JPH1135184A - Separating claw for copying machine formed of polyimide resin crystallized in metal mold - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve surface smoothness, and improve a slidingly movable characteristic, eliminate the necessity of post-annealing, and remarkably reduce a cost by constituting a separating claw of a specific thermoplastic polyimide resin crystallized in a metal mold or this composition. SOLUTION: A separating claw is molded with a resin composition containing a thermoplastic crystalline polyimide resin, and is crystallized in a metal mold. The thermoplastic crystalline polyimide resin has a repetitive structural unit of formula I [in the formula, X1 represents direct bonding, -So2 -, -CO2 -, -C(CH3 )2 -, -C(CF3 )2 - or -S-. R1 , R2 , R3 and R4 represent respectively hydrogen, an alkyl group, an alkoxy group, a halogenated alkyl group, a halogenated alkoxy group or a halogen group. Y1 represents a group selected from a group composed of formula II] or the like. Two kinds or more are added from carbon black, a bisimide compound and a polyaryl ether ketone resin. Therefore, the necessity of post-annealing is eliminated, and it can contribute to cost reduction.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a separating claw for a copying machine comprising a thermoplastic polyimide resin which crystallizes in a mold or a thermoplastic polyimide resin composition which crystallizes in a mold.
It has excellent surface smoothness, good sliding characteristics, and does not require post-annealing, so that the cost is significantly reduced.

[0002]

2. Description of the Prior Art The present inventors have developed a separating claw for a copying machine, which is disclosed in Japanese Patent Application Laid-Open Nos. 62-236858 and 62-2.
Although thermoplastic polyimide is used as disclosed in Japanese Patent No. 53655, the crystallization rate in a mold is low, and it is difficult to obtain a crystallized product during injection molding. Even if it can be obtained, there are various problems such as the mold temperature being extremely high and the mold being seized at the time of molding and the product being deformed at the time of protrusion. However, the present inventors have found that the crystallization rate can be significantly improved by adding a specific graphite to a thermoplastic polyimide as disclosed in JP-A-07-190369. This time, the inventors of the present invention proposed a conventional method for producing a copying machine separation claw made of a thermoplastic polyimide resin which crystallizes in a mold or a thermoplastic polyimide resin composition which crystallizes in a mold (Japanese Patent Application Laid-Open No. 01-257784). The present invention has been completed by finding that the performance and manufacturing cost can be remarkably improved as compared with those obtained.

[0003]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a separating claw for a copying machine which has excellent surface smoothness, good sliding characteristics, does not require post-annealing, and significantly reduces the cost.

[0004]

SUMMARY OF THE INVENTION According to the present invention, a surface smoothness is improved by using a copying machine separating claw made of a thermoplastic polyimide resin which crystallizes in a mold or a thermoplastic polyimide resin composition which crystallizes in a mold. It has been found that a separation claw for a copying machine is obtained which has excellent sliding properties, does not require post-annealing, and significantly reduces the cost, thereby completing the present invention. That is, the present invention is specified by the following items [1] to [5].

[1] A crystalline polyimide resin having a repeating structural unit represented by the general formula (1) (Formula 13):

[0006]

Embedded image (X ₁ is a direct _{bond, -SO 2 -, - CO 2} -, - C (C
_{H 3) 2 -, - C} (CF 3) 2 -, or a -S-. R
₁ , R ₂ , R ₃ and R ₄ are each hydrogen, an alkyl group, an alkoxy group, a halogenated alkyl group, a halogenated alkoxy group or a halogen group. Y ₁ is the general formula (2)
It is at least one group selected from the group consisting of (Formula 14).

