JP2001234049A - Polyarylate/polyimide resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a composition excellent in heat resistance, mechanical characteristics and chemical resistance, good in moldability and capable of being molded at a low mold temperature. SOLUTION: This resin composition comprises a polyimide having a specific repeating unit and a crystalline polyarylate having a specified repeating unit.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a resin composition comprising a polyarylate and a polyimide (in this specification, a "resin composition comprising a polyarylate and a polyimide" is referred to as a "polyarylate / polyimide resin composition"). And a molded article made of them. More specifically, the present invention relates to a novel resin composition comprising polyarylate and polyimide having excellent heat resistance, dimensional stability, and heat resistance, and a molded article comprising the same.

[0002]

2. Description of the Related Art Conventionally, crystalline heat-resistant polymers have been disclosed in JP-B-38-16793, JP-B-63-49610.
PR, Tokiko 63-49611, Tokiko 1-4
No. 7285 discloses a p-phenylene isophthalate-based polymer obtained by copolymerizing 4,4'-dihydroxydiphenyl, resorcin, 2,2-bis (4-hydroxyphenyl) propane, substituted hydroquinone and the like. .

[0003] These polymers are crystalline and have a melting point (T
m), a high secondary transition point (Tg), and excellent heat resistance.
As disclosed in Japanese Patent Publication No. 3-49611 and Japanese Patent Publication No. Hei 1-47285, it is a polymer useful as a film or the like.

However, these polymers generally have a high viscosity and are generally high in viscosity for injection molding, as can be seen from the fact that the polymerization reaction is carried out in a solvent having a high boiling point according to the method described in JP-B-38-16793. When used as a resin, there are problems that the fluidity is poor and precise parts cannot be molded, and that the molding must be performed at a high mold temperature due to a high secondary transition point.

[0005]

SUMMARY OF THE INVENTION In view of the above-mentioned problems, the present invention has a mold temperature of 140 ° C. or lower, preferably 110 ° C., without impairing the excellent properties such as heat resistance of the polymer.
It is an object of the present invention to provide a technical means that enables injection molding even if the temperature is reduced below, and further improves crystallinity to improve dimensional stability.

[0006]

As a result of repeated studies, the present inventors have found that the above-mentioned problems can be solved by blending a specific polyimide with the above-mentioned novel crystalline polyarylate. The present invention has been achieved.

That is, the present invention is as follows. 1. The repeating unit is substantially the following formula (1)

[0008]

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(Here, Ar ₀ may have a linking group selected from the group consisting of a direct bond, a carbonyl group, a sulfonyl group, and an alkylene containing a substituent of a halogen atom. An aromatic hydrocarbon group,
R ¹ is a group selected from the group consisting of an aliphatic hydrocarbon group having 2 to 30 carbon atoms and an alicyclic hydrocarbon group having 4 to 30 carbon atoms. ) And a polyimide (A)
The repeating unit is represented by the following formulas (2-1) and (2-2)

[0010]

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(Where Ar ₁ is an aromatic hydrocarbon group having 6 to 18 carbon atoms, and the ratio of (2-2) to the total of (2-1) and (2-2) is 10 to 10) And a crystalline polyarylate (B) comprising a repeating unit represented by the following formula: wherein the polyimide (A) and the crystalline polyarylate (B) are contained in the resin composition.
Weight ratio of 0.05 to 99.95 to 99.95
A resin composition that is between 0.05 and 0.05.

2. 2. The resin composition according to the above 1, wherein the polyimide and the polyarylate are compatible with each other.

