JP4462412B2 - Resin composition - Google Patents

Description

  The present invention relates to a novel resin composition excellent in extrusion moldability and injection moldability and excellent in heat resistance, fluidity and strength during melting, toughness, and sliding properties.

  An aromatic polyamideimide resin (hereinafter sometimes abbreviated as PAI resin) is a plastic material having excellent heat resistance, mechanical strength, electrical properties, chemical resistance, and self-lubricating properties. However, except for varnish and film applications, the melt fluidity is inferior, and most of them are often difficult to injection mold. Therefore, the present situation is that molding is performed by the compression molding method.

  On the other hand, polyarylene sulfide resins (hereinafter sometimes abbreviated as PAS resins) represented by polyphenylene sulfide resins (hereinafter sometimes abbreviated as PPS) are excellent in heat resistance, electrical properties, and solvent resistance. In particular, the melt fluidity is excellent. It is also known to give excellent mechanical strength, rigidity and dimensional stability by strengthening with a filler or the like.

It has been proposed that a resin composition having excellent heat resistance, mechanical strength, and fluidity can be obtained by combining these PAI resin and PAS resin (see Patent Document 1 and Patent Document 2).
However, even in the above resin composition, the PAI resin is not well compatibilized, and a material having good melt fluidity, toughness, and mechanical strength after compounding has not been obtained. Therefore, it was unsuitable for uses such as precision molding and thin molding.

Japanese Patent No. 2868043 JP-A-11-293109

  An object of the present invention is to improve the compatibility of a resin composition composed of a PAI resin and a PAS resin in view of the above-described drawbacks, and to facilitate complexing by melt kneading. Moreover, it is providing the resin composition excellent in the fluidity | liquidity at the time of a melt | dissolution, intensity | strength, toughness, and heat resistance.

That is, the present invention provides (1) an aromatic polyamide having a weight average molecular weight (Mw) of 1,000 to 100,000 and an amino group contained in the molecule of 0.00002 to 0.002 mol / g. 5 to 60 parts by weight of imide resin (A), (2) 95 to 40 parts by weight of polyarylene sulfide resin (B), and (3) 0.01 to 100 parts by weight in total of (A) and (B) A resin composition comprising 10 parts by weight of an episulfide compound (C).
Moreover, this invention includes the molded article which consists of this resin composition.
Further, the present invention is a method for improving the melt fluidity of a resin composition comprising an aromatic polyamideimide resin and a polyarylene sulfide resin, wherein the weight average molecular weight (Mw) is 1,000 to 100,000, and Resin composition consisting of 5 to 60 parts by weight of aromatic polyamideimide resin (A) and 95 to 40 parts by weight of polyarylene sulfide resin (B) in which the amino group contained in the molecule is 0.00002 to 0.002 mol / g The method includes adding 0.01 to 10 parts by weight of the episulfide compound (C) to the product.

  According to the present invention, a specific (A) aromatic polyamideimide resin, (B) polyarylene sulfide resin, and (C) an episulfide compound are blended at a specific ratio, so that the compatibility is improved and the composite is formed at the time of melting. In addition, it is possible to provide a resin composition excellent in fluidity, strength, toughness, and heat resistance when melted.

<Aromatic polyamideimide resin (A)>
The aromatic polyamideimide resin (PAI resin) which is the component (A) of the resin composition of the present invention is represented by the following general formula (I).

（Ａｒ_１は炭素数６〜１８の２価の芳香族基、炭素数６〜１８の２価の脂環族基または炭素数２〜１２の２価の脂肪族基である。Ａｒ_２は炭素数６〜１８の３価の芳香族基、ｎは４〜４００の整数を表す）
Ａｒ_１の炭素数６〜１８の２価の芳香族基として、置換若しくは非置換のアリーレン基が挙げられる。アリーレン基としてフェニレン基、ナフタレン基、ビフェニリレン基、ベンジレン基（トルエン−ジイル基）、１，４−フェニレンビス（メチレン）基が挙げられる。置換基としては、メチル基、エチル基、プロピル基等の炭素数１〜３のアルキル基、塩素原子、臭素原子等のハロゲン原子が挙げられる。

(Ar ₁ is a bivalent aromatic group having 6 to 18 carbon atoms, a divalent alicyclic group having 6 to 18 carbon atoms, or a divalent aliphatic group having 2 to 12 carbon atoms. Ar ₂ is carbon. A trivalent aromatic group of formula 6-18, n represents an integer of 4-400)
Examples of the divalent aromatic group having 6 to 18 carbon atoms of Ar ₁ include a substituted or unsubstituted arylene group. Examples of the arylene group include a phenylene group, a naphthalene group, a biphenylylene group, a benzylene group (toluene-diyl group), and a 1,4-phenylenebis (methylene) group. Examples of the substituent include alkyl groups having 1 to 3 carbon atoms such as a methyl group, an ethyl group, and a propyl group, and halogen atoms such as a chlorine atom and a bromine atom.

Ar _{1 includes} an aromatic group represented by the following formula.

（式中、Ｚは、−ＣＨ_２−、−Ｃ（ＣＨ_３）_２−、−ＳＯ_２−、−Ｓ−、−ＣＯ−または−Ｏ−である）

(In the formula, Z is —CH ₂ —, —C (CH ₃ ) ₂ —, —SO ₂ —, —S—, —CO— or —O—).

  More specifically, an aromatic group represented by the following formula can be given.

Examples of the divalent alicyclic group having 6 to 18 carbon atoms of Ar ₁ include a substituted or unsubstituted cycloalkylene group. Specific examples include the following cycloalkylene groups.

Ａｒ_１の炭素数２〜１２の２価の脂肪族基として、炭素数２〜１２のアルキレン基が挙げられる。より具体的には−（ＣＨ_２）_ｍ−で表される基（ｍ＝２〜１２）が挙げられる。

Examples of the divalent aliphatic group having 2 to 12 carbon atoms of Ar ₁ include an alkylene group having 2 to 12 carbon atoms. More specifically, groups represented by — (CH ₂ ) _m — (m = 2 to 12) can be mentioned.