[0007]

Embedded image And / or a crystalline polyimide resin having a repeating structural unit of the general formula (3) (Formula 15)

[0008]

Embedded image (R ₅ and R ₆ are each a hydrogen, an alkyl group, an alkoxy group, a halogenated alkyl group, a halogenated alkoxy group, or a halogen group, and n is an integer of 0 to 4. Y ₂ is This is the same as the definition of Y _{1 in} the general formula (1).) For 100 parts by weight, carbon black as the component (A) and general formula (4) as the component (B)

[0009]

Embedded image (R ₇ represents a divalent aromatic group having 6 to 30 carbon atoms represented by X ₂
Is represented by the general formula (5)

[0010]

Embedded image Represents at least one divalent group selected from the group consisting of X ₃ is a direct bond, an ether bond, a sulfide bond, a hydrocarbon group having 1 to 10 carbon atoms, a carbonyl group,
Hexafluorinated isopropylidene group, having 6 to 6 carbon atoms
At least one member selected from the group consisting of 18 aromatic groups
Represents a species of divalent group. A) a bisimide compound represented by
And / or general formula (6)

[0011]

Embedded image (R ₈ is —C _n H _{2n + 1} — (n = 0 to 3) or a monovalent aromatic group having 6 to 30 carbon atoms, and Y ₃ is a general formula (7) )

[0012]

Embedded image And a tetravalent group consisting of Y ₄ represents a direct bond, an ether bond, a sulfide bond, a hydrocarbon group having 1 to 10 carbon atoms, a carbonyl group, a sulfonyl group, a hexafluorinated isopropylidene group, or an aromatic group having 6 to 18 carbon atoms. Represents at least one divalent group selected from the group consisting of: At least one of the bisimide compounds represented by
As component (C), a polyetheretherketone resin having a repeating structural unit represented by general formula (8):

[0013]

Embedded image A polyether ketone resin having a repeating structural unit of the general formula (9)

[0014]

Embedded image A polyether ketone ether ketone ketone resin having a repeating structural unit represented by the following general formula (10):

[0015]

Embedded image A polyether ketone ketone resin having a repeating structural unit represented by the following general formula (11):

[0016]

Embedded image Of at least one polyaryletherketone resin selected from the group consisting of component (A), component (B), and component (C), at least two components of 0.2 to 2
A separating claw for a copying machine, comprising a resin composition containing 00 parts by weight.

[2] The carbon black has a crystallite size (Lc) in the C-axis direction of 1 to 20 nm.
2. Separating claws for a copying machine described in 2.

[3] The bisimide compound has the general formula (1)
2) (Formula 24)

[0019]

Embedded image The separation claw for a copying machine according to [1] or [2], wherein

[4] With respect to 100 parts by weight of the resin composition,
Further comprising 5 to 100 parts by weight of fibrous reinforcing material,
The separating claw for a copying machine according to any one of [1] to [3].

[5] Separation for a copying machine characterized by using a thermoplastic crystalline polyimide resin that crystallizes in a mold and / or a thermoplastic crystalline polyimide resin composition that crystallizes in a mold. nail.

[0022]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention is obtained by molding a resin composition containing a thermoplastic crystalline polyimide resin and crystallizing it in a mold. Among the thermoplastic crystalline polyimide resins in the present invention, particularly, the general formula (13)

[0023]

Embedded image Polyimide (manufactured by Mitsui Toatsu Chemicals, Inc .: AU
RUM, melting point 388 ° C.) is optimal.

The resin composition used in the present invention has a mold temperature of 2
By molding at 50 ° C. or higher, it is completely crystallized in a mold. By completely crystallizing in a mold, the heat resistance inherent to the polyimide resin is exhibited, and a crystallized molded product with little dimensional change due to a method such as post-crystallization can be obtained. When using the resin composition, the mold temperature is in the range of 230 to 280 ° C. Preferably 240-2
It is in the range of 70C, more preferably in the range of 245-265C, most preferably in the range of 250-260C. 2
If the mold temperature exceeds 80 ° C., the molded product may not be released. At a mold temperature of less than 230 ° C., crystallization of the crystalline polyimide resin does not sufficiently proceed, and the heat resistance at a high temperature peculiar to the polyimide resin cannot be exhibited as it is. When a molded article is taken out in an amorphous state and then crystallized, deformation may increase with the post-crystallization, and a shape that can withstand use may not be maintained. Also, other thermoplastic crystalline polyimides that can be crystallized in a mold have no problem for use in the application of the present invention.