3. Formulas (2-1) and (2-2)
Wherein Ar ₁ is

[0014]

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The composition according to the above item 1 or 2, wherein the composition is one or more selected from the group consisting of:

4. Formulas (2-1) and (2-2)
Wherein Ar ₁ is

[0017]

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The composition according to any one of the above 1 to 3, wherein

5. In the above formula (1), Ar ₀ is

[0020]

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The composition according to any one of the above items 1 to 4, wherein the composition is one or more aromatic groups selected from the group consisting of:

6. In the above formula (1), R ¹ is at least one selected from the group consisting of nonamethylene, decamethylene, undecanemethylene and dodecamethylene groups, wherein the composition according to any one of the above items 1 to 5, object.

7. The polyimide (A) has the following formula (1-
2) and (1-3)

[0024]

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The resin composition as described in any one of the above items 1 to 6, which comprises one or both of the components represented by the following formulas:

8. A molded article comprising the resin composition according to any one of the above 1 to 7.

9. A flexible printed circuit board using the resin composition according to any one of the above 1 to 7.

10. A rigid printed board using the resin composition according to any one of the above 1 to 7.

(11) An automotive material using the resin composition according to any one of the above 1 to 7.

12. A connector using the resin composition according to any one of the above 1 to 7.

13. An electronic component housing using the resin composition according to any one of the above 1 to 7.

That is, the present invention relates to such a resin composition, wherein the polymer chain substantially comprises an aromatic dicarboxylic acid residue, a hydroquinone residue, and a 4,4′-dihydroxydiphenyl residue. It is a resin composition comprising a mixture of linearly copolymerized polyarylate and polyimide.

In the polyarylate constituting the resin composition of the present invention, the polymer chain is substantially composed of the following repeating unit (2-1) and the following repeating unit (2-2):

[0034]

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The ratio (copolymer molar fraction) of each repeating unit of (2-1) and (2-2) is 90/10
It is a 65/35 substantially linear random copolymer.

The polyarylate is a crystalline, non-liquid crystalline (optically isotropic) random copolymer substantially composed of the above-mentioned repeating units.

The mole fraction of (2-1) and (2-2) [(2
If -1) / (2-2)] is larger than 90/10, the melting point of the polymer increases and the melt viscosity also increases.
Moldability is undesirably lowered, and if it is less than 65/35, the melting point and crystallinity of the polymer are lowered, and heat resistance is deteriorated, which is not preferable. The above molar fraction [(2-1)
/ (2-2)] is more preferably 85/15 to 70.
/ 30.

The molar fraction [(2-1) / (2-
2)] is actually the difference between the hydroquinone residue and 4,4 ′
The ratio may be determined as the ratio to the dihydroxydiphenyl residue.

In this polyarylate, Ar ₁ is preferably

[0040]

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And is more preferably selected from the group consisting of

[0042]

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Is a repeating unit.

The method for producing the polyarylate is not particularly limited. Examples thereof include a method in which an aromatic dicarboxylic acid diphenyl ester, hydroquinone, and 4,4'-dihydroxydiphenyl are heated and polycondensed in the presence of a catalyst; A method of heating and polycondensing an acid, hydroquinone and 4,4′-dihydroxydiphenyl in the presence of a phenol which may have a substituent and a catalyst can be mentioned. In the present invention, the latter method can be preferably used as a method for producing a polymer, but is not limited thereto.

Since the polyarylate obtained by the above method has a relatively high melt viscosity, when the degree of polymerization is increased by melt polymerization, it is preferable to use a ruder type reactor or the like in combination.

The polymerization reaction is carried out by flowing an inert gas under reduced pressure to forcibly remove water and phenol components formed as a result of the reaction and, if necessary, excess dihydroxy compounds such as hydroquinone outside the reaction system. Is preferred.

The molecular weight of the polyarylate in the present invention is not particularly limited, but is generally in a phenol / tetrachloroethane mixed solvent (weight ratio 6/4) at a temperature of 35 ° C.
The intrinsic viscosity measured at a concentration of 1.2 g / dl is 0.1 to 1
0.0 is preferred. The lower limit is more preferably 0.1.
5, more preferably 0.25, and the upper limit is even more preferably 7.

