1% weight loss temperature Td of polyamide resin
Td of each polyamide resin of Production Examples 1 to 5, Comparative Production Example 1, and Comparative Resin Examples 2 to 3 was measured by thermogravimetric analysis (TGA) using THERMOGRAVIMETRIC ANALYZER TGA-50 manufactured by Shimadzu Corporation.
The temperature was raised from room temperature to 500 ° C. at a rate of 10 ° C./min under a nitrogen stream of 20 ml / min, and Td was measured.

(5) Test Film and Plate Molding Conditions (5-1) Test Film Film was formed using a vacuum press TMB-10 manufactured by Toho Machinery Co., Ltd. to obtain a saturated water absorption test film.
Under a reduced pressure atmosphere of 500 to 700 Pa,
In the case of using PA6-1-3 as the polyamide resin, 300 ° C.,
In the case of using PA 6-4 to 6 as the polyamide resin, 340 ° C.,
When PA6 is used as a polyamide resin,
290 ° C when PA66 is used as the polyamide resin
After 5 minutes of heating and melting,
The film was formed by pressing at 5 MPa for 1 minute.
Next, the reduced-pressure atmosphere was returned to normal pressure, and then cooled and crystallized at room temperature of 5 MPa for 1 minute to obtain a test film.

(5-2) Test plate Resin temperature When PA6-1 to PA6-3 are used as the polyamide resin,
In the case of using PA 6-4 to 6 as the polyamide resin, 340 ° C.,
When PA6 is used as a polyamide resin,
290 ° C when PA66 is used as the polyamide resin
A test plate was obtained by molding with an electrophotographic apparatus part having a mold temperature of 80 ° C.
The injection molding conditions were: injection pressure: primary pressure 650 kg / cm ² , injection time: 11 seconds, cooling time: 20 seconds.

(6) Saturated water absorption rate of polyamide resin or polyamide resin composition A test film (dimensions: 20 mm × 10 mm, thickness 0.25 mm; mass about 0.05 g) is immersed in ion-exchanged water at 23 ° C.,
The test film was taken out every predetermined time, and the mass of the film was measured.
When the rate of increase in the test film mass was continued three times within the range of 0.2%, it was determined that the absorption of moisture into the test film reached saturation,
The saturated water absorption (%) was calculated by the following formula (1) from the mass (Xg) of the test film before being immersed in water and the mass (Yg) of the test film when saturation was reached.
Saturated water absorption (%) = 100 × (Y−X) / X (1)
The water absorption rate (equilibrium water absorption) calculated by the formula (1) from the weight (Yg) immediately after forming the test film and the weight (Yg) when the film reached equilibrium at a humidity of 65% and a temperature of 23 ° C. after forming the film. Rate) is the wet water absorption.

(7) Chemical resistance of polyamide resin After the test film (dimensions: 20 mm × 10 mm, thickness 0.25 mm; mass about 0.05 g) was immersed in the chemicals listed below for 7 days, the weight residual ratio of the film (%) And changes in appearance were observed. Tests were conducted on samples immersed in concentrated hydrochloric acid, 64% sulfuric acid, 30% NaOH aqueous solution, and 5% K ₂ MnO ₄ at 23 ° C. and benzyl alcohol at 50 ° C.

(8) Hydrolysis resistance of polyamide resin A test film (dimensions: 20 mm × 10 mm, thickness 0.25 mm; mass about 0.05 g) was placed in an autoclave, and water (pH = 7), 0.5 mol / l The weight residual ratio (%) and appearance change after treatment for 60 minutes at 121 ° C. in sulfuric acid (pH = 1) or 1 mol / l sodium hydroxide aqueous solution (pH = 14) were examined.

(9) Mechanical properties of polyamide resin or polyamide resin composition
What was evaluated at 23 ° C. without conditioning immediately after molding was dried,
What was evaluated at 23 ° C. after conditioning at a humidity of 65% and a temperature of 23 ° C. after molding was described in the table as wet.

(9-1) Tensile strength: Measured according to ASTM D638 using a test plate formed into a dumbbell shape of a Type I test piece described in ASTM D638.
The tensile strength before and after the treatment at 150 ° C. for 12 hours is the tensile strength before and after the treatment at 150 ° C. for 12 hours. The specimen is placed in an oven in which a test plate formed into a dumbbell shape of a Type I test piece is set at 150 ° C. for 12 hours. , Measured according to ASTM D638.
(9-2) Flexural modulus: Measured according to ASTM D790 using a test plate.
(9-3) Deflection temperature under load (thermal deformation temperature): Measured with a load of 1.82 MPa in accordance with ASTM D648 using a test plate.

(10) Water absorption rate of polyamide resin Except that it was placed under conditions of 23 ° C. and humidity 65% RH using a test film (dimensions: 20 mm × 10 mm, thickness 0.25 mm; mass about 0.05 g). (6) The water absorption (%) was calculated according to the method for measuring saturated water absorption.

(11) Surface resistance value Using a 4261ALCR meter manufactured by Yokogawa Hewlett-Packard Co., the test plate was measured at three arbitrary locations at intervals of 1 cm, and the average value was determined.
The surface resistance value before and after the treatment at 150 ° C. for 12 hours was measured in accordance with ASTM D638 by placing the test piece in an oven in which a test plate formed into a dumbbell shape of Type I test piece was set at 150 ° C. for 12 hours.

(12) Smoothness of seamless belt-like film The average surface roughness of the seamless belt-like film was measured under the following conditions.
Using a Surfcom 570A type surface shape measuring device manufactured by Tokyo Seimitsu Co., Ltd., the average surface roughness of 5 mm in length was measured at a vertical magnification of 50000 times at the same position in the film width direction of the inflation film. A measuring needle having a radius of 5 μm was operated at a speed of 0.03 mm / s in the direction parallel to the molding direction. A case where the average surface roughness was 1 μm or less was evaluated as “◯”, and a case where the average surface roughness was larger than 1 μm was determined as “X”.

From Table 1, the polyamide resin composition for electrophotographic apparatus parts of the present invention has low water absorption compared to materials such as nylon 6 and nylon 66, excellent chemical resistance and hydrolysis resistance, and under wet conditions. It has excellent mechanical properties, and has a wider moldable temperature range than polyamide resin (PX6-6) using 1,6-hexanediamine alone as a diamine component, and is excellent in melt moldability. It can be seen that it can be molded to produce an electrophotographic apparatus component that is excellent in conductivity, surface smoothness and mechanical properties at high temperatures.
In addition, the polyamide resin composition using PX6-6 could not be melt-kneaded and molded because Td-Tm was small.

Claims (4)

A polyamide resin composition for an electrophotographic apparatus comprising a polyamide resin (component A) and a conductive filler (component B),
The component A is composed of a unit derived from a dicarboxylic acid and a unit derived from a diamine,
The dicarboxylic acid comprises oxalic acid (compound a);
The diamine comprises 1,6-hexanediamine (compound b) and 2-methyl-1,5-pentanediamine (compound c);
A polyamide resin composition for an electrophotographic apparatus component, wherein the molar ratio of the compound b to the compound c is 99: 1 to 50:50.   Furthermore, the polyamide resin composition for electrophotographic apparatus components of Claim 1 containing layered silicate (component C).   An electrophotographic apparatus part obtained by molding the polyamide resin composition for an electrophotographic apparatus part according to claim 1 or 2.   The electrophotographic apparatus component according to claim 3, wherein the electrophotographic apparatus component is a belt or a roll.