The melting point of the crystalline polyimide resin used in the resin composition used in the present invention is preferably from 250 ° C. to 500 ° C. More preferably at least 250 ° C and 450 ° C
It is as follows. If the temperature is lower than 250 ° C., a resin composition having high heat resistance cannot be obtained, which does not fit the gist of the present invention. On the other hand, at a temperature of 500 ° C. or more, the melting point is too high, and ordinary injection molding is difficult.

The amount of carbon black is 100
The appropriate amount is 0.1 to 50 parts by weight based on parts by weight. Preferably from 0.5 to 40 parts by weight, more preferably from 1 to 30 parts by weight.
Parts by weight. If the amount of the carbon black is less than 0.1 part by weight, the injection molding may not be completely crystallized with the resin composition depending on the kind of the crystalline polyimide resin and the carbon black. If it exceeds 50 parts by weight, problems such as a decrease in mechanical properties of the resin composition and a decrease in fluidity occur.

The average primary particle size of carbon black is 1 to 1
00 nm is appropriate. Preferably it is 1 to 80 nm, more preferably 10 to 80 nm. The smaller the average primary particle size of carbon black, the greater the effect of promoting crystallization of the resin. If it exceeds 100 nm, the effect of accelerating the crystallization of the resin is poor, and it is difficult to normally obtain carbon black having a thickness of 1 nm or less. Here, the average primary particle size is an average value of diameters of single particles of carbon black (particles forming aggregated particles). The crystallite size Lc in the C-axis direction of carbon black is appropriately in the range of 1 to 20 nm. Preferably it is 3 to 15 nm, more preferably 4 to 10 nm. The greater the Lc of the carbon black, the greater the effect of promoting crystallization of the resin. Lc is 1
If it is less than nm, the effect of accelerating the crystallization of the resin is poor, and it is usually difficult to obtain carbon black having a thickness of more than 20 nm. The C-axis direction means an axial direction perpendicular to a plane on the three-dimensional coordinates (hereinafter, referred to as a C-axis direction). Here, carbon black is effective as a crystal nucleating agent, but Lc is Even if graphite satisfying the above is used, the effect of the present resin composition cannot be exceeded. This is because graphite and carbon black have different average primary particle diameters and have a remarkable difference in the crystallization promoting effect.

The carbon black used in the present invention includes Mitsubishi Carbon Black (Mitsubishi Kasei Kogyo), Seast, Toka Black (Tokai Carbon), Denka Black (Denka), Ketjen (Akzo), RABEN (Colombian Carbon), Acetylene black or the like is used. Of these, talker black and acetylene black are preferred. Most preferred is Toka Black.
These carbon blacks are used alone or in combination of two or more.

The bisimide compounds used in the present invention are roughly classified into two types. One is a bisimide compound represented by the formula (C) (hereinafter, this type of bisimide compound is sometimes referred to as a type A bisimide compound), and the other is a bisimide compound represented by the formula (D) (hereinafter, this type of bisimide compound). The bisimide compound is sometimes referred to as a type B bisimide compound.) Among them, the general formula (12)

[0030]

Embedded image The bisimide compound represented by is particularly preferable. These bisimide compounds can be produced by the following reaction. That is, the type A bisimide compound is theoretically reacted with 1 mol of the diamine compound by 2 mol of dicarboxylic anhydride in an organic solvent in a conventional manner, and the type B bisimide compound is 1 mol of the diimide compound. Can be produced by a method in which 2 moles of a monoamine compound are theoretically reacted in an organic solvent with respect to the tetracarboxylic dianhydride. The reaction method is not particularly limited as long as a desired bisimide compound can be obtained.