The polyimide constituting the resin composition of the present invention has the following repeating units.

[0049]

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(Where Ar ₀ may have a linking group selected from the group consisting of a direct bond, a carbonyl group, a sulfonyl group and an alkylene containing a substituent of a halogen atom. An aromatic hydrocarbon group,
R ¹ is a divalent residue obtained by removing two amino groups from an aliphatic diamine having 2 to 30 carbon atoms and a divalent residue having 4 to 3 carbon atoms.
It is at least one group selected from the group consisting of divalent residues obtained by removing two amino groups from 0 alicyclic diamines. )).

As the aromatic hydrocarbon, for example, the following formula:

[0052]

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Or

[0054]

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(Where X is a single bond, a carbonyl group, a sulfonyl group, an alkylene group having 1 to 3 carbon atoms, or
To 3) haloalkylene groups). One or more of these may be present together in the polymer chain.

In general, the following formula

[0057]

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The group represented by the following formula is preferred, and more preferably

[0059]

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And particularly preferably a group represented by the following formula:

[0061]

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This is a group represented by

In the formula (1), R ¹ has 2 to 30 carbon atoms.
Or a divalent residue obtained by removing two amino groups from an alicyclic diamine having 4 to 30 carbon atoms. R ¹ can be composed of one or a combination of two or more selected from these residues.

The divalent residue obtained by removing two amino groups from an aliphatic diamine having 2 to 30 carbon atoms includes, for example,

[0065]

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(Where n is 2 to 30), for example, ethylene, propylene, trimethylene, tetramethylene, dimethylpropylene, hexamethylene, octamethylene, decamethylene, undecamethylene, dodecamethylene, eicosa Methylene, triacontamethylene, furthermore 2,2,4-trimethylhexamethylene,
2,4,4-trimethylhexamethylene and the like can be mentioned.

The divalent residue obtained by removing two amino groups from an alicyclic diamine having 4 to 30 carbon atoms includes, for example,

[0068]

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The following groups can be mentioned. Of these, the following formula

[0070]

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A group represented by the following formula is preferred.

The repeating unit represented by the above formula (1) in the present invention includes the following formula (1-1)

[0073]

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(Where the definition of Ar ₀ is the same as in the above formula (1)) or a repeating unit represented by the following formula (1):
-2)

[0075]

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(Where the definition of Ar ₀ is the same as in the above formula (1), and m is an integer of 9 to 12). 1)

[0077]

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The repeating unit represented by the following formula or the following formula (1-
2-1)

[0079]

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(Where m is 10 and / or 12) is particularly preferred.

The above polyimide is produced by a known method.
can do. For example, Ar ₀Inducing
A dihydrate of tetracarboxylic acid as a raw material¹
Polyamic acid from a diamine capable of inducing
And then heat ring-closed, or
, Carbodiimide, triphenyl phosphite, etc.
Method for chemical ring closure using a cyclizing agent, the above tetracarboxylic acid
And the above R¹Can be induced
A method of heating and decarboxylating and polymerizing
Examples can be given.

Examples of the tetracarboxylic dianhydride used in the above method include pyromellitic dianhydride,
3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride and 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride can be exemplified.

As the diamine, ethylenediamine, 1,2-propanediamine, 1,3-propanediamine, 2,2-dimethyl-1,3-propanediamine,
1,6-hexamethylenediamine, 1,8-octamethylenediamine, 1,10-decamethylenediamine, 1,
11-undecamethylenediamine, 1,12-dodecamethylenediamine, 2,2,4-trimethylhexamethylenediamine, 2,4,4-trimethylhexamethylenediamine, isophoronediamine, 1,3-cyclohexanediamine, 1,4 -Cyclohexanediamine, 1,4-
Cyclohexanedimethylamine, 4-methyl-1,3-
Cyclohexanediamine, p-xylylenediamine and the like can be mentioned.