Specific examples of Ar ₁ include those described above, but two or more kinds of compounds may be mixed and used.
Particularly preferable examples are as follows.

Ａｒ_２は炭素数６〜１８の３価の芳香族基である。芳香族基として置換若しくは非置換のフェニル−トリイル（phenyl−trily）基、下記式

Ar ₂ is a trivalent aromatic group having 6 to 18 carbon atoms. A substituted or unsubstituted phenyl-trily group as an aromatic group, the following formula

で表される芳香族基（Ｙは、−ＣＯ−、−Ｏ−ＣＯ−）が挙げられる。

The aromatic group represented by these (Y is -CO-, -O-CO-) is mentioned.

  More specifically, the following are exemplified, but two or more kinds of compounds may be mixed and used.

The PAI resin is produced by, for example, an acid chloride method in which an aromatic diamine and trimellitic anhydride monochloride are polymerized (for example, Japanese Examined Patent Publication No. 46-15513), a polymerization reaction of aromatic diisocyanate and trimellitic anhydride. Known isocyanate methods (for example, Japanese Patent Publication No. 44-19274), direct polymerization methods in which aromatic diamine and trimellitic anhydride are heated to 200 to 250 ° C. (for example, Japanese Patent Publication No. 49-4077). Any manufacturing method can be used.
As the PAI resin used in the present invention, those having a weight average molecular weight (Mw) in terms of PEG using GPC of 1,000 to 100,000 can be used. Preferably, the weight average molecular weight in terms of PEG is 1,000 to 50,000, more preferably 1,000 to 30,000.

The weight average molecular weight in terms of PEG can be measured under the following conditions using LC-6A and RID-6A (detector) manufactured by Shimadzu Corporation. The weight average molecular weight in terms of PEG can be obtained by measuring PEG having a known molecular weight and preparing a calibration curve.
Column used: shodex KD-806M
Eluent: N, N-dimethylformamide Column temperature: 50 ° C.
Eluent flow rate: 0.5 ml / min

Moreover, what the amino group contained in the molecule | numerator of the PAI resin used for this invention is 0.00002-0.002 mol / g measured by neutralization titration using hydrochloric acid can be used. Preferably, it is 0.00005-0.001 mol / g.
For neutralization titration, PAI resin was dissolved in dimethylformamide, 0.1 mol / l hydrochloric acid was added dropwise, and the neutralization point was judged using a potentiometer.

<Polyarylene sulfide resin (B)>
The polyarylene sulfide resin (PAS resin) which is the component (B) of the resin composition of the present invention is the following general formula (II)
[-Ar-S-] (II)
(In the formula, -Ar- is an arylene group.)
An aromatic polymer having a repeating unit of arylene sulfide represented by
When [-Ar-S-] is defined as 1 mol (basic mol), the PAS resin used in the present invention usually has this repeating unit of 50 mol% or more, preferably 70 mol% or more, more preferably 90 mol%. It is a polymer containing above.
Examples of the arylene group include a p-phenylene group, an m-phenylene group, a substituted phenylene group (the substituent is preferably an alkyl group having 1 to 6 carbon atoms, or a phenyl group), p, p′-di. Examples thereof include a phenylene sulfone group, p, p′-biphenylene group, p, p′-diphenylenecarbonyl group, and naphthylene group. As the PAS resin, polymers having the same arylene group can be preferably used. However, from the viewpoint of processability and heat resistance, a copolymer containing two or more arylene groups can also be used.

Among these PAS resins, a PPS resin having a repeating unit of p-phenylene sulfide as a main constituent element is particularly preferable because it has excellent processability and is easily industrially available. In addition, polyarylene ketone sulfide, polyarylene ketone ketone sulfide, and the like can be used.
Specific examples of the copolymer include a random or block copolymer having a repeating unit of p-phenylene sulfide and a repeating unit of m-phenylene sulfide, a random or block copolymer having a repeating unit of phenylene sulfide and a repeating unit of arylene ketone sulfide, and phenylene sulfide. And a random or block copolymer having a repeating unit of arylene ketone ketone sulfide and a random or block copolymer having a repeating unit of phenylene sulfide and a repeating unit of arylene sulfone sulfide. These PAS resins are preferably crystalline polymers.

The PAS resin is preferably a linear polymer from the viewpoint of toughness and strength. Such a PAS resin can be obtained by a known method (for example, Japanese Patent Publication No. 63-33775) in which an alkali metal sulfide and a dihalogen-substituted aromatic compound are subjected to a polymerization reaction in a polar solvent.
Examples of the alkali metal sulfide include lithium sulfide, sodium sulfide, potassium sulfide, rubidium sulfide, and cesium sulfide. Sodium sulfide produced by reacting NaSH and NaOH in the reaction system can also be used.
Examples of the dihalogen-substituted aromatic compound include p-dichlorobenzene, m-dichlorobenzene, 2,5-dichlorotoluene, p-dibromobenzene, 2,6-dichloronaphthalene, 1-methoxy-2,5-dichlorobenzene, 4 , 4'-dichlorobiphenyl, 3,5-dichlorobenzoic acid, p, p'-dichlorodiphenyl ether, 4,4'-dichlorodiphenyl sulfone, 4,4'-dichlorodiphenyl sulfoxide, 4,4'-dichlorodiphenyl ketone, etc. Can be mentioned. These can be used alone or in combination of two or more.

  In order to introduce some branched structure or crosslinked structure into the PAS resin, a small amount of a polyhalogen-substituted aromatic compound having 3 or more halogen substituents per molecule can be used in combination. Preferred examples of the polyhalogen-substituted aromatic compound include 1,2,3-trichlorobenzene, 1,2,3-tribromobenzene, 1,2,4-trichlorobenzene, 1,2,4-tribromobenzene, Mention may be made of trihalogen-substituted aromatic compounds such as 1,3,5-trichlorobenzene, 1,3,5-tribromobenzene, 1,3-dichloro-5-bromobenzene, and alkyl-substituted products thereof. These can be used alone or in combination of two or more. Among these, 1,2,4-trichlorobenzene, 1,3,5-trichlorobenzene, and 1,2,3-trichlorobenzene are more preferable from the viewpoints of economy, reactivity, and physical properties.