Hereinafter, the production of the bisimide compound will be described in detail. The essential raw material compound used for obtaining the bisimide compound of the present invention is specifically o-phenylenediamine, m-phenylenediamine as a diamine compound used for production of a type A bisimide compound,
p-phenylenediamine, 1,3-bis (3-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (3-aminophenoxy) benzene, 1,4-bis ( 4-aminophenoxy)
Benzene, 4,4'-bis (3-aminophenoxy) biphenyl, 3,4'-bis (3-aminophenoxy) biphenyl, 3,3'-bis (3-aminophenoxy) biphenyl, 4,4'-bis (4-aminophenoxy) biphenyl, 3,4'-bis (4-aminophenoxy) biphenyl, 3,3'-bis (4-aminophenoxy) biphenyl and the like can be mentioned. Specific examples of the dicarboxylic anhydride include phthalic anhydride, 2,3-naphthalenedicarboxylic anhydride, 1,8-naphthalenedicarboxylic anhydride, and 2,3-anthracene dicarboxylic anhydride.

The tetracarboxylic dianhydride used for producing the type B bisimide compound includes pyromellitic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,4,4 3 ', 4'-biphenyltetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride and the like can be mentioned. In addition, aniline, p-toluidine, 4
-N-ethylaniline, 4-aminobiphenyl, 4-amino-p-terphenyl and the like. In the production of the type A or type B bisimide compound, the above-mentioned essential starting compounds are used, respectively.
Other diamine compounds as long as the effects of the bisimide compound in the present invention are not inhibited, dicarboxylic anhydride,
(Production of a type A bisimide compound), or a tetracarboxylic dianhydride or a monoamine compound (production of a type B bisimide compound) may be contained.

As the method for producing the bisimide compound, a known imidization reaction can be applied. The amount of the starting compound used is one of the diamino compound in the type A bisimide compound.
It is sufficient that the dicarboxylic anhydride is at least twice equivalent to the equivalent, but in consideration of the complexity of post-treatment, cost, etc., 2 to 2 equivalents are used.
It is desirable to use 2.5 times equivalent, more preferably in the range of 2.05 to 2.10 times. In the type B bisimide compound, it is sufficient that the monoamine is at least twice equivalent to 1 equivalent of tetracarboxylic dianhydride. It is desirable to use 5 times equivalent, more preferably in the range of 2.05 to 2.10 times. The reaction is particularly preferably performed in an organic solvent. The solvent used here is preferably N, N-
Although dimethylacetamide is used, other solvents that can be used include N, N-dimethylformamide, N, N-diethylacetamide, N, N-dimethoxyacetamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-
2-imidazolidinone, N-methylcaprolactam,
1,2-dimethoxyethane, bis (2-methoxyethyl) ether, 1,2-bis (2-methoxyethoxy)
Ethane, bis [2- (2-methoxyethoxy) ethyl]
Ether, tetrahydrofuran, 1,3-dioxane,
1,4-dioxane, pyrroline, picoline, dimethyl sulfoxide, dimethyl sulfone, tetramethylurea hexamethylphosphoramide, phenol, o-cresol, m-cresol, p-cresol, p-chlorophenol, anisole, benzene, toluene, Xylene and the like can be mentioned. These may be used alone or in combination of two or more.

The reaction temperature is usually 250 ° C. or lower, preferably 150 ° C. or lower. The reaction pressure is not particularly limited, and the reaction can be sufficiently performed at normal pressure. The reaction time varies depending on the type of the starting compound, the type of the solvent and the reaction temperature, and usually 4 to 24 hours is sufficient.

Further, as a method of imidation, bisamic acid as a precursor is heated to 100 to 300 ° C. to imidize it, or is chemically imidized using an imidizing agent such as acetic anhydride to obtain a bisamide acid. A bisimide compound having a structure in which two molecules of water are dehydrated from an acid is obtained. The amount of the bisimide compound is suitably 0.1 to 50 parts by weight based on 100 parts by weight of the crystalline polyimide resin. Preferably it is 0.5 to 40 parts by weight, more preferably 1 to 30 parts by weight, most preferably 10 to 20 parts by weight. If the amount of the bisimide compound is less than 0.1 parts by weight, the resin composition of the crystalline polyimide resin or the bisimide compound is insufficient because the injection molded product may not be completely crystallized in some cases. If it exceeds 50 parts by weight, problems such as a decrease in mechanical properties of the resin composition occur. As the polyaryletherketone resin used in the present invention, a general commercially available ordinary polyaryletherketone resin can be used without any problem. Specifically, polyetheretherketone (melting point 334 ° C.) represented by formulas (E) to (H),
Examples thereof include polyether ketone (melting point 373 ° C.), polyether ketone ether ketone ketone (melting point 371 ° C.), polyether ketone ketone (melting point 305 ° C. to 360 ° C.), and the like. These may be used alone or in combination of two or more.