As the diisocyanate component, ethylene diisocyanate, 1,2-propane diisocyanate, 1,3-propane diisocyanate, 2,2-dimethyl-1,3-propane diisocyanate, 1,6-hexamethylene diisocyanate, 1,8- Octamethylene diisocyanate, 1,10-decamethylene diisocyanate, 1,11-undecamethylene diisocyanate, 1,12-dodecamethylene diisocyanate, 2,
2,4-trimethylhexamethylene diisocyanate,
2,4,4-trimethylhexamethylene diisocyanate, isophorone diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, 1,4-cyclohexanedimethyl isocyanate, 4-methyl-1,3-cyclohexane diisocyanate, p-xylylene And diisocyanates.

The molecular weight of the polyimide in the present invention is not particularly limited. Generally, when the polyimide is dissolved in a phenol / tetrachloroethane mixed solvent (weight ratio: 6/4), the temperature is 35 ° C. and the concentration is 1.2 g / dl. The measured ultimate concentration is preferably 0.1 to 12.0. The lower limit is more preferably 0.15, more preferably 0.25, and the upper limit is still more preferably 10.

The compounding ratio of the above-mentioned polyarylate and polyimide in the resin composition of the present invention is such that the amount of the crystalline polyarylate is 99.95 to 0.05 parts by weight with respect to the amount of the polyimide being 0.05 to 99.95 parts by weight. It is a ratio that becomes a part. If the amount of polyimide is less than the above range, the effect of the present invention is poor, and if it is too large, the properties of polyarylate are undesirably deteriorated.

In the present invention, a plurality of polymers can be used in combination as polyimide. In this case, the total amount of the plurality of polymers may be within the above range.

As the polyimide of the present invention, the above-mentioned polyimides can be used, but preferably those comprising a pyromellitic acid residue and a linear aliphatic diamine residue.

It is desirable that the polyimide and the polyarylate are compatible with each other in the resin composition according to the present invention, because the MFR described later can be made larger. This compatibility can be confirmed by the fact that there is only one peak appearing in the melting point when measured by a differential scanning calorimeter (DSC).

Further, the resin composition of the present invention can contain various additives as required. Additives include glass fiber, metal fiber, aramid fiber, ceramic fiber, potassium titanate whisker, fibrous reinforcing agents such as carbon fiber, talc, calcium carbonate, mica, clay, titanium oxide, aluminum oxide, metal powder, etc. Fillers, heat stabilizers such as phosphate esters and phosphites, light stabilizers, ultraviolet absorbers, lubricants, pigments, flame retardants, flame retardant aids, plasticizers, crystal nuclei Agents and the like.

Further, other resins can be blended as long as the physical properties of the resin composition according to the present invention are not impaired.

The above-mentioned polyarylate and polyimide or, if necessary, other additives and other resin are mixed together when the polyarylate and polyimide are both soluble in an organic solvent, dissolved and mixed in an organic solvent. It can be prepared by a method of removing an organic solvent. This method is very effective especially when the glass transition temperature of the resin composition of the present invention is high.

Mixing can also be carried out using a twin-screw extruder as long as the polymer does not decompose and at least one polymer flows within a temperature range.

Further, it can be produced by a method in which polyarylate is mixed and polymerized in the presence of polyimide.

The resin composition of the present invention produced as described above is molded into various molded products by utilizing a usual melt molding method, for example, an injection molding method, a compression molding method, or an extrusion molding method. be able to.

The polyarylate used in the present invention is:
Since it can be produced by a melt polymerization method using inexpensive raw materials, it can be produced industrially at a very low cost, and the obtained polymer has a non-liquid crystalline (isotropic) having a melting point of 300 ° C. or more. ) Is a crystalline polymer.

By mixing polyimide with this polyarylate, not only a molded article having excellent heat resistance, mechanical properties, and chemical resistance can be obtained, but also the moldability is good and the mold temperature is particularly low. It has the feature that molding conditions can be selected. Moreover, it is excellent in economical efficiency and is extremely useful as a resin for molding.

