JPS62236858A - Polyimide resin composition - Google Patents

Abstract

PURPOSE:To obtain a polyimide resin compsn. having excellent heat resistance, dimensional stability, mechanical strength, etc., by blending a polyimide resin composed of a specified repeating unit with glass fiber. CONSTITUTION:A polyimide resin compsn. is obtd. by blending 100pts.wt. polyimide resin composed of a repeating unit of formula I with 5-100pts.wt. glass fiber. In the formula I, Y is a single bond or a group selected from the group consisting of a 1-10 C bivalent hydrocarbon, hexafluorinated isopropylidene, carbonyl, thio, sulfinyl, sulfonyl oxide groups; and R is a tetravalent group selected from the group consisting of a 2 C or higher aliph. group, an alicyclic group, a monocyclic group, a condensed polycyclic arom. group and a non- condensed cyclic arom. group, wherein arom. groups are linked with each other through a crosslinking member.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a novel polyimide resin composition having excellent heat resistance, dimensional stability, mechanical strength, etc.

[Conventional technology]

Traditionally, polyimides obtained by the reaction of tetracarboxylic dianhydrides and diamines have various excellent physical properties and good heat resistance, so it is expected that they will continue to be widely used in fields where heat resistance is required. ing.

Many of the polyimides that have been developed so far have excellent properties, but some have excellent heat resistance but poor processability, and resins developed for the purpose of improving processability have poor heat resistance and solvent resistance. Polyimide (manufactured by Dubon; trade name: Kapton+) consisting of a basic skeleton as shown in
Vespel) is a polyimide that does not have a clear glass transition temperature and has excellent heat resistance, but it is difficult to process when used as a molding material and must be processed using techniques such as sintering. Furthermore, when used as a material for electrical and electronic parts, it has a property of high water absorption, which adversely affects dimensional stability, insulation properties, and soldering heat resistance.

In addition, polyetherimide having a basic skeleton as represented by formula (III) (
0LTEN (manufactured by General Oshikutric Co., Ltd.) is a resin with excellent processability, but its glass transition temperature is 217.
℃, and is soluble in halogenated hydrocarbons such as methylene chloride, making it an unsatisfactory resin in terms of heat resistance and solvent resistance.

[Problems to be Solved by the Invention] An object of the present invention is to obtain a novel polyimide resin composition excellent in heat resistance, dimensional stability, mechanical strength, etc.

[Means for solving problems]

As a result of intensive research to achieve the above object, the present inventors found that a polyimide resin composition consisting of a new polyimide and a specific amount of glass fiber is particularly effective, and completed the present invention. .

That is, the polyimide resin composition of the present invention has (in the formula Y
is a direct bond, a divalent hydrocarbon group having 1 to 10 carbon atoms, a hexafluorinated isopropylidene group, a carbonyl group, a thio group,
Represents a group selected from the group consisting of a sulfinyl group, a sulfonyl group, or an oxide, R is an aliphatic group having 2 or more carbon atoms,
Cycloaliphatic group, monocyclic aromatic group, fused polycyclic aromatic group,
Represents a tetravalent group selected from the group consisting of non-fused cyclic aromatic groups in which aromatic groups are interconnected directly or through a bridge member. ) Polyimide resin 100 having a repeating unit represented by
This is a polyimide resin composition consisting of 5 to 100 parts by weight of glass fiber and 5 to 100 parts by weight of glass fiber.

The polyimide resin that can be used in the present invention is shown in formula (IV) (where Y is a direct bond, a divalent hydrocarbon group having 1 to 10 carbon atoms,
Hexafluorinated isopropylidene group, carbonyl group,
Represents a group selected from the group consisting of a thio group, a sulfinyl group, a sulfonyl group, or an oxide. ) It is a polyimide obtained by cyclodehydration of a polyamic acid obtained by reacting an ether diamine with one or more types of tetracarboxylic dianhydride.

Ether diamines include bis(4-(3-aminophenoxy)phenyl)methane, 1,1-his(4-(3-
-aminophenoxy)phenyl)ethane, 1.2-(4
-(3-aminophenoxy)phenyl)in, 2,2
-bis(4-(3-aminophenoxy)phenyl)propane, 2.2-his(4-(3-aminophenoxy)
phenyl)butane, 2,2-bis(4-aminophenoxy)phenyl)-1,1,1,3,3,3-hexafluoropropane, 4,4-bis(3-aminophenoxy)
Biphenyl, bis(4-(3-aminophenoxy)phenyl)ketone, bis(4-(3-aminophenoxy)phenyl)sulfide, bis(4-(3-aminophenoxy)phenyl)sulfoxide, bis(4-(3- Examples include aminophenoxy)phenyl)sulfone, bis(4-(3-aminophenoxy)phenyl)ether, and these may be used alone or in combination of two or more.