The amount of the polyaryl ether ketone resin is suitably from 1 to 100 parts by weight based on 100 parts by weight of the crystalline polyimide resin. Preferably it is 20 to 90 parts by weight, more preferably 30 to 80 parts by weight. If the amount of the polyaryletherketone resin is less than 1 part by weight, the resin composition of the crystalline polyimide resin or the polyaryletherketone resin is insufficient because the injection-molded product may not be completely crystallized depending on the kind of the resin. If it exceeds 100 parts by weight, problems such as a decrease in mechanical properties of the crystalline polyimide resin composition occur.

The crystalline polyimide resin is selected from the group consisting of (1) carbon black, (2) bisimide compound, and (3) polyaryl ether ketone resin.
Add more than one type. (1) Carbon black and bisimide compound (2) Bisimide compound and polyaryl ether ketone resin (3) Both combinations of carbon black and polyaryl ether ketone resin are effective, but (4) carbon black, bisimide compound and poly It is most effective to add three kinds of aryl ether ketone resins in combination.

The total amount of (1) carbon black, (2) bisimide compound, and (3) polyaryl ether ketone resin is in the range of 0.2 to 200 parts by weight based on 100 parts by weight of the crystalline polyimide resin. Preferably it is in the range of 1 to 180 parts by weight, more preferably 5 to 150 parts by weight, most preferably 10 to 100 parts by weight.
If the amount is less than 0.2 parts by weight, depending on the type of the crystalline polyimide resin, carbon black, bisimide compound, or polyaryletherketone, the resin composition may not be completely crystallized from the injection-molded product, which is insufficient. Also 200
If the amount is more than 10 parts by weight, problems such as a decrease in mechanical properties and a decrease in fluidity of the resin composition occur.

In the present invention, an oligomer or dimer of a crystalline polyimide resin, an oligomer or dimer of a polyaryl ether ketone resin, an oligomer or dimer of a polyether nitrile resin, an oligomer or dimer of a polyphenylene sulfide resin, It is also possible to add a substance, all of which have a crystallization promoting effect. In addition, other thermoplastic resins can be added in an appropriate amount according to the purpose within a range not to impair the purpose of the present invention. Examples of the thermoplastic resin that can be blended include polyethylene, polypropylene, polystyrene, polycarbonate, polyester, polyamide, polyamideimide, polyphenylene ether, polyacetal, polyetherimide, polyethersulfone, and polysulfone.

It is also possible to mix a thermosetting resin. Examples of the thermosetting resin include a phenol resin and an epoxy resin. Furthermore, the incorporation of a filler is important in this application. As filler, silica stone powder,
Abrasion resistance improving materials such as molybdenum disulfide and fluororesin, carbon fiber, glass fiber, aromatic polyamide fiber, alumina fiber, boron fiber, silicon carbide fiber, potassium titanate whisker, aluminum borate whisker, carbon whisker, asbestos, metal Fibers, reinforcing materials such as ceramic fibers, flame retardant materials such as antimony trioxide, magnesium carbonate and calcium carbonate, materials for improving electric properties such as clay and mica, materials for improving tracking resistance such as asbestos and silica, barium sulfate, Acid resistance improving materials such as silica and calcium metasilicate, heat conductivity improving materials such as iron powder, zinc powder, aluminum powder, and copper powder, and other polybenzimidazole resins, silicon resins, glass beads, talc, diatomaceous earth, and alumina , Shirasubarun, hydrated alumina, metal oxide, colorant, release Agents, various stabilizers, plasticizers and the like. Of these, at least one selected from carbon fibers, glass fibers, whiskers (titanium oxide, aluminum borate, carbon, potassium titanate), talc, glass beads, glass flakes and silica is preferred.
The resin composition used in the present invention can be produced by a generally known method, but the following method is particularly preferable.