Therefore, the resin composition of the present invention has heat resistance,
This is a new resin composition with excellent mechanical properties and moldability, and uses excellent heat resistance to provide flexible printed circuit boards, rigid printed circuit boards, housings and connectors for electric and electronic parts, and good mechanical properties. It is utilized as a material suitable for automotive parts and various other molded products.

[0099]

According to the resin composition of the present invention, a molded article which is excellent in heat resistance, mechanical properties and chemical resistance, has good moldability and can be molded at a low mold temperature can be obtained.

[0100]

The present invention will be described below with reference to examples, but the present invention is not limited to these examples. Unless otherwise specified in the following examples, “parts” means “parts by weight”.

The analysis method was as follows. The intrinsic viscosity ([η]) was measured using a phenol / 1,1,2,2-tetrachloroethane mixed solvent (weight ratio 6/4). The crystallization temperature (Tmc) was 38 at 20 ° C./min when measured with a DSC-7 differential scanning calorimeter.
This is the value when the temperature is raised to 0 ° C. and then lowered at 20 ° C./min. The melt viscosity is a value measured at a temperature of 335 ° C. and a load of 2.16 kgf using a melt flow rate (MFR) measuring device based on JIS-K7210.

Example 1 A polyimide was synthesized as follows. In a 5 L separateable flask equipped with Dean Stark, condenser, stirrer and nitrogen inlet,
260 g of 1,12-dodecamethylenediamine (1.3 m
ol) and 283 g (1.3 mol) of pyromellitic anhydride
Was heated to 160 ° C. using a mixed solution of 2 L of N-methylpyrrolidone and 0.5 L of toluene as a solvent, and a polymerization and ring-closing reaction were carried out while distilling water out of the system with a Dean-Stark apparatus. The distilled water was the theoretical amount of 47 ml. When kept at the same temperature for 4 hours, a precipitate of polyimide crystal was formed. After cooling, the reaction solution was filtered when the reaction solution dropped to 80 ° C. or lower, washed with acetone, washed with hot water, and dried at 120 ° C. with a drier.
The obtained polymer had [η] = 1.1.

The polyarylate was synthesized as follows. 100 parts of isophthalic acid, 80 parts of hydroquinone,
30 parts of 4,4'-dihydroxydiphenyl, 100 parts of phenol, and 0.05 part of antimony trioxide were charged into a reaction system equipped with a stirrer and a distilling system, and charged with nitrogen under pressure.
Heated to 0 ° C. Pressure from 5 kg / cm ² to 2 kg / c
The reaction was carried out for 5 hours while gradually lowering to m ² and distilling water generated by the reaction out of the system. During this time, 23 parts of water were produced.

Next, the pressure in the reaction system was returned to normal pressure, and the reaction was carried out for 60 minutes while distilling off volatile components in a nitrogen stream. During this time, the reaction temperature was raised from 280 ° C to 340 ° C.

Then, the inside of the system was gradually evacuated, and after 60 minutes, the reaction was carried out under a high vacuum of about 0.5 mmHg for 50 minutes to obtain a polymer having an intrinsic viscosity of 0.84.

One part by weight of the obtained polyimide and 9 parts by weight of polyarylate were dissolved in a mixed solvent of phenol / 2,4,6-trichlorophenol (weight ratio: 6/4) to prepare a 5% by weight dope. After diluting with hexane to precipitate crystals, the crystals were filtered, washed three times with methanol, and then dried at 150 ° C. with a vacuum dryer. Table 1 shows the physical properties of the obtained resin composition.

As a result of differential scanning calorimetry, the melting point was 338 ° C.
At only one place, and it was confirmed that the polyimide and polyarylate in this composition were compatible with each other.