  As the polar solvent, N-alkylpyrrolidone such as N-methyl-2-pyrrolidone, 1,3-dialkyl-2-imidazolidinone, tetraalkylurea, aprotic organic amide solvent represented by hexaalkylphosphate triamide, It is preferable because the stability of the reaction system is high and a high molecular weight polymer is easily obtained.

  The PAS resin has a melt viscosity of usually 10 to 600 Pa · s, preferably 50 to 550 Pa · s, more preferably 70 to 550 Pa · s, measured at a temperature of 310 ° C. and a shear rate of 1200 / sec. When two or more kinds of PAS resins having different melt viscosities are blended and used, it is preferable that the melt viscosity of the blend is in the above range. Further, it is particularly desirable that the PAS resin has a melt viscosity of 100 Pa · s or more from the viewpoint of mechanical strength, toughness, and the like. If the melt viscosity of the PAS resin is too small, physical properties such as mechanical strength and toughness may be insufficient. If the melt viscosity of the PAS resin is too large, the melt fluidity will be insufficient, and the injection moldability and extrusion moldability may be insufficient.

  The PAS resin can be used after the completion of the polymerization, but further, an aqueous solution containing an acid such as hydrochloric acid or acetic acid, a solution treated with a water-organic solvent mixed solution, or a salt solution such as ammonium chloride. It is preferable to use a material that has been treated with the above. In particular, when a PAS resin that has been washed until the pH in a mixed solvent adjusted to acetone: water = 1: 2 (volume ratio) is 8 or less is used, the melt flowability and mechanical properties of the resin composition are increased. The physical properties can be further improved.

  The PAS resin is desirably a granular material having an average particle diameter of 100 μm or more. If the average particle size of the PAS resin is too small, the feed amount is limited during melt extrusion by the extruder, so the residence time of the resin composition in the extruder becomes long, and problems such as deterioration of the resin composition occur. May occur. Further, it is not desirable in terms of manufacturing efficiency.

<Episulfide compound (C)>
The episulfide compound as component (C) is a compound having one or more episulfide groups in the molecule.
As the episulfide compound, a compound represented by the following general formula (III) is preferably used.

（式中、Ｘ_１はそれぞれ独立に水素原子または一般式：Ｅ−Ｒ_２−Ｘ_２−を表し、Ｅはエピスルフィド基またはエポキシ基を表し、エピスルフィド基は分子中に必ず１つ以上含まれる。
ここで、エピスルフィド基は下記式で表される。

(Wherein, X ₁ is each independently a hydrogen atom or a general formula: E-R 2 _-X 2 _- represents, E is represents an episulfide group or an epoxy group, episulfide group is always included one or more in a molecule.
Here, the episulfide group is represented by the following formula.

Ｘ_２はそれぞれ独立に炭素数１〜６の２価の炭化水素基、エーテル結合（−Ｏ−）、チオエーテル結合（−Ｓ−）、ジスルフィド結合（−Ｓ−Ｓ−）、カルボニル結合（−ＣＯ−）、エステル結合（−ＣＯＯ−）、アミド結合（−ＮＨＣＯ−）、または単結合を表す。
２価の炭化水素基として炭素数１〜３の脂肪族炭化水素基が好ましい。脂肪族炭化水素基としてアルカン−ジイル基が好ましい。アルカン−ジイル基としてメチレン基、トリメチレン基などの炭素数１〜３のアルキレン基、エタン−ジイル基が挙げられる。
Ｘ_３はそれぞれ独立に、水素原子または炭素数１〜２４の１価の炭化水素基、ビニル基、ヒドロキシ基、アミノ基、ウレイド基、イソシアネート基、エピスルフィド基、エポキシ基、およびメルカプト基を表す。
１価の炭化水素基として、炭素数１〜２４の脂肪族基、置換若しくは非置換の芳香族基が挙げられる。脂肪族基としてメチル基、エチル基、プロピル基、ブチル基、ヘキシル基などの炭素数１〜６のアルキル基が好ましい。芳香族基として、フェニル基、ベンジル基が好ましい。
Ｒ_１はそれぞれ独立に炭素数１〜２４の４価の炭化水素基を表す。炭化水素基として炭素数１〜６の４価の脂肪族基、炭素数６〜８の４価の脂環族基または炭素数６〜１５の４価の芳香族基が挙げられる。脂肪族基として炭素数１〜６のアルカン−テトライル基、脂環族炭化水素基として炭素数１〜８のシクロアルカン−テトライル基、芳香族炭化水素基として炭素数６〜１５のアレーン−テトライル基が好ましい。
Ｒ_２はそれぞれ独立に炭素数１〜２４の２価の炭化水素基を表す。炭化水素基として炭素数１〜３の脂肪族炭化水素基が好ましい。脂肪族炭化水素基としてアルカン−ジイル基が好ましい。アルカン−ジイル基としてメチレン基、エチレン基、プロピレン基などの炭素数１〜３のアルキレン基、エタン−ジイル基が挙げられる。ｎは０以上２０以下の整数を表す。）