(1) Crystalline polyimide resin powder, carbon black, bisimide compound, polyaryletherketone resin powder, fibrous reinforcing material such as carbon fiber, and other additives are mortar, hensial mixer, drum blender, tumbler blender, The mixture is preliminarily mixed using a ball mill, a ribbon blender or the like, and then kneaded with a generally known melt extruder, melt mixer, hot roll, or the like, and then pelletized or powdered. (2) A crystalline polyimide resin powder, carbon black, a bisimide compound, a polyaryletherketone resin powder, and other additives are dissolved or suspended in an organic solvent in advance, and the solution or suspension is reinforced with fibrous materials such as carbon fibers. The material is immersed, then the solvent is removed in a hot air oven and then pelletized or powdered. In this case, examples of the solvent used include N, N-dimethylformamide, N, N-dimethylacetamide, N, N-diethylacetamide, N, N-dimethylmethoxyacetamide, N-methyl-2-pyrrolidone, 3-dimethyl-
2-imidazolidinone, N-methylcaprolactam,
1,2-dimethoxyethane, bis (2-methoxyethyl) ether, 1,2-bis (2-methoxyethoxy)
Ethane, bis [2- (2-methoxyethoxy) ethyl]
Ether, tetrahydrofuran, 1,3-dioxane,
Examples thereof include 1,4-dioxane, pyridine, picoline, dimethylsulfoxide, dimethylsulfone, tetramethylurea, and hexamethylphosphoramide. These organic solvents may be used alone or in combination of two or more.

The resin composition used in the present invention is molded by a known molding method such as an injection molding method, an extrusion molding method and a compression molding method, and is put into practical use. In the present invention, the surface properties are remarkably improved as compared with the post-annealing by crystallization of the mold during injection molding. This improvement in surface properties significantly improves the properties of the separating claw, ie, the friction and wear properties. Compared to the amorphous separation nail made by the conventional method, the surface property is clearly superior in the mold crystallized mold. In addition, by crystallization in the mold during injection molding, the dimensional accuracy can be more easily predicted than in the case of post-annealing, and the dimensional accuracy can be accurately controlled in practice. In other words, the tip shape serving as the key point of the separation claw can be molded with high precision, and the separation operation for the copying machine is surely improved. Further, in the crystallized product in the mold, oriented crystallization in the skin layer of the molded product is progressing, and the impact strength such as the Izod impact strength is improved as compared with the annealed product. (There is no orientation crystallization in the skin layer in the post-annealed product.) The appearance is extremely good. Finally, it is obvious that crystallization in the mold does not require crystallization by post-annealing, which greatly contributes to cost reduction.

[0043]

【Example】

Synthesis Example of Bisimide Compound 4,4′-bis (3-aminophenoxy) biphenyl 3 was placed in a vessel equipped with a stirrer, a reflux condenser, and a nitrogen inlet tube.
6.8 g (0.1 mol), 32.56 g of phthalic anhydride
(0.22 mol), 1.39 g of γ-picoline and 80.08 g of m-cresol, and heated to 150 ° C. while stirring under a nitrogen atmosphere. Thereafter, the reaction was carried out at 150 ° C. for 3 hours, during which 3.6 ml of water was distilled off. After completion of the reaction, the reaction mixture was cooled to room temperature, charged with about 20 ml of methanol, and then the bisimide powder was separated by filtration. After washing this bisimide powder with methanol, it was heated at 50 ° C. /
After drying at 180 ° C. for 6 hours for 12 hours,
0.6 g (96.5% yield) was obtained.