Further, using this resin, a barrel temperature of 3
At 50 ° C, mold temperature 140 ° C, 10cmX10cmX3
When a flat plate having a thickness of mm was molded, the molding was smooth and a good molded product was obtained.

The obtained resin composition has a high Tmc despite having a large MFR, and is a flexible printed circuit board, a rigid printed circuit board, a heat-resistant housing for electric and electronic parts, a connector, and a heat-resistant part for an automobile engine room. It was shown to be excellent.

Comparative Example 1 The polyarylate of Example 1 was dissolved in a phenol / 2,4,6-trichlorophenol mixed solvent (weight ratio: 6/4) to prepare a 5% by weight dope, which was diluted with methanol. After depositing crystals by filtration, the resultant was filtered, washed with methanol three times, and dried at 150 ° C. with a vacuum dryer. Table 1 shows the physical properties of the obtained resin composition. Using this resin, 10cmX10
When a flat plate of cm × 3 mm was formed, the barrel temperature was 35
Even at 0 ° C. and a mold temperature of 140 ° C., a sufficient discharge amount could not be obtained, and a normal molded product could not be obtained.

[0111]

[Table 1]

 ──────────────────────────────────────────────────続 き Continuing from the front page (72) Inventor Jiro Jonobu 2-1 Hinode-cho, Iwakuni-shi, Yamaguchi Pref. FD010 FD060 4J043 PA08 QB31 RA35 SA06 SB01 SB02 TA14 TB01 TB02 UA041 UA121 UA122 UA132 UA761 UA771 UB011 UB152 UB302 UB401 VA021 VA022 VA052 ZA12 ZB50 ZB52 ZB53 ZB55

Claims (13)

[Claims] The repeating unit substantially has the following formula (1): (Here, Ar ₀ may have a linking group selected from the group consisting of a direct bond, a carbonyl group, a sulfonyl group, and an alkylene containing a substituent of a halogen atom, and an aromatic carbon atom having 6 to 15 carbon atoms. A hydrogen group, R ¹ is an aliphatic hydrocarbon group having 2 to 30 carbon atoms and 4 to
A group selected from the group consisting of 30 alicyclic hydrocarbon groups. And a repeating unit represented by the following formulas (2-1) and (2-2): (Here, Ar ₁ is an aromatic hydrocarbon group having 6 to 18 carbon atoms, and the ratio of (2-2) to the total of (2-1) and (2-2) is 10 to 35 mol%. A) a crystalline polyarylate (B) comprising a repeating unit represented by the following formula:
Wherein the weight ratio of the polyimide (A) and the crystalline polyarylate (B) in the resin composition is 0.05 to 99.95 to
A resin composition that is between 99.95 and 0.05. 2. The resin composition according to claim 1, wherein the polyimide (A) and the polyarylate (B) are compatible. 3. In the above formulas (2-1) and (2-2), Ar ₁ is The composition according to claim 1, wherein the composition is one or more selected from the group consisting of: 4. In the above formulas (2-1) and (2-2), Ar ₁ is The composition according to any one of claims 1 to 3, wherein 5. In the above formula (1), Ar ₀ is The composition according to any one of claims 1 to 4, wherein the composition is one or more aromatic groups selected from the group consisting of: 6. The method according to claim 1, wherein in the formula (1), R ¹ is one or more selected from the group consisting of nonamethylene, decamethylene, undecanemethylene, and dodecamethylene. A composition according to any of the above. 7. The polyimide (A) is mainly composed of the following formula (1)
-2), (1-3) and The resin composition according to any one of claims 1 to 6, comprising one or both of the components represented by: 8. A molded article comprising the resin composition according to claim 1. 9. A flexible printed circuit board using the resin composition according to claim 1. 10. A rigid printed circuit board using the resin composition according to claim 1. 11. An automotive material using the resin composition according to claim 1. 12. A connector using the resin composition according to claim 1. 13. An electronic component housing using the resin composition according to claim 1.