X ₂ is independently a divalent hydrocarbon group having 1 to 6 carbon atoms, an ether bond (—O—), a thioether bond (—S—), a disulfide bond (—S—S—), a carbonyl bond (—CO -), An ester bond (-COO-), an amide bond (-NHCO-), or a single bond.
An aliphatic hydrocarbon group having 1 to 3 carbon atoms is preferred as the divalent hydrocarbon group. An alkane-diyl group is preferred as the aliphatic hydrocarbon group. Examples of the alkane-diyl group include an alkylene group having 1 to 3 carbon atoms such as a methylene group and a trimethylene group, and an ethane-diyl group.
X ₃ each independently represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 24 carbon atoms, a vinyl group, a hydroxy group, an amino group, a ureido group, an isocyanate group, an episulfide group, an epoxy group, and a mercapto group.
Examples of the monovalent hydrocarbon group include an aliphatic group having 1 to 24 carbon atoms and a substituted or unsubstituted aromatic group. As the aliphatic group, an alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group, and a hexyl group is preferable. As the aromatic group, a phenyl group and a benzyl group are preferable.
R ₁ each independently represents a tetravalent hydrocarbon group having 1 to 24 carbon atoms. Examples of the hydrocarbon group include a tetravalent aliphatic group having 1 to 6 carbon atoms, a tetravalent alicyclic group having 6 to 8 carbon atoms, and a tetravalent aromatic group having 6 to 15 carbon atoms. C1-C6 alkane-tetrayl group as an aliphatic group, C1-C8 cycloalkane-tetrayl group as an alicyclic hydrocarbon group, C6-C15 arene-tetrayl group as an aromatic hydrocarbon group Is preferred.
R ₂ each independently represents a divalent hydrocarbon group having 1 to 24 carbon atoms. An aliphatic hydrocarbon group having 1 to 3 carbon atoms is preferred as the hydrocarbon group. An alkane-diyl group is preferred as the aliphatic hydrocarbon group. Examples of the alkane-diyl group include an alkylene group having 1 to 3 carbon atoms such as a methylene group, an ethylene group, and a propylene group, and an ethane-diyl group. n represents an integer of 0 or more and 20 or less. )

The episulfide compound (C) is preferably a compound represented by the following general formula (III-1). The general formula (III-1) is a case where n = 0 and X ₁ = E—R ₂ —X ₂ — in the general formula (III).

（式中、Ｒ_２は、メチレン基、エチレン基またはエタン−１，１−ジイル基を表す。Ｘ_２は、単結合、−Ｏ−、アルカン−ジイル基を表す。アルカン−ジイル基としてメチレン基、エチレン基、トリメチレン基が挙げられる。Ｘ_３は、メチル基、エチル基、プロピル基、ブチル基などの炭素数１〜６のアルキル基、−ＯＨ、フェニル基またはベンジル基を表す。）

(Wherein R ₂ represents a methylene group, an ethylene group or an ethane-1,1-diyl group. X ₂ represents a single bond, —O— or an alkane-diyl group. A methylene group as the alkane-diyl group) X ₃ represents an alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group, a propyl group, or a butyl group, —OH, a phenyl group, or a benzyl group.

The episulfide compound (C) is preferably a compound represented by the following general formula (III-2). In the general formula (III-2), n = 1, X ₁ = E—CH ₂ —X ₂ —, X ₁ = H in (), X ₃ = H in (), ( ₂ ) X ₂ = single bond.

（式中、Ｘ_２は、単結合、−Ｏ−、−Ｓ−または−Ｓ−Ｓ−を表す。Ｘ_３は、−ＳＨまたはエピスルフィド基を表す。Ｒ_１は、炭素数１〜６のアルカン−テトライル基、炭素数６〜８のシクロアルカン−テトライル基または炭素数６〜１５のアレーン−テトライル基を表す。）
アルカン−テトライル基として、メタン−テトライル基、エタン−テトライル基、プロパン−テトライル基、ブタン−テトライル基、ペンタン−テトライル基などが挙げられる。シクロアルカン−テトライル基としてシクロヘキサン−テトライル基などが挙げられる。アレーン−テトライル基として、ベンゼン−テトライル基、キシレン−テトライル基、ジフェニル−テトライル基、ジフェニルメタン−テトライル基、ジフェニルプロパン−テトライル基などが挙げられる。

(In the formula, X ₂ represents a single bond, —O—, —S— or —S—S—. X ₃ represents —SH or an episulfide group. R ₁ represents an alkane having 1 to 6 carbon atoms. -Represents a tetrayl group, a cycloalkane-tetrayl group having 6 to 8 carbon atoms or an arene-tetrayl group having 6 to 15 carbon atoms.)
Examples of the alkane-tetrayl group include a methane-tetrayl group, an ethane-tetrayl group, a propane-tetrayl group, a butane-tetrayl group, and a pentane-tetrayl group. Examples of the cycloalkane-tetrayl group include a cyclohexane-tetrayl group. Examples of the arene-tetrayl group include a benzene-tetrayl group, a xylene-tetrayl group, a diphenyl-tetrayl group, a diphenylmethane-tetrayl group, and a diphenylpropane-tetrayl group.

Furthermore, the episulfide compound (C) is preferably a compound represented by the following general formula (III-3). General formula (III-3) is a case where n = 1, X ₁ = E—CH ₂ —X ₂ —), X ₃ = H, and X ₂ = single bond in general formula (III).

（式中、Ｘ_２は、それぞれ独立に―Ｓ―または−Ｏ−を表す。Ｒ_１は、炭素数１〜５のアルカン−テトライル基、炭素数６〜８のシクロアルカン−テトライル基または炭素数６〜１５のアレーン−テトライル基を表す。）
アルカン−テトライル基として、メタン−テトライル基、エタン−テトライル基、プロパン−テトライル基、ブタン−テトライル基、ペンタン−テトライル基などが挙げられる。シクロアルカン−テトライル基としてシクロヘキサン−テトライル基などが挙げられる。アレーン−テトライル基として、ベンゼン−テトライル基、キシレン−テトライル基、ジフェニル−テトライル基、ジフェニルメタン−テトライル基、ジフェニルプロパン−テトライル基などが挙げられる。
本発明で好適に用いられるエピスルフィド化合物を以下に例示するが、これらを単独で用いてもよく、また２種類以上を併用しても良い。

(In the formula, each X ₂ independently represents —S— or —O—. R ₁ represents an alkane-tetrayl group having 1 to 5 carbon atoms, a cycloalkane-tetrayl group having 6 to 8 carbon atoms, or a carbon number. Represents 6 to 15 arene-tetrayl groups.)
Examples of the alkane-tetrayl group include a methane-tetrayl group, an ethane-tetrayl group, a propane-tetrayl group, a butane-tetrayl group, and a pentane-tetrayl group. Examples of the cycloalkane-tetrayl group include a cyclohexane-tetrayl group. Examples of the arene-tetrayl group include a benzene-tetrayl group, a xylene-tetrayl group, a diphenyl-tetrayl group, a diphenylmethane-tetrayl group, and a diphenylpropane-tetrayl group.
Although the episulfide compound used suitably by this invention is illustrated below, these may be used independently and may use 2 or more types together.