Example 1 54 parts by weight of a crystalline polyimide resin (AURUM PL450 (Mitsui Toatsu Chemicals)), 5 parts by weight of carbon black (Toka Black (Tokai Carbon)), 5 parts by weight of the bisimide compound obtained in the synthesis example, A mixture of 36 parts by weight of a polyaryletherketone resin (PEK22P (VICTREX)) was supplied from a front hopper, and 20 parts by weight of carbon fiber was supplied from a side feeder to 100 parts by weight of a resin composition to obtain a 40 mm diameter. Was melt-kneaded at 410 ° C. to obtain pellets. The obtained pellets were subjected to a cylinder temperature of 410 ° C., a mold temperature of 260 ° C., and an injection pressure of 100 k by an injection molding machine having a mold clamping force of 400 tons.
It was molded under the conditions of g / cm ² to obtain an ASTM bending test piece and a Suzuki-type friction and wear test piece.

Friction Coefficient, Specific Wear A Suzuki friction wear test was performed under the conditions of SUS304, non-lubricated 7H, surface pressure of 5 kg / cm ² , and speed of 50 m / min as a mating material. After 7 hours, the friction coefficient and the specific wear amount were measured. Shrinkage The MD / TD shrinkage of the bending test piece was measured. Appearance (gloss) The 60 ° specular gloss was measured. The flexural modulus was measured according to ASTM D790. Surface roughness was measured using a surface roughness meter. Ra was determined.

Comparative Example 1 100 parts by weight of a crystalline polyimide resin (AURUM PL450 (Mitsui Toatsu Chemicals)) was supplied from a front hopper, and 20 parts by weight of carbon fiber was supplied from a side feeder to 100 parts by weight of a resin composition. The mixture was melt-kneaded at 410 ° C. with an extruder having a diameter of 40 mm to obtain pellets. The obtained pellets were subjected to an injection molding machine with a mold clamping force of 400 tons, cylinder temperature 410 ° C., mold temperature 260 ° C., injection pressure 1
An ASTM bending test piece and a Suzuki-type friction and wear test piece were obtained by molding under the condition of 00 kg / cm 2. A for test piece
Post-annealing was performed at 260 ° C. * 10H → 300 ° C. * 2H for both the STM bending test piece and the Suzuki friction and wear test piece. Various measurement methods were the same as in Example 1.

The following X-ray measuring apparatus was used for measuring Lc of carbon black. Apparatus: RINT-1500SYST manufactured by Rigaku Corporation
EM tube: Cu Tube voltage: 50 kV Tube current: 200 mA Scanning axis: 2θ / θ Goniometer: Wide-angle goniometer Sampling width: 0.020 ° Scanning speed: 8.000 ° / min Diverging slit: 1 ° Scattering slit: 1 ° Light receiving Slit: 0.15 mm θ Offset angle: 0.000 degree Use of monochromator Receiving slit: 0.60 mm Use of aluminum standard sample holder Lc is the following Scherrer's formula (Equation 1) according to the peak position and half width of (002) plane. Was calculated.

[0048]

Lc = Dhkl = (K × λ) / (β × cos θ) (where K = 0.9, λ: measured X-ray wavelength, β: spread of diffraction line due to crystallite size, θ : Bragg angle of diffraction line.) Lc of Toka Black used in the experiment was 5 nm.

Example 2 Separation claws for a copying machine were obtained by injection molding using the composition used in Example 1. The obtained separating claw was attached to a predetermined position in contact with a heating roller (PFA coating) fixing device of a copying machine. This separation claw is good with no damage to the roller, does not adhere toner, does not show its own wear, and fully satisfies the characteristics required for separation claw for copiers even after long use. I was

Comparative Example 2 The same procedure was performed as in Example 2 except that the composition obtained in Comparative Example 1 was used. The separation claw was damaged by the roller, and the toner was also stained. Further, the tip of the separation claw was significantly worn as compared with Example 2, and its life was about 1/3 as compared with Example 2.

[0051]

[Table 1] Example 1 Comparative Example 1係数 Coefficient of friction 0.10 0.19 Specific wear ^* 50 130 Shrinkage% 0 0.7 0.9 Appearance Gloss% 90 83 Flexural modulus kg / mm ² 3000 2200 Surface roughness μm 0.2 0.4 mm ─────────────── [Legend] ^* 10 (E-10) cm ³ / kgfm

[0052]

As described above, the separation claw of a copying machine made of a thermoplastic polyimide resin which crystallizes in a mold or a thermoplastic polyimide resin composition which crystallizes in a mold has a remarkably improved function as a separation claw. It can be suitably used in various copying machines.