(In the formula, R is an aliphatic group having 2 or more carbon atoms, a cycloaliphatic group,
It represents a tetravalent group selected from the group consisting of a monocyclic aromatic group, a fused polycyclic aromatic group, and a non-fused cyclic aromatic group in which aromatic groups are interconnected directly or through a bridge member. ) is a tetracarboxylic dianhydride represented by

That is, the tetracarboxylic acids used include ethylenetetracarboxylic dianhydride, cyclopencune carboxylic dianhydride, pyromellitic dianhydride, 3.3', 4.
4'-benzophenonetetracarboxylic dianhydride, 2.
2',3,3°-benzophenonetetracarboxylic dianhydride, 3.3',4,4°-biphenyltetracarboxylic dianhydride, 2.2',3.3'-biphenyltetracarboxylic dianhydride 2,2°-bis(314-dicarboxyphenyl)propanihydride, 2,2”-bis(2
, 3-dicarboxyphenyl)propanihydride, bis(3,4-dicarboxyphenyl)ether diamine,
Bis(3,4-dicarboxyphenyl)sulfone dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, bis(2,3-dicarboxyphenyl)
Methanide dianhydride, bis(3,4-dicarboxyphenyl)methane dianhydride, 2.3,6.7-naphthalenetetracarboxylic dianhydride, 1.4,5.8-naphthalenetetracarboxylic dianhydride, 1,2,5.6-naphthalenetetracarboxylic dianhydride, 1.2,3.4-benzenetetracarboxylic dianhydride, 3,4.9.10-perylenetetracarboxylic dianhydride, 2. Examples include 3,6.7-anthracenecarboxylic dianhydride and 1,2,7.8-phenanthrenecarboxylic dianhydride.

These tetracarboxylic dianhydrides may be used alone or in combination of two or more.

Ether diamine and tetracarboxylic dianhydride are usually prepared using a known method to obtain a polyamide acid formula (where Y is a direct bond, a divalent hydrocarbon group having 1 to 10 carbon atoms, a hexafluorinated isopropylidene group, Represents a group selected from the group consisting of a carbonyl group, a thio group, a sulfinyl group, a sulfonyl group, or an oxide, and R is an aliphatic group having 2 or more carbon atoms, a cycloaliphatic group, a monocyclic aromatic group, or a fused (Represents a tetravalent group selected from the group consisting of a cyclic aromatic group and a non-fused cyclic aromatic group in which aromatic groups are interconnected directly or through a bridge member.) Glass fibers are made from various types of molten glass. It is made into a thin fiber with a predetermined diameter by being rapidly cooled while being drawn using the above method, and refers to strands made by binding single fibers together using a sizing agent, or roving made by uniformly aligning the strands into a bundle. Both can be used in the present invention. In order to make the glass fibers compatible with the base resin of the present invention, silane coupling agents such as aminosilane and epoxysilane, chromic chloride, and other surface treatment agents depending on the purpose can be used.

The length of the glass fiber in the present invention greatly affects the physical properties of the molded product obtained and the workability during production of the molded product. Generally, as the length of the glass fiber increases, the physical properties of the molded article improve, but on the contrary, the workability during production of the molded article deteriorates. For this reason,
In the present invention, the length of the glass fiber is 0.1 to 5 mm.
, preferably in the range of 0.3 to 4 mm, since the physical properties and workability of the molded product are well-balanced.

The glass fiber in the present invention is 5 to 100 parts by weight, preferably 10 to 50 parts by weight, based on 100 parts by weight of the polyimide resin.
Weight parts can be used. If the amount is less than 5 parts by weight, the reinforcing effect peculiar to glass fiber, which is a feature of the present invention, cannot be obtained. On the other hand, if 100 parts by weight or more is used, the fluidity of the composition during molding will deteriorate, making it difficult to obtain a satisfactory molded product.

The polyimide resin composition according to the present invention can be produced by generally known methods, but the following method is particularly preferred.

(11 Polyimide powder, glass fiber in a mortar, Henschel mixer, drum blender, tumbler blender,
After preliminary mixing using a ball mill, ribbon blender, etc., the mixture is kneaded using a commonly known melt mixer, hot roll, etc., and then made into pellets or powder.