Ｒ_２：メチレン基、エタン−１，１−ジイル基
Ｘ_２：単結合
Ｘ_３：炭素数１〜６のアルキル基 (A-1) When the episulfide compound is a compound represented by the general formula (III-1).

R ₂ : methylene group, ethane-1,1-diyl group X ₂ : single bond X ₃ : alkyl group having 1 to 6 carbon atoms

Ｒ_２：メチレン基
Ｘ_２：−Ｏ−
Ｘ_３：炭素数１〜６のアルキル基、フェニル基、ベンジル基 (A-2) When the episulfide compound is a compound represented by the general formula (III-1).

R ₂ : Methylene group X ₂ : —O—
X ₃ : C 1-6 alkyl group, phenyl group, benzyl group

Ｒ_２：メチレン基、エタン−１，１−ジイル基
Ｘ_２：単結合、アルカン−ジイル基
Ｘ_３：−ＯＨ (A-3) When the episulfide compound is a compound represented by the general formula (III-1).

R ₂ : methylene group, ethane-1,1-diyl group X ₂ : single bond, alkane-diyl group X ₃ : —OH

Ｒ_２：メチレン基
Ｘ_２：単結合、アルカン−ジイル基
Ｘ_３：−ＯＨ (A-4) When the episulfide compound is a compound represented by the general formula (III-1).

R ₂ : Methylene group X ₂ : Single bond, alkane-diyl group X ₃ : —OH

Ｘ_２：―Ｏ―、―Ｓ―、−Ｓ−Ｓ−、単結合
Ｘ_３：−Ｅ、−ＳＨ
Ｒ_１：メタン−テトライル、べンゼン−テトライル (B) When the episulfide compound is a compound represented by the general formula (III-2).

X ₂ : —O—, —S—, —S—S—, single bond X ₃ : —E, —SH
R ₁ : methane-tetrayl, benzene-tetrayl

Ｘ_２：―Ｏ―、―Ｓ―
Ｒ_１：アルカン−テトライル (C-1) When the episulfide compound is a compound represented by the general formula (III-3).

X ₂ : —O—, —S—
R ₁ : Alkane-tetrayl

Ｘ_２：―Ｏ―、―Ｓ―
Ｒ_１：炭素数６〜８のシクロアルカン−テトライル基 (C-2) The case where the episulfide compound is a compound represented by the general formula (III-3).

X ₂ : —O—, —S—
R ₁ : a cycloalkane-tetrayl group having 6 to 8 carbon atoms

Ｘ_２：―Ｏ―、―Ｓ―
Ｒ_１：アレーン−テトライル基 (C-3) When the episulfide compound is a compound represented by the general formula (III-3).

X ₂ : —O—, —S—
R ₁ : arene-tetrayl group

(D) Other

  Moreover, in this invention, the compound which substituted a part of episulfide group of the said compound by the epoxy group can be used. More preferably, methylthioglycidyl ether, propylthioglycidyl ether, butylthioglycidyl ether, phenylthioglycidyl ether, benzylthioglycidyl ether, 2,3-episulfide-1-propanol, 2,3-episulfide-1-butanol, 3, 4-episulfide-1-butanol, 3,4-episulfide-2-butanol, bisthioglycidyl sulfide, bisthioglycidyl ether.

  PAI resin content in this invention is 5-60 weight part with respect to a total of 100 weight part of PAI resin and PAS resin, Preferably it is 20-50 weight part, More preferably, it is 30-50 weight part. The PAS resin content in the present invention is 95 to 40 parts by weight, preferably 80 to 50 parts by weight, and more preferably 70 to 50 parts by weight with respect to a total of 100 parts by weight of the PAI resin and the PAS resin. The content of the episulfide compound in the present invention is usually 0.01 to 10 parts by weight, preferably 0.01 to 8 parts by weight, more preferably 0.03 to 100 parts by weight based on the total of 100 parts by weight of the PAI resin and the PAS resin. 6 parts by weight.

  The resin composition of the present invention is produced by melt-kneading PAI resin, PAS resin and episulfide compound. The melt-kneading temperature is 250 to 400 ° C, preferably 280 to 360 ° C. The kneading method can be carried out with an extruder, a kneader, a Banbury mixer, a mixing roll or the like, but a preferred method is a method using a biaxial extruder.

  Other components such as fillers, pigments, lubricants, plasticizers, stabilizers, UV agents, flame retardants, flame retardant auxiliary additives, and other resins are suitable for the resin composition of the present invention. Can be formulated.

  Examples of fillers include glass beads, wollastonite, mica, talc, kaolin, silicon dioxide, clay, asbestos, calcium carbonate, magnesium hydroxide, silica, diatomaceous earth, graphite, carborundum, and molybdenum disulfide. Mineral fillers such as glass fiber, milled fiber, potassium titanate fiber, boron fiber, silicon carbide fiber, and the like. The filler can be used in an amount of 1 to 70% by weight of the resin composition. Preferred fillers are glass fiber, milled fiber, carbon fiber, and potassium titanate fiber, and those treated with a silane coupling agent such as urethane or amino can also be suitably used.