Continued on the front page (72) Inventor Kiba Friend 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Prefecture Inside Mitsui Toatsu Chemicals Co., Ltd. (72) Inventor Tomoaki Sato 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Mitsui Toatsu Chemicals (72) Inventor Koichi Sano 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Mitsui Toatsu Chemicals Co., Ltd.

Claims (5)

[Claims] 1. A crystalline polyimide resin having a repeating structural unit represented by the following general formula (1): (X ₁ is a direct _{bond, -SO 2 -, - CO 2} -, - C (C
_{H 3) 2 -, - C} (CF 3) 2 -, or a -S-. R
₁ , R ₂ , R ₃ and R ₄ are each hydrogen, an alkyl group, an alkoxy group, a halogenated alkyl group, a halogenated alkoxy group or a halogen group. Y ₁ is the general formula (2)
It is at least one group selected from the group consisting of (Chem. 2). Embedded image And / or a crystalline polyimide resin having a repeating structural unit of the general formula (3) (formula 3): (R ₅ and R ₆ are each a hydrogen, an alkyl group, an alkoxy group, a halogenated alkyl group, a halogenated alkoxy group, or a halogen group, and n is an integer of 0 to 4. Y ₂ is It is the same as the definition of Y _{1 in} the general formula (1).) For 100 parts by weight, carbon black is used as the component (A), and general formula (4) is used as the component (B). 4] (R ₇ represents a divalent aromatic group having 6 to 30 carbon atoms represented by X ₂
Is represented by the general formula (5): Represents at least one divalent group selected from the group consisting of X ₃ is a direct bond, an ether bond, a sulfide bond, a hydrocarbon group having 1 to 10 carbon atoms, a carbonyl group,
Hexafluorinated isopropylidene group, having 6 to 6 carbon atoms
At least one member selected from the group consisting of 18 aromatic groups
Represents a species of divalent group. A) a bisimide compound represented by
And / or general formula (6) (R ₈ is —C _n H _{2n + 1} — (n = 0 to 3) or a monovalent aromatic group having 6 to 30 carbon atoms, and Y ₃ is a general formula (7) ) And a tetravalent group consisting of Y ₄ is a direct bond, an ether bond, a sulfide bond, a hydrocarbon group having 1 to 10 carbon atoms, a carbonyl group, a sulfonyl group, an isopropylidene group hexafluorinated, or an aromatic group having 6 to 18 carbon atoms. Represents at least one divalent group selected from the group consisting of: At least one of the bisimide compounds represented by
A polyetheretherketone resin having a repeating structural unit represented by the general formula (8) as the component (C): A polyether ketone resin having a repeating structural unit represented by the general formula (9): A polyether ketone ether ketone ketone resin having a repeating structural unit represented by the following general formula (10): A polyether ketone ketone resin having a repeating structural unit represented by the following general formula (11): Of at least one polyaryletherketone resin selected from the group consisting of component (A), component (B), and component (C), at least two components of 0.2 to 2
A separating claw for a copying machine, comprising a resin composition containing 00 parts by weight. 2. The separating claw for a copying machine according to claim 1, wherein the crystallite size (Lc) in the C-axis direction of the carbon black is 1 to 20 nm. 3. The bisimide compound represented by the general formula (12)
(Chemical formula 12) The separation claw for a copying machine according to claim 1, wherein the separation claw is represented by: 4. The separation nail for a copying machine according to claim 1, further comprising 5 to 100 parts by weight of a fibrous reinforcing material based on 100 parts by weight of the resin composition. 5. A separating claw for a copying machine, wherein a thermoplastic crystalline polyimide resin crystallized in a mold and / or a thermoplastic crystalline polyimide resin composition crystallized in a mold are used. .