(2) Polyimide powder is dissolved or suspended in an organic solvent in advance, glass fibers are impregnated with this solution or suspension, and then the solvent is removed in a hot air oven, and then pelletized or powdered.

In this case, examples of the solvent include N,N-dimethylformamide, N,N-dimethylacetamide, N,N-diethylacetamide, N,N-dimethylmethoxyacetamide, 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.
Examples include 4-dioxane, pyridine, picoline, dimethylsulfoxide, dimethylsulfone, tetramethylurea, hexamethylphosphoramide, and the like. Further, these organic solvents may be used alone or in combination of two or more.

(3) Glass fibers were impregnated into a solution of a polyamic acid having a repeating unit represented by formula (■), which is a precursor of the polyimide of the present invention, dissolved in the organic solvent.
After heat treatment at ~400°C or chemical imidization using a commonly used imidizing agent, the solvent is removed and the mixture is made into pellets or powder.

The composition of the present invention may contain conventional additives such as antioxidants, heat stabilizers, ultraviolet absorbers, flame retardant aids, antistatic agents, lubricants, colorants, etc., to the extent that the purpose of the present invention is not impaired. One or more additives can be added.

In addition, other thermoplastic resins (e.g., polyethylene, polypropylene, polyamide, polycarbonate, polysulfone, polyethersulfone, polyetherketone, modified polyphenylene oxide, polyphenylene sulfide, etc.), thermosetting resins/resins (e.g., phenolic resin,
Fillers such as epoxy resin, etc.) or clay, mica, silica, graphite, glass beads, alumina, and calcium carbonate can also be blended in appropriate amounts depending on the purpose.

The polyimide resin composition of the present invention is molded by a known molding method such as an injection molding method, an extrusion molding method, a compression molding method, or a rotary molding method, and is put into practical use.

〔Example〕

The present invention will be explained below using examples.

Synthesis Example-1 186 g (1.0 mol) of 4,4'-dihydroxybiphenyl and 4 m-dinitrobenzene were placed in a glass reaction vessel.
38 g (2.6 mol), 363 g of potassium carbonate and N
.

Charge 2000 ml of N-dimethylformamide to 145
React at ~150°C for 16 hours. After the reaction is completed, cool and filter) [NO2 is removed, and then the solvent in the filtrate is distilled off under reduced pressure, cooled to 65°C, and methanol 2000
ml and stirred for 1 hour. The crystals were separated by filtration, washed with water, washed with methanol, and dried to obtain brown crystals of 4,4'-bis(3-nitrophenoxy)biphenyl.

Yield: 426 g (Yield: 99.'iχ) Next, crude 4,4''-bis(3
100 g (0.23 mol) of -nitrophenoxy)biphenyl, activated carbon Log, 1 g of ferric chloride hexahydrate and 500 ml of methyl cellosolve are charged and stirred under reflux for 30 minutes. Next, 46g of hydrazine hydrate at 70-80℃
(0.92 mol) was added dropwise over 3 hours. After the dropwise addition was completed, the reaction was completed by stirring at 70 to 80°C for 5 hours.