Examples of the pigment include titanium oxide, zinc sulfide, and zinc oxide.
Representative examples of the lubricant include mineral oil, silicon oil, ethylene wax, polypropylene wax, metal salts such as sodium stearate, metal salts such as sodium montanate, and montanic acid amide.
Examples of the plasticizer include generally used silane compounds and phthalic acid compounds such as dimethyl phthalate and dioctyl phthalate. Moreover, generally used ultraviolet absorbers, colorants, and the like can be used.
Examples of the flame retardant include phosphoric acid esters such as triphenyl phosphate, brominated compounds such as decabromobiphenyl, pentabromotoluene, and brominated epoxy resin; nitrogen-containing phosphorus compounds such as melamine derivatives. Flame retardant aids may be used, examples of which include compounds such as antimony, boron and zinc.

  Examples of other resins include polyesters such as epoxy resin, phenoxy resin, polyethylene terephthalate, polybutylene terephthalate, fluororesins such as tetrafluoroethylene, polyphenylene ether, polysulfone, polycarbonate, polyether ketone, polyetherimide And aromatic resins such as polyetheretherketone.

  As described above, the present invention is a resin composition comprising (A) a PAI resin, (B) a PAS resin, and (C) an episulfide compound. Moreover, this invention includes the molded article which consists of this resin composition. Molding is performed by a normal injection molding method, the cylinder temperature is in the range of 290 to 360 ° C., and the mold is desirably 120 to 160 ° C. in order to obtain sufficient heat resistance. Further, it is desirable to perform heat treatment after molding for the purpose of improving heat resistance and removing residual stress. In particular, when molding is performed at a mold temperature lower than 120 ° C., heat treatment is preferable. The heat treatment method is not particularly limited, and for example, a normal hot air oven, a microwave oven or an oven range is used. The heat treatment temperature may be 150 to 300 ° C., preferably 180 to 280 ° C., most preferably 200 to 260 ° C. for 30 seconds to 48 hours, preferably 1 to 36 hours under normal pressure or reduced pressure.

The present invention is a method for improving the melt fluidity of a resin composition comprising an aromatic polyamideimide resin and a polyarylene sulfide resin, wherein the weight average molecular weight (Mw) is 1,000 to 100,000, and the molecule A resin composition comprising 5 to 60 parts by weight of an aromatic polyamideimide resin (A) and 95 to 40 parts by weight of a polyarylene sulfide resin (B) having an amino group contained therein of 0.00002 to 0.002 mol / g. The method includes adding 0.01 to 10 parts by weight of the episulfide compound (C). Here, the components (A), (B) and (C), and the amounts used thereof are as described for the resin composition.
The present invention also provides an aromatic polyamideimide resin having a weight average molecular weight (Mw) of 1,000 to 100,000 and an amino group contained in the molecule of 0.00002 to 0.002 mol / g ( This includes the use of an episulfide compound as a melt fluidity imparting agent for a resin composition comprising A) 5 to 60 parts by weight and polyarylene sulfide resin (B) 95 to 40 parts by weight.

  The present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

<Synthesis Example 1: Synthesis of PAI resin (1)>
3 L of N-methylpyrrolidone having a water content of 15 ppm was charged into a reactor equipped with a 5 liter stirrer, thermometer, and reflux condenser equipped with a drying tube filled with calcium chloride at the tip. To this was added 555 g (50 mol%) of trimellitic anhydride, and then 503 g (50 mol%) of 2,4-tolylene diisocyanate. The water content in the system at the time of addition of trimellitic anhydride was 30 ppm. Initially, 30 minutes from room temperature was required, and the temperature of the contents was 120 ° C., and this temperature was maintained for 8 hours.
After completion of the polymerization, the polymerization solution was dropped into methanol having a volume twice that of N-methylpyrrolidone under strong stirring to precipitate a polymer. The precipitated polymer was filtered off with suction, washed well with methanol, and dried under reduced pressure at 200 ° C. to obtain a polyamideimide resin (PAI resin (1)).
When the weight average molecular weight in terms of PEG (polyethylene glycol) was measured using GPC, Mw was 9,000. The measurement conditions are as follows.
GPC model: Shimadzu Corporation LC-6A and detector RID-6A
Column used: shodex KD-806M
Eluent: N, N-dimethylformamide Column temperature: 50 ° C.
Eluent flow rate: 0.5 ml / min
Calibration curve: PEG having a known molecular weight was measured and prepared.
Moreover, when the polyamideimide resin was dissolved in dimethylformamide and neutralization titration using hydrochloric acid was performed, the amino group contained in the molecule was 0.0001 mol / g.

<Synthesis Example 2: Synthesis of PAI resin (2)>
A reactor equipped with a 5 liter stirrer was charged with 1.5 liters of acetone and 1.5 liters of water, then 202 g of triethylamine, 421 g (50 mol%) of trimellitic chloride anhydride, and 244 g of m-tolylenediamine. (50 mol%) was added. The mixture was stirred at room temperature for 2 hours, and the precipitated polymer was filtered off with suction, washed well with methanol, and dried under reduced pressure at 200 ° C. for 24 hours to obtain a polyamideimide resin (PAI resin (2)).
As in Synthesis Example 1, the weight average molecular weight in terms of PEG was measured using GPC, and Mw = 7,000 (solvent dimethylformamide). When polyamideimide resin was dissolved in dimethylformamide and neutralization titration using hydrochloric acid was performed, the amino group contained in the molecule was 0.00007 mol / g.

<Synthesis Example 3: Synthesis of PAI resin (3)>
After adding trimellitic anhydride and 2,4-tolylene diisocyanate in Synthesis Example 1, it took 50 minutes from room temperature to bring the content temperature to 200 ° C., and this temperature was maintained for 6 hours. Thereafter, after the polymer was precipitated, a polyamideimide resin (PAI resin (3)) was obtained in the same manner as in Synthesis Example 1.
In the same manner as in Synthesis Example 1, the weight average molecular weight in terms of PEG was measured using GPC, and it was Mw = 120,000 (solvent dimethylformamide). When the polyamideimide resin was dissolved in dimethylformamide and neutralization titration using hydrochloric acid was performed, the amino group contained in the molecule was 0.00008 mol / g.

<Synthesis Example 4: Synthesis of PAI resin (4)>
After adding trimellitic anhydride and 2,4-tolylene diisocyanate in Synthesis Example 1, it took 20 minutes from room temperature to bring the content temperature to 90 ° C., and this temperature was maintained for 50 minutes. Subsequently, the temperature was raised to 115 ° C., and this temperature was maintained for 8 hours. Thereafter, a polyamideimide resin (PAI resin (4)) was obtained in the same manner as in Synthesis Example 1.
In the same manner as in Synthesis Example 1, when the weight average molecular weight in terms of PEG was measured using GPC, it was Mw = 8,000 (solvent dimethylformamide). When polyamideimide resin was dissolved in dimethylformamide and neutralization titration using hydrochloric acid was performed, the amino group contained in the molecule was 0.000001 mol / g.

Example 1
PAI resin (1) 49.5 wt% produced in Synthesis Example 1 and PAS resin (DIC-PPS-LR03, manufactured by Dainippon Ink & Chemicals, Inc., repeating unit is p-phenylene, temperature 310 ° C., shear rate 1200 / sec. The melt viscosity measured in step 1 was 49.5 wt% and phenylthioglycidyl ether 1 wt% were blended, melt-kneaded at 320 ° C. using a twin-screw extruder, and pelletized to produce a resin composition.
(Measurement of melt fluidity)
The melt fluidity was measured from the pellets (Toyo Seiki Seisakusho Capillograph 1B, 350 ° C., share rate = 1200 sec ⁻¹ ).
(Measurement of bending strength, flexural modulus, bending strain, thermal deformation temperature)
This pellet was injection-molded to obtain a 1/8 inch thick bending test piece. Using this test piece, bending strength, bending elastic modulus, bending strain, and thermal deformation temperature were measured.
The bending strength, flexural modulus, and bending strain were measured using Shimadzu Corporation Autograph AG5000B (measuring conditions: 23 ° C., ASTM D790).
The heat distortion temperature (DTUL) was measured by using Yasuda Seiki Co., Ltd. HD-500-PC under a load of 18.6 kg / cm ² under a nitrogen atmosphere (ASTM D648).
Table 10 shows the measurement results.

Example 2
A resin composition was produced and evaluated in the same manner as in Example 1 except that bisthioglycidyl sulfide was used as the episulfide compound. The results are shown in Table 10.

Example 3
46 wt% of PAI resin (1) produced in Synthesis Example 1 and 46 wt% of PAS resin (DIC-PPS-LR03 manufactured by Dainippon Ink & Chemicals, Inc.) and 8 wt% of phenylthioglycidyl ether were blended. The resin composition was manufactured by the method of and evaluated. The results are shown in Table 10.

Example 4
49.5 wt% of PAI resin (2) produced in Synthesis Example 1 and 49.5 wt% of PAS resin (DIC-PPS-LR03, manufactured by Dainippon Ink & Chemicals, Inc.) and 1 wt% of phenylthioglycidyl ether were blended. A resin composition was produced in the same manner as in Example 1 and evaluated. The results are shown in Table 10.

Example 5
A resin composition was produced and evaluated in the same manner as in Example 1 except that 2,3-episulfide-1-propanol was used as the episulfide compound. The results are shown in Table 10.

Example 6
A resin composition was produced and evaluated in the same manner as in Example 1 except that 2,2-bis {4- (2,3-epithiopropyloxy) phenyl} propane was used as the episulfide compound. The results are shown in Table 10.

Comparative Example 1
Resin was prepared in the same manner as in Example 1 except that 50 wt% of PAI resin (1) produced in Synthesis Example 1 and 50 wt% of PAS resin (DIC-PPS-LR03 manufactured by Dainippon Ink & Chemicals, Inc.) were blended. Compositions were made and evaluated. The results are shown in Table 10.

Comparative Example 2
40 wt% of PAI resin (1) produced in Synthesis Example 1 and 40 wt% of PAS resin (DIC-PPS-LR03 manufactured by Dainippon Ink & Chemicals, Inc.) and 20 wt% of phenylthioglycidyl ether were blended. The resin composition was manufactured by the method of and evaluated. The results are shown in Table 10.

Comparative Example 3
PAI resin (1) 40 wt% produced in Synthesis Example 1 and PAS resin (DIC-PPS-LR03 manufactured by Dainippon Ink & Chemicals, Inc.) 40 wt% and bisthioglycidyl sulfide 20 wt% were blended. The resin composition was manufactured by the method of and evaluated. The results are shown in Table 10.

Comparative Example 4
A resin composition was produced in the same manner as in Example 1 except that the PAI resin (3) produced in Synthesis Example 3 was used, and the physical properties were measured. The results are shown in Table 10.

Comparative Example 5
A resin composition was produced in the same manner as in Example 1 except that the PAI resin (4) produced in Synthesis Example 4 was used, and the physical properties were measured. The results are shown in Table 10.

表中の記号は以下の通りである。
ＰＡＩ樹脂（１）：合成例１のＰＡＩ樹脂
ＰＡＩ樹脂（２）：合成例２のＰＡＩ樹脂
ＰＡＩ樹脂（３）：合成例３のＰＡＩ樹脂
ＰＡＩ樹脂（４）：合成例４のＰＡＩ樹脂
ＰＡＳ樹脂：ポリアリーレンスルフィド樹脂
大日本インキ化学工業（株）製 ＤＩＣ−ＰＰＳ−ＬＲ０３
ＥＰＳ化合物（１）：フェニルチオグリシジルエーテル
ＥＰＳ化合物（２）：ビスチオグリシジルスルフィド
ＥＰＳ化合物（３）：２，３−エピスルフィド−１−プロパノール
ＥＰＳ化合物（４）：２，２−ビス｛４−（２，３−エピチオプロピルオキシ）フェニル｝プロパン
ＤＴＵＬ：熱変形温度

The symbols in the table are as follows.
PAI resin (1): PAI resin of Synthesis Example 1 PAI resin (2): PAI resin of Synthesis Example 2 PAI resin (3): PAI resin of Synthesis Example 3 PAI resin (4): PAI resin of Synthesis Example 4 PAS resin : Polyarylene sulfide resin DIC-PPS-LR03 manufactured by Dainippon Ink & Chemicals, Inc.
EPS compound (1): phenylthioglycidyl ether EPS compound (2): bisthioglycidyl sulfide EPS compound (3): 2,3-episulfide-1-propanol EPS compound (4): 2,2-bis {4- ( 2,3-epithiopropyloxy) phenyl} propane DTUL: heat distortion temperature

Claims (12)

(1) Aromatic polyamideimide resin (A) 5 having a weight average molecular weight (Mw) of 1,000 to 100,000 and an amino group contained in the molecule of 0.00002 to 0.002 mol / g. ˜60 parts by weight, (2) 0.01 to 10 parts by weight of the episulfide compound (95) to 40 parts by weight of the polyarylene sulfide resin (B) and (3) 100 parts by weight of (A) and (B) ( A resin composition comprising C). The resin composition according to claim 1, wherein the aromatic polyamideimide resin (A) has a weight average molecular weight (Mw) of 1,000 to 50,000. The resin composition according to claim 1, wherein the amino group contained in the aromatic polyamideimide resin (A) is 0.00005 to 0.001 mol / g. The resin composition according to claim 1, wherein the polyarylene sulfide resin (B) has a melt viscosity of 10 to 600 Pa · s measured at a temperature of 310 ° C and a shear rate of 1200 / sec. The resin composition according to claim 1, wherein the episulfide compound (C) is a compound represented by the following general formula (III).

(Wherein, X ₁ is each independently a hydrogen atom or a general formula: E-R 2 _-X 2 _- represents, E is represents an episulfide group or an epoxy group, episulfide group is always included one or more in a molecule. X ₂ each independently represents a divalent hydrocarbon group having 1 to 6 carbon atoms, an ether bond, a thioether bond, a disulfide bond, a carbonyl bond, an ester bond, an amide bond, or a single bond, and each X ₃ independently represents R ₁ represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 24 carbon atoms, a vinyl group, a hydroxyl group, an amino group, a ureido group, an isocyanate group, an episulfide group, an epoxy group, and a mercapto group. represents a tetravalent hydrocarbon group having 1 to 24, a divalent .n representing a hydrocarbon group of 0 to 20 integer from 1 to 24 carbon atoms _{R 2} are each independently It is.) The resin composition according to claim 1, wherein the episulfide compound (C) is at least one compound selected from the group consisting of the following general formulas (III-1), (III-2) and (III-3).

(In the formula, R ₂ represents a methylene group, an ethylene group or an ethane-1,1-diyl group. X ₂ represents a single bond, —O—, a methylene group, an ethylene group or a trimethylene group. X ₃ represents Represents an alkyl group having 1 to 6 carbon atoms, —OH, a phenyl group or a benzyl group.)

(Wherein X ₂ represents a single bond, —O—, —S— or —S—S—. X ₃ represents —SH or an episulfide group. R ₁ represents a methane-tetrayl group or a benzene-tetrayl group. Represents a group.)

(In the formula, each X ₂ independently represents —S— or —O—. R ₁ represents an alkane-tetrayl group having 1 to 5 carbon atoms, a cycloalkane-tetrayl group having 6 to 8 carbon atoms, or a carbon number. Represents 6 to 15 arene-tetrayl groups.) The resin composition according to claim 1, wherein the episulfide compound (C) is a compound represented by the following general formula (III-1).

(In the formula, R ₂ represents a methylene group, an ethylene group or an ethane-1,1-diyl group. X ₂ represents a single bond, —O—, a methylene group, an ethylene group or a trimethylene group. X ₃ represents Represents an alkyl group having 1 to 6 carbon atoms, —OH, a phenyl group or a benzyl group.) The resin composition according to claim 1, wherein the episulfide compound (C) is a compound represented by the following general formula (III-2).

(Wherein X ₂ represents a single bond, —O—, —S— or —S—S—. X ₃ represents —SH or an episulfide group. R ₁ represents a methane-tetrayl group or a benzene-tetrayl group. Represents a group.) The resin composition according to claim 1, wherein the episulfide compound (C) is a compound represented by the following general formula (III-3).

(In the formula, X ₂ represents —S— or —O—. R ₁ represents an alkane-tetrayl group having 1 to 5 carbon atoms, a cycloalkane-tetrayl group having 6 to 8 carbon atoms, or 6 to 15 carbon atoms. Represents an arene-tetrayl group.) A molded article comprising the resin composition according to claim 1. A method for improving the melt fluidity of a resin composition comprising an aromatic polyamideimide resin and a polyarylene sulfide resin, having a weight average molecular weight (Mw) of 1,000 to 100,000 and contained in the molecule For a resin composition comprising 5 to 60 parts by weight of an aromatic polyamideimide resin (A) having an amino group of 0.00002 to 0.002 mol / g and 95 to 40 parts by weight of a polyarylene sulfide resin (B), A method comprising adding 0.01 to 10 parts by weight of an episulfide compound (C). The method according to claim 11, wherein the episulfide compound (C) is a compound represented by the following general formula (III).

(Wherein, _{X 1} is each independently a hydrogen atom or a general formula: _{E-R 2} -X 2 - represents,
E represents an episulfide group or an epoxy group, and at least one episulfide group is necessarily contained in the molecule. X ₂ each independently represents a divalent hydrocarbon group having 1 to 6 carbon atoms, an ether bond, a thioether bond, a disulfide bond, a carbonyl bond, an ester bond, an amide bond, or a single bond. X ₃ each independently represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 24 carbon atoms, a vinyl group, a hydroxyl group, an amino group, a ureido group, an isocyanate group, an episulfide group, an epoxy group, and a mercapto group. R ₁ each independently represents a tetravalent hydrocarbon group having