JPH0987517A - Polyimide resin composition - Google Patents

Abstract

(57) Abstract: A fluororesin is contained in an amount of 1 to 40 parts by weight with respect to a total amount of 100 parts by weight of a resin composition comprising 40 to 95 parts by weight of a polyimide resin and 60 to 5 parts by weight of a polyallyl ether ketone. A polyimide-based resin composition comprising: [Effect] A high-strength / high-heat-resistant resin composition having excellent dimensional stability against water absorption, high sliding characteristics, and chemical resistance was obtained.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyimide resin composition having extremely high dimensional stability against water absorption, good sliding properties and good mechanical properties.

[0002]

2. Description of the Related Art Conventionally, a polyimide resin has been well known as an engineering plastic excellent in mechanical, chemical, thermal properties and abrasion resistance, and is widely used in sliding members (Japanese Patent Laid-Open No. 5-179231). It is used in various industrial fields. Further, recently, based on the inherent high heat resistance, sliding characteristics, and mechanical properties of polyimide resins, attempts have been made to develop them into parts that require sealability rather than valve materials as a metal substitute. However, the polyimide resin alone has a large dimensional change due to water absorption and is difficult to be used in a field requiring extremely high dimensional accuracy.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a polyimide resin composition having extremely high dimensional stability against water absorption and excellent sliding properties, mechanical properties, chemical resistance and the like. .

[0004]

Means for Solving the Problems The inventors of the present invention have made earnest studies to achieve the above-mentioned objects, and as a result, polyimide resin 4
1 to 40 parts by weight with respect to 100 parts by weight of a resin composition consisting of 0 to 95 parts by weight and 60 to 5 parts by weight of polyallyl ether ketone.
It was found that a polyimide resin composition having extremely high dimensional stability against water absorption can be obtained by adding a weight part of a fluororesin, and the present invention has been completed. That is,
The present invention provides 1) a polyimide resin having a repeating unit represented by the formula (1) [Chemical formula 5] and / or a polymer molecule thereof having essentially no substituents or an amine or a dicarboxylic acid anhydride. Fluorocarbon resin 40 having a melt flow index of 400-15.0 g / 10 min at 400 ° C. and 10 kg with respect to 60-99 parts by weight of a polyimide resin which is an aromatic ring substituted with a non-reactive group.
To 1 part by weight of the polyimide resin composition,

[0005]

Embedded image (In the formula, X is selected from the group consisting of direct bond, sulfur, divalent hydrocarbon group having 1 to 10 carbon atoms, hexafluorinated isopropylidene group, carbonyl group, thio group, sulfonyl group and ether group. Represents at least one group, Y ₁ ,
Y ₂ , Y ₃ and Y ₄ are each hydrogen and have 1 carbon atom
To a lower alkyl group having 1 to 6 carbon atoms, a lower alkoxy group having 1 to 6 carbon atoms, a chlorine and / or bromine group, and R ₁
Have 6 to 27 carbon atoms, and an aliphatic group, a cycloaliphatic group, a monocyclic aromatic group, a condensed polycyclic aromatic group and / or an aromatic group are directly or cross-linked with each other. Represents a tetravalent group which is a non-fused polycyclic aromatic group. 2) When a polyimide having a repeating unit represented by the formula (1) is used to produce the polyimide, the compound represented by the general formula (2)

[0006]

[Chemical 6] And / or general formula (3)

[0007]

Embedded image V—NH ₂ (3) (In the formula, Z and V each have 6 to 15 carbon atoms, and a monocyclic aromatic group, a condensed polycyclic aromatic group, or an aromatic group is a direct or cross-linking member. Represents at least one divalent group selected from the group consisting of non-condensed polycyclic aromatic groups interconnected with each other.) Coexisting with an aromatic dicarboxylic acid anhydride and / or an aromatic monoamine The polyimide resin composition according to 1 above, which contains a polyimide resin obtained by capping the molecular ends of the polymer obtained by the reaction below, 3) Polyallyl ether ketone is represented by formulas (4) to (7) The polyimide resin composition as described in 1) or 2) above, which is at least one selected from the group having a repeating unit