After cooling, filter to remove the catalyst, drain into 500 ml of water and filter the crystals. To this, 48g of 35χ hydrochloric acid and 50
540 ml of χ isopropyl alcohol (IPA)/water was added and dissolved by heating, and when the mixture was allowed to cool, 4,4′-bis(3-aminophenoxy)biphenyl hydrochloride was precipitated. After filtering this, 540ml of 50χ IPA/water was added and dissolved by heating, 5g of activated carbon was added and filtered, neutralized with aqueous ammonia, and the crystals were filtered, washed with water, dried, and 4.4'-bis(
3-Aminophenoxy)biphenyl was obtained. Yield 72.
0g (Yield 85χ) Colorless crystals mp, 144-b Purity 99.6χ (by high performance liquid chromatography) CHN Elemental analysis Calculated value (χ)*78.26 5.43 7.
61 analysis value (χ) 78.56 5.21 7.66)
C241h. Gate S as Nz02: 368 (
M”), 340.184I R(KBr, cm-'
): 3400 and 3310 (NHZ group), 1200
(Ether bond) Synthesis example-2 2,2-bis(4-hydroxyphenyl)propane (85.6 g < 0.375 mol), m
- 151.2 g (0.9 mol) of dinitrobenzene, 124.6 g of potassium carbonate and 660 ml of N,N-dimethylformamide are charged and reacted at 145-150° C. for 10 hours. After the reaction was completed, the KNO□ was removed by cooling and filtration, and then the solvent in the filtrate was distilled off under reduced pressure.
℃, charged with 450 ml of methanol, and stirred for 1.0 hour. The crystals were separated by filtration, washed with water, washed with methanol, and dried to obtain yellowish brown crystals of 2,2-his(4-(3-nitrophenoxy)phenyl)propane. Yield: 164.8 g.
(Yield 93.5χ) Next, crude 2,2-bisC4-C3-nitrophenoxy)phenyl]propane 1 was placed in a 500 ml glass reaction vessel.
00g (0.21mol), activated carbon Log, ferric chloride.
1 g of hexahydrate and 300 ml of methyl cellosolve are charged and stirred under reflux for 30 minutes. Next, 42 g (0.84 mol) of hydrazine hydrate is added dropwise over 2 hours at 70-80°C. The mixture is further stirred at 70-80°C for 5 hours. After cooling, the catalyst is removed by filtration, and 150 ml of methyl cellosolve is distilled off. Add 270g of 20χ hydrochloric acid aqueous solution, and add 3 ml of salt.
When 0 g is added and cooled to 20 to 25° C. with stirring, crystals are precipitated. After filtering this, it is neutralized with aqueous ammonia in 30xIPA/water to precipitate crystals. This was filtered, washed with water, dried, and then recrystallized from a mixed solvent of benzene and n-hexane to obtain 2,2-bis[4-(3-aminophenoxy)phenyl]propane. Yield 69.2g
(Yield 75χ) Colorless crystal mp, I06~108℃ Purity 99.5χ (by high performance liquid chromatography) HN Elemental analysis Calculated value (χ)* 79.02 6.34
6.83 Analysis value (χ) 79.21 6.40
6.71 pieces) MS as CtH2bNzO□: 470 (M"), 455 (M
H3)"I R(KBrScm-'): 3460 and 3370 (Nl2 group), 1200 (ether bond) Synthesis Example-3 218 g (1 mol) of 4,4-dihydroxydiphenyl sulfide, m- in a 3A' glass reaction vessel Dinitrobenzene 403g (2.4 mol), potassium carbonate 331
g (24 mol) and N,N-dimethylformamide 2.5E were charged and reacted at 145-150°C for 20 minutes. After the reaction was completed, the mixture was cooled and filtered, and the solvent was distilled off from the filtrate under reduced pressure. After cooling to 65°C, methanol 800ml
and stirred for 1 hour. Filter the obtained crystals,
After washing with methanol and drying, 4,4゛-bis(3
-Nitrophenoxy)diphenyl sulfide crystal 42
9g (yield: 92.3χ) was obtained.

Then, 428 g (0.93 mol) of this crude product was placed in a 31 glass reaction vessel, 22.6 g of activated carbon, 0.9 g of iron dichloride hexahydrate, and 1.5 p of methyl cellosolve were charged, and the mixture was heated under reflux. I stirred it for 30 minutes. Then 110-1
After 115.2 g (3.1 mol) of hydrazine hydrate was added dropwise over 2 hours at 15°C, the mixture was further stirred under reflux for 3.5 hours. After cooling, the catalyst was filtered off, and the solution was concentrated under reduced pressure. Next, 205 ml of 35x hydrochloric acid, 1120 ml of water, and 480 ml of isopropyl alcohol were added and dissolved by heating. After that, 20 g of activated carbon was charged and hot-filtered. Then, 112 g of common salt was added and cooled, and the precipitated hydrochloride crystals were filtered off. The obtained crystals are neutralized with aqueous ammonia using a conventional method to obtain the desired 4,4-bis(3-aminophenoxy).
Diphenylsulfide was obtained. Yield 265g (yield 6
6χ).

Colorless crystal mp, 112-113℃ (corr) Purity 99.9% or more HNS Elemental analysis Calculated value (X) * 71. '975.037
．． 00 B, 01 analysis value (χ > 71.904.54
MS (FD): 400 (M”) IR (KBr,
cm-'): 3390 and 3300 (NHZ group),
1220 (ether bond) Examples 1 to 6 In a container equipped with a stirrer, a reflux condenser, and a nitrogen introduction tube, 36.8 kg (100 mol) of 4,4'-bis(3-aminophenoxy)bisphenol and N , 175.8 kg of N-dimethylacetamide was charged, and 21.8 kg (1 kg) of pyromellitic dianhydride was charged under a nitrogen atmosphere at room temperature.
00 mol) was added in portions while being careful not to increase the solution temperature, and the mixture was stirred at room temperature for about 20 hours. The logarithmic viscosity of the polyamic acid thus obtained was 2.47 L11/g.

Furthermore, N, N-
After adding 337.5 kg of dimethylacetamide and heating to 70°C under a nitrogen atmosphere while stirring, 26. I
Kg (26 mol) of acetic anhydride and 9.05 Kg (9
When triethylamine (mol) was added dropwise, yellow polyimide powder began to precipitate in the tube for about 10 minutes after the completion of the dropwise addition, but after stirring under heating for an additional 2 hours, it was filtered under heat to obtain polyimide powder. This polyimide powder was washed with methanol and then dried under reduced pressure at 150°C for 5 hours to obtain 34.5 kg (yield: 98χ) of polyimide powder.

The fiber length is 3 m per 100 parts by weight of the obtained polyimide powder.
Silane-treated glass fiber with m5 fiber diameter of 13 μm (
C5-3PE-476S (manufactured by Nittobo Co., Ltd.) was added in the amount shown in Table 1, mixed with a drum blender mixer (manufactured by Yoda Seisakusho), and then
After melt-kneading at a temperature of 0° C., the strands were air-cooled and cut to obtain pellets.

The obtained pellets are injection molded (Arburg injection molding machine (
(maximum mold clamping force 35 tons) injection pressure 500 kg/d, cylinder temperature 400°C, mold temperature 180°C) to obtain tensile test pieces, bending test pieces, Izotsu impact test pieces, and mold shrinkage rate measurement test pieces. Ta. Tensile test piece is ASTM D-
638, bending test pieces to ASTM D-790, Izot impact test pieces to ASTM D-256, heat distortion temperature to ASTM D-648, mold shrinkage rate to ASTM
When the test was carried out according to D-955, the results shown in Table 1 were obtained.

Example-7 N,N-dimethylacetamide (DMAC) was added to 100 parts by weight of polyimide powder obtained in the same manner as in Example-1.
) 150 parts by weight were added to form a suspension solution, and to this was added 30 parts by weight of silane-treated glass fibers (manufactured by Nittobo Co., Ltd., C5-3PE-'476S) with a fiber length of 3 mm and a fiber diameter of 13 μm. , evenly dispersed. Further, this was pre-dried for 20 hours in a hot air open at 200°C, and then dried under reduced pressure at 150°C for 5 hours in a vacuum dryer to completely remove the solvent, thereby obtaining a glass fiber-impregnated powder. A test piece for measuring physical properties was obtained by pelletizing and injection molding in the same manner as in Examples 1 to 6. The obtained test pieces were subjected to the same operations as in Examples 1 to 6, and the results shown in Table 1 were obtained.

Example 8 In the same manner as Examples 1 to 6, 400 parts by weight of the polyamic acid solution was impregnated with 30 parts by weight of the glass fibers used in Examples 1 to 6 (manufactured by Nittobo Co., Ltd., C5-3PR-4765). After that, the same operation as in Example 7 was performed to obtain a glass fiber-impregnated powder. Thereafter, the same operations as in Example 7 were carried out to obtain the results shown in Table 1.

Examples 9 to 11 and Comparative Examples 1 to 3 Example 12JJ based on 100 parts by weight of polyimide powder obtained from the diamine carboxylic anhydride shown in Table 1.

Glass fiber used in ~6 (manufactured by Nittobo Co., Ltd., C5-3P
H-4765) was added in the amount shown in Table 1. Hereinafter, the same operations as in Examples 1 to 6 were performed to obtain the results shown in Table 1.

[Effects of the Invention] The polyimide resin composition of the present invention has excellent heat resistance, dimensional stability, mechanical strength, etc., and is expected to have a wide range of applications such as electrical and electronic parts and automobile parts. The effect is great.

Claims (1)

[Claims] Formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, Y is a direct bond, a divalent hydrocarbon group having 1 to 10 carbon atoms,
Hexafluorinated isopropylidene group, carbonyl group,
Represents a group selected from the group consisting of a thio group, a sulfinyl group, a sulfonyl group, or an oxide, and R is an aliphatic group having 2 or more carbon atoms, a cycloaliphatic group, a monocyclic aromatic group, or a fused polycyclic aromatic group. represents a tetravalent group selected from the group consisting of non-fused cyclic aromatic groups in which aromatic groups are interconnected directly or through a bridge member. ) Polyimide resin 100 having a repeating unit represented by
and 5 to 100 parts by weight of glass fiber.