[0008]

Embedded image 4) A fluororesin having a melt flow index at 400 ° C. and 10 kg of 4.0 to 15.0 g / 10 min or less is at least one selected from the group consisting of the following (a) to (f): 2. The polyimide resin composition according to claim 1, wherein (a) a tetrafluoroethylene resin having a repeating structural unit represented by — (CF ₂ CF ₂ ) — in the molecule. (B) in the _{molecule, - (CF 2 CF 2)} - and - [CF (CF ₃₎ CF _2] - tetrafluoroethylene resin having recurring structural units represented by - hexafluoropropylene copolymer resin. (C) in the molecule, - (CF ₂ CF ₂₎ - and - _{[CF (OC m F 2m +1)} CF 2 ] (wherein, m is a positive integer) 4 having a repeating structural unit represented by the Fluorinated ethylene-perfluoroalkyl vinyl ether copolymer resin. In (d) _{molecules, - (CF 2 CF 2)} - and - (CH ₂ CH ₂₎ - tetrafluoroethylene having a repeating structural unit represented by - ethylene copolymer resin. In (e) _{molecules, - (CH 2 CH 2)} - and - (CFClCF ₂₎ - trifluorochloroethylene having a repeating structural unit represented by - ethylene copolymer resin. In (f) _{molecular, - (CF 2 CH 2)} - vinylidene fluoride resin having a repeating structural unit represented by. It is.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION A diamine component used as a raw material for a polyimide resin having a repeating unit represented by the formula (1) as a basic skeleton in a polyimide resin composition used in the present invention is represented by the formula (8)

[0010]

Embedded image (In the formula, X and Y ₁ , Y ₂ , Y ₃ and Y ₄ are the same as above)
And the formula (9) [Formula 10]

[0011]

Embedded image (Wherein R ₁ is the same as described above) is reacted with one or more tetracarboxylic dianhydrides in the presence or absence of an organic solvent, and the resulting polyamic acid is chemically or thermally reacted. Can be imidized to produce. The reaction temperature is usually 250 ° C. or lower, and the reaction pressure is not particularly limited, and it can be sufficiently carried out at normal pressure. The reaction time varies depending on the tetracarboxylic dianhydride used, the type of solvent, and the reaction temperature, and the reaction is usually performed for a time sufficient to complete the production of the polyamic acid as an intermediate product. A reaction time of 24 hours, sometimes 1 hour or less, is sufficient.

By such a reaction, a polyamic acid corresponding to the repeating unit of the formula (1) is obtained, and then the polyamic acid is dehydrated by heating at 100 to 400 ° C., or chemically synthesized by using a commonly used imidizing agent. By imidizing, a polyimide having a repeating structural unit of formula (1) is obtained. Further, it is also possible to obtain a polyimide by simultaneously performing generation of polyamic acid and thermal imidization reaction.

The etherdiamine of the formula (2) used in this method is as follows: [4- (3-aminophenoxy) phenyl] wherein X in the formula (2) is an aliphatic group.
Methane, 1,1-bis [4- (3-aminophenoxy)
Phenyl] ethane, 1,2-bis [4- (3-aminophenoxy) phenyl] ethane, 2,2-bis [4- (3
-Aminophenoxy) phenyl] propane, 2- [4-
(3-aminophenoxy) phenyl] -2- [4- (3
-Aminophenoxy) -3-methylphenyl] propane, 2,2-bis [4- (3-aminophenoxy) -3
-Methylphenyl] propane, 2- [4- (3-aminophenoxy) phenyl] -2- [4- (3-aminophenoxy) -3,5-dimethylphenyl] propane, 2,
2-bis [4- (3-aminophenoxy) -3,5-dimethylphenyl] propane, 2,2-bis [4- (3-
Aminophenoxy) phenyl] butane, 2,2-bis [4- (3-aminophenoxy) phenyl] -1,1,
1,3,3,3-hexafluoropropane, in which X in the formula is a direct bond, 4,4'-bis (3-aminophenoxy) biphenyl, 4,4'-bis (3-aminophenoxy)- 3-methylbiphenyl, 4,4'-bis (3-aminophenoxy) -3,3'-dimethylbiphenyl, 4,4'-bis (3-aminophenoxy) -3,
5-dimethylbiphenyl, 4,4'-bis (3-aminophenoxy) -3,3 ', 5,5'-tetramethylbiphenyl, 4,4'-bis (3-aminophenoxy)-
3,3'-dichlorobiphenyl, 4,4'-bis (3-
Aminophenoxy) -3,5-dichlorobiphenyl,
4,4′-bis (3-aminophenoxy) -3,3 ′,
5,5'-tetrachlorobiphenyl, 4,4'-bis (3-aminophenoxy) -3,3'-dibromobiphenyl, 4,4'-bis (3-aminophenoxy) -3,
5-dibromobiphenyl, 4,4′-bis (3-aminophenoxy) -3,3 ′, 5,5′-tetrabromobiphenyl, wherein X in the formula is a —CO— group, and bis [4
-(3-aminophenoxy) phenyl] ketone, bis [4- {4- (4-aminophenoxy) phenoxy} phenyl] ketone, wherein X in the formula is a -S- group, bis [4- (3- Aminophenoxy) phenyl] sulfide, bis [4- (3-aminophenoxy) -3-methoxyphenyl] sulfide, [4- (3-aminophenoxy) phenyl] [4- (3-aminophenoxy) 3,5
-Dimethoxyphenyl] sulfide, bis [4- (3-
Aminophenoxy) -3,5-dimethoxyphenyl] sulfide, wherein X in the formula is a —SO ₂ — group, bis [4- (3-aminophenoxy) phenyl] sulfone,
Bis [4- {4- (4-aminophenoxy) phenoxy} phenyl] sulfone, wherein X in the formula is an —O— group, bis [4- (3-aminophenoxy) phenyl]
Ether, bis [4- (4-aminophenoxy) phenyl] ether, wherein X in the formula is 1,4
-Bis [4- (3-aminophenoxy) phenoxy] benzene, 1,4-bis [4- (4-aminophenoxy)
Phenoxy] benzene, 1,4-bis [4- (3-aminophenoxy) benzoyl] benzene, 1,3-bis [4- (3-aminophenoxy) benzoyl] benzene, bis [4- {4- (4- Aminophenoxy) phenoxy} phenyl] sulfone and the like can be mentioned, and these can be used alone or in admixture of two or more.

Further, other diamines can be mixed and used as long as the melt flowability of the thermoplastic polyimide resin is not impaired. Examples of diamines that can be mixed and used include m-aminobenzylamine, p-aminobenzylamine, 3,3′-diaminodiphenyl ether,
3,4′-diaminodiphenyl ether, 4,4′-diaminodiphenyl ether, 3,3′-diaminodiphenyl sulfide, 3,4′-diaminodiphenyl sulfide, 4,4′-diaminodiphenyl sulfide, 3,
3'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminobenzophenone, 3,
4'-diaminobenzophenone, 4,4'-diaminobenzophenone, 1,3-bis (3-aminophenoxy)
Benzene, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (3-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene,
2,2-bis [4- (4-aminophenoxy) phenyl] propane, 4,4′-bis (4-aminophenoxy) biphenyl, 4,4′-bis (4-aminophenoxy) phenyl] ketone, bis [ 4-aminophenoxy)
Examples thereof include phenyl] sulfide and bis [4- (4-aminophenoxy) phenyl] sulfone, and these diamines are usually used by mixing 30% by weight or less, preferably 5% by weight or less.

Further, as a specific example of the tetracarboxylic dianhydride which is one of the starting materials used for producing the polyimide represented by the formula (1), R ₁ in the formula in the formula (9) is It is defined as at least one selected from the group consisting of the following (a) to (e). (A) C4-C9 aliphatic group (b) C4-C9 cycloaliphatic group (c) Monocyclic aromatic group represented by the following formula

[0016]

Embedded image (D) Fused polycyclic aromatic group represented by the following formula

[0017]

[Chemical 12] (E) A non-condensed polycyclic aromatic group in which aromatic groups represented by the following formula [Chemical Formula 13] are connected to each other directly or by a crosslinking member.

[0018]

Embedded image Specifically, ethylene tetracarboxylic dianhydride R ₁ is an aliphatic group in the formula, butane tetracarboxylic dianhydride, cyclopentane tetracarboxylic is as R ₁ in the formula is a cycloaliphatic radical Carboxylic dianhydride, wherein R _{1 in the} formula is a monocyclic aliphatic group, pyromellitic dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride, R 1 in the formula Is represented by the following formula [Formula 14],

[0019]

Embedded image 3,3 ′, 4,4′- in which X _{1 in} the formula is a —CO— group
Benzophenone tetracarboxylic dianhydride, 2,2 ',
3,3′-benzophenone tetracarboxylic acid dianhydride,
3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, in which X _{1 in} the formula is a direct bond, 2,2 ′, 3,
3′-biphenyltetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride in which X _{1 in} the formula is an aliphatic group, 2,2-bis (2,2)
3-dicarboxyphenyl) propane dianhydride, 1,1
-Bis (2,3-dicarboxyphenyl) ethane dianhydride, bis (2,3-dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, in the formula Bis (3,4-) in which X ₁ is an -O- group
Dicarboxyphenyl) ether dianhydride, X in the formula
Bis (3,4-dicarboxyphenyl) sulfone dianhydride in which ₁ is a —SO 2 — group, and 2,3,6,7 in which R ₁ in the formula (9) is a condensed polycyclic aromatic group -Naphthalene tetracarboxylic dianhydride, 1,4,5,8-naphthalene tetracarboxylic dianhydride, 1,2,5,6-naphthalene tetracarboxylic dianhydride, 3,4,9,10-perylene Tetracarboxylic acid dianhydride, 2,3,6,7-anthracene tetracarboxylic acid dianhydride, 1,2,7,8
-Phenanthrenetetracarboxylic dianhydride, R _{1 in} the formula is another one such as bis (3,4dicarboxy) (p-phenylenedioxy) dianhydride,
These tetracarboxylic dianhydrides are used alone or in combination of two or more.

The polyimide resin represented by the formula (1) used in the present invention has the general formula (2):

[0021]

[Chemical 15] And / or general formula (3)

[0022]

Embedded image V—NH ₂ (3) (wherein Z and V each have 6 to 15 carbon atoms, and a monocyclic aromatic group, a condensed polycyclic aromatic group, or an aromatic group is a direct or bridging member. At least one divalent and one selected from the group consisting of non-fused polycyclic aromatic groups interconnected by
Represents a valence group. ) A polyimide resin in which a molecular end of a polymer obtained by reacting an aromatic dicarboxylic acid anhydride and / or an aromatic monoamine represented by the formula (1) in the coexistence is sealed.

Examples of the carboxylic acid anhydride represented by the general formula (2) include phthalic anhydride, 2,3-benzophenone dicarboxylic acid anhydride, 3,4-benzophenone dicarboxylic acid anhydride and 2,3-dicarboxylic acid. Carboxyphenyl phenyl ether anhydride, 3,4-dicarboxyphenyl phenyl ether anhydride, 2,3-biphenyl dicarboxylic acid anhydride, 3,4-biphenyl dicarboxylic acid anhydride, 2,
3-dicarboxyphenyl phenyl sulfone anhydride,
3,4-dicarboxyphenylphenyl sulfone anhydride, 2,3-dicarboxyphenylphenyl sulfide anhydride, 3,4-dicarboxyphenylphenyl sulfide anhydride, 1,2-naphthalenedicarboxylic acid anhydride,
2,3-naphthalenedicarboxylic acid anhydride, 1,8-naphthalenedicarboxylic acid anhydride, 1,2-anthracene dicarboxylic acid anhydride, 2,3-anthracene dicarboxylic acid anhydride, 1,9-anthracene dicarboxylic acid anhydride, etc. Is a dicarboxylic acid anhydride. Any of these may be used alone or in combination of two or more kinds.

Of these carboxylic acid anhydrides, phthalic anhydride is most preferable from the viewpoint of performance and practical use of the polyimide obtained. When the carboxylic acid anhydride is used, the amount thereof is 0.001 to 1.0 mol ratio per 1 mol of the aromatic diamine represented by the general formula (8). 0.001
If it is less than the molar amount, the viscosity is increased during high temperature molding, which causes deterioration of molding processability. Further, if it exceeds 1.0 mol, the mechanical properties are deteriorated. The preferred amount used is 0.01 to 0.
5 mole ratio.

Examples of the aromatic monoamine represented by the general formula (3) include aniline, o-toluidine,
m-toluidine, p-toluidine, 2,3-xylidine, 2,6-xylidine, 3,4-xylidine, 3,5
-Xylidine, o-chloroaniline, m-chloroaniline, p-chloroaniline, o-bromoaniline, m-bromoaniline, p-bromoaniline, o-nitroaniline, m-nitroaniline, p-nitroaniline, o- Aminophenol, m-aminophenol, p-aminophenol, o-anisidine, m-anisidine, p-anisidine, o-phenidine, m-phenidine, p-phenidine, o-aminobenzaldehyde, m-aminobenzaldehyde, p-amino Benzaldehyde, o-aminobenzonitrile, m-aminobenzonitrile, p-aminobenzonitrile, 2-aminobiphenyl, 3-aminobiphenyl, 4-aminobiphenyl, 2-aminophenylphenyl ether, 3-aminophenylphenyl ether, 4 -Amino E alkenyl phenyl ether, 2-aminobenzophenone, 3-aminobenzophenone, 4-aminobenzophenone, 2-aminophenyl phenyl sulfide, 3-aminophenyl phenyl sulfide, 4
Aminophenylphenyl sulfide, 2-aminophenylphenylsulfone, 3-aminophenylphenylsulfone, 4-aminophenylphenylsulfone, α-naphthylamine, β-naphthylamine, 1-amino-2-naphthol, 2-amino-1-naphthol, 4-amino-
1-naphthol, 5-amino-1-naphthol, 5-amino-2-naphthol, 7-amino-2-naphthol,
8-amino-1-naphthol, 8-amino-2-naphthol, 1-aminoanthracene, 2-aminoanthracene, 9-aminoanthracene and the like can be mentioned. These aromatic monoamines may be substituted with a group having no reactivity with amine or dicarboxylic acid anhydride,
There is no problem even if they are used alone or as a mixture of two or more kinds.

When the aromatic monoamine is used, the amount thereof is 0.001 to 1.0 mol ratio per 1 mol of the tetracarboxylic dianhydride represented by the general formula (9). 0.0
If it is less than 01 mol, the viscosity is increased during high temperature molding, which causes deterioration of molding processability. On the other hand, if the molar ratio exceeds 1.0, the mechanical properties will deteriorate. The preferred amount used is 0.0
It is a ratio of 1 to 0.5 mol.

The fluororesin used in the present invention is preferably at least one selected from the group consisting of the following (a) to (f). (A) in the _{molecule, - (CF 2 CF 2)} - in the tetrafluoroethylene resin (b) molecules having a repeating structural unit represented _{by, - (CF 2 CF 2)} - and - [CF (CF ₃ ) CF ₂ ]-tetrafluoroethylene resin having a repeating structural unit represented by -hexafluoropropylene copolymer resin (c)-(CF ₂ CF ₂ )-and-[CF (OC _m F _2m +1) CF ₂ ] (in the formula, m is a positive integer) Tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer resin (d) having a repeating structural unit represented by the formula:-(CF ₂ CF ₂ ) - and - (CH ₂ CH ₂₎ - ethylene copolymer (e) in the molecule, - - repeating structural units tetrafluoroethylene having represented by (CH ₂ CH ₂₎ - and - (CFClCF ₂₎ − Iterative structure represented by Ethylene copolymer resin, in (f) molecule - - trifluorochloroethylene having units (CF ₂ CH ₂₎ - vinylidene fluoride resin having a repeating structural unit represented by, and the like.

The resin composition used in the present invention is 1 part with respect to 100 parts by weight of the resin composition comprising 40 to 95 parts by weight and 60 to 5 parts by weight of the polyimide resin having the repeating unit represented by the formula (1). The polyimide resin composition is characterized by containing ˜40 parts by weight of a fluororesin.

The addition amount of the polyallyl ether ketone used in the present invention is 60 to 5 parts by weight of polyallyl ether ketone with respect to 40 to 95 parts by weight of the polyimide resin having the repeating unit represented by the formula (1). The amount of polyallyl ether is preferably 15 to 50 parts by weight with respect to 85 to 50 parts by weight of the polyimide resin. More preferably, it is 30 to 50 parts by weight of polyallyl ether ketone with respect to 70 to 50 parts by weight of polyimide resin. If the amount of polyallyl ether ketone added exceeds 60 parts by weight, the heat resistance of the polyimide decreases, which is not preferable. If the amount of polyallyl ether ketone added is less than 5 parts by weight, the water absorption rate increases, which is not preferable. The addition amount of the polyallyl ether ketone is 60 to 5 per 100 parts by weight of the total amount of the polyimide resin having the repeating unit represented by the formula (1) and the polyallyl ether ketone.
The amount is parts by weight, preferably 60 to 10 parts by weight, more preferably 50 to 20 parts by weight.

The amount of the fluororesin used in the present invention is 100 parts by weight of a resin composition comprising 40 to 95 parts by weight and 60 to 5 parts by weight of a polyimide resin having a repeating unit represented by the formula (1). , 1 to 40 parts by weight. When the amount of the fluororesin added exceeds 40 parts by weight, the mechanical strength of the composition is lowered, which is not preferable. Addition amount of fluororesin is 1
If it is less than the weight part, the effect of imparting the sliding property is not remarkable.
The addition amount of the fluororesin is 1 to 40 with respect to 100 parts by weight of the total amount of the polyimide resin and the polyallyl ether ketone.
It is 5 parts by weight, preferably 5 to 35 parts by weight, and more preferably 5 to 30 parts by weight.

Furthermore, the value of the melt index of the fluororesin used in the present invention at 400 ° C. and 10 kg is 4.0 to 15.0 g / 10 min. It is. The melt index value of the fluororesin at 400 ° C. and 10 kg was 15.0 g / 10 min. If it exceeds the range, the impact strength decreases, which is not preferable. The melt index value of the fluororesin at 400 ° C. and 10 kg was 4.0 g / 10 min.
Below this, the effect on the dimensional stability against water absorption is not remarkable.

The polyimide resin having a repeating unit represented by the formula (1) usually has an inherent viscosity of 0.35 to 1.0 d.
1 / g, preferably 0.40 to 0.90 dl / g, more preferably 0.40 to 0.80 dl / g, still more preferably 0.40 to 0.70 dl / g. When the logarithmic viscosity exceeds the above range and is 0.35 or less, mechanical properties, durability and sliding characteristics are insufficient, and when it is 1.0 or more, moldability is deteriorated and injection molding becomes difficult. This logarithmic viscosity was 0.5 g / 1 in a mixed solvent of parachlorophenol / phenol (90/10 weight ratio).
It is heated and dissolved in 00 ml of a solvent and then cooled to 35 ° C. for measurement.

If necessary, the present resin composition contains glass fiber, carbon fiber, optical fiber, ceramic fiber, potassium titanate fiber, metal fiber, boron fiber, silicon carbide fiber,
You may contain at least 1 sort (s) selected from the group which consists of asbestos, a rock wool fiber, and an aramid fiber. Further, the present resin composition, if necessary, calcium carbonate,
Mica, glass beads, graphite, molybdenum disulfide, clay, silica, alumina, talc, diatomaceous earth,
Hydrated alumina, filler such as shirasu balloon, lubricant, mold release agent, stabilizer, colorant, crystal nucleating agent, liquid crystal polymer, thermoplastic resin (for example, polyetherimide, polyethernitrile, polyamideimide, poly Ether sulfone, polysulfone, polyarylate and / or polyphenylene sulfide) and a thermosetting resin (for example, epoxy resin, polybenzimidazole resin, polyimide resin, etc.) are used in combination within a range that does not impair the characteristics of the resin composition. Good.

The present resin composition imparts the low water absorption inherent to polyallyl ether ketone by adding a polyallyl ether ketone partially compatible with polyimide, and further a fluororesin having a specific melt viscosity is added. Addition improves the dimensional stability against water absorption, and is particularly useful in the field where sealing properties are required.

[0035]

The present invention will be described below in detail with reference to examples and comparative examples. Example 1 AURUM PD450 (Mitsui Toatsu Chemical) as a polyimide resin and PEEK as a polyallyl ether ketone
150P (Mitsui Toatsu Chemical), 400 as fluororesin
Melt flow index (M
I) is 12.0 g / 10 min. After blending and mixing the tetrafluoroethylene resin PTFE of (1) in the proportions shown in Table 1, the mixture was melt-kneaded at 410 ° C. by a twin-screw extruder to obtain pellets. The obtained pellets were supplied to an injection molding machine (cylinder temperature of 380 to 410 ° C., injection pressure of 1000 Kg / cm 2, mold temperature of 160 ° C.) to mold test pieces specified by each test method described later. In addition, each test method is as follows. 1) Melt flow index (MI) According to JIS K 7210. However, the temperature and the load were 400 ° C. and 10 kg. 2) Tensile strength The tensile strength was determined according to ASTM D-638. 3) Izod impact strength It carried out according to ASTM D-256. 4) Heat distortion temperature (HDT) The heat distortion temperature was measured according to ASTM D-648. 5) Coefficient of friction Sliding load 10 kg / c using thrust type friction and wear tester
m ² , sliding speed 10 m / min, mating material stainless steel 4
Determine the coefficient of kinetic friction at 5C, without lubrication, and after 1 hour of operation. 6) Dimensional change rate after water absorption A test piece according to JIS K 7209 is immersed in hot water at 95 ° C for 500 hours, and the size immediately after taking out is measured, and this is taken as the size after water absorption. The change rate from the dimension measured in advance before hot water immersion was calculated from the formula I. The results are shown in Table 1.

Examples 2 to 6 The same procedure as in Example 1 was carried out except that the compositions shown in Examples 2 to 6 in Table 1 were used. The results are shown in Table 1.

Example 7 Carbon fiber manufactured by Toho Rayon Co., Ltd. (HTA-C6-T
X) The same procedure as in Example 1 was carried out except that carbon fiber was used and the composition shown in Example 7 of Table 1 was used. The results are shown in Table 1.

Comparative Examples 1 to 7 Test pieces were prepared in the same manner as in Example 1 and their properties were measured. The obtained results are also shown in Table 1.

[0039]

[Table 1]

[0040]

The resin composition of the present invention is a high-strength / high-heat-resistant resin composition having extremely excellent dimensional stability against water absorption, high sliding characteristics, and chemical resistance. Therefore, it is a very useful material used for structural members, mechanical parts, automobile parts, and base materials for space aircraft that require these physical properties, and has a very great industrial application effect.

Front Page Continuation (72) Inventor Masahiko Yamaki 2-1, Tango Dori, Minami-ku, Nagoya-shi, Aichi Mitsui Toatsu Chemical Co., Ltd.

Claims (4)

[Claims] 1. A repeating unit represented by the formula (1)
40-95 parts by weight of a polyimide resin having a rank and polyary
Of a resin composition comprising 60 to 5 parts by weight of luther ketone
Melt flow index for 100 parts by weight
Value at 400 ℃, 10kg is 4.0-15.0g / 1
Substantially contains 1 to 40 parts by weight of a fluororesin of 0 min.
A polyimide-based resin composition having. [Chemical 1](In the formula, X is a direct connection, sulfur, and a divalent carbon having 1 to 10 carbon atoms.
Hydrogen fluoride group, hexafluorinated isopropylidene group, cal
Consists of bonyl group, thio group, sulfonyl group, ether group
Represents at least one group selected from the group: Y₁, Y
₂, Y_ThreeAnd Y _FourAre hydrogen and low carbon numbers 1 to 6, respectively.
Grade alkyl group, lower alkoxy group having 1 to 6 carbon atoms, chlorine
And / or represents a bromine group, and R₁Is carbon number 6
To 27 and an aliphatic group, a cycloaliphatic group, a monocyclic aromatic group
An aromatic group, a condensed polycyclic aromatic group and / or an aromatic group
Non-fused polycyclic aromas, either directly or interconnected by cross-linking members
It represents a tetravalent group which is a group. ) 2. A polyimide having a repeating unit represented by the formula (1) has the following general formula (2): [Chemical Formula 2] And / or general formula (3) [Chemical formula 3] V-NH ₂ (3) (In the formula, Z and V each have 6 to 15 carbon atoms, and are a monocyclic aromatic group and a condensed polycyclic group. At least one divalent and one selected from the group consisting of aromatic groups and non-condensed polycyclic aromatic groups in which aromatic groups are connected to each other directly or by a cross-linking member.
Represents a valence group. The polyimide resin composition according to claim 1, comprising a polyimide resin obtained by reacting an aromatic dicarboxylic acid anhydride and / or an aromatic monoamine represented by the formula (1) in the coexistence and sealing the molecular end of the polymer. 3. The polyallyl ether ketone is represented by the formula (4):
(7) The polyimide resin composition according to claim 1 or 2, which is at least one selected from the group having a repeating unit represented by [Chemical Formula 4]. Embedded image 4. A melt flow index of 400 ° C.,
The polyimide resin composition according to claim 1, wherein the fluororesin having a value at 10 kg of 4.0 to 15.0 g / 10 min or less is at least one selected from the group consisting of the following (a) to (f). Stuff. In (a) _{molecule, - (CF 2 CF 2)} - tetrafluoroethylene resin having a repeating structural unit represented by. (B) in the _{molecule, - (CF 2 CF 2)} - and - [CF (CF ₃₎ CF _2] - tetrafluoroethylene resin having recurring structural units represented by - hexafluoropropylene copolymer resin. (C) in the molecule, - (CF ₂ CF ₂₎ - and - _{[CF (OC m F 2m +1)} CF 2 ] (wherein, m is a positive integer) 4 having a repeating structural unit represented by the Fluorinated ethylene-perfluoroalkyl vinyl ether copolymer resin. In (d) _{molecules, - (CF 2 CF 2)} - and - (CH ₂ CH ₂₎ - tetrafluoroethylene having a repeating structural unit represented by - ethylene copolymer resin. In (e) _{molecules, - (CH 2 CH 2)} - and - (CFClCF ₂₎ - trifluorochloroethylene having a repeating structural unit represented by - ethylene copolymer resin. In (f) _{molecular, - (CF 2 CH 2)} - vinylidene fluoride resin having a repeating structural unit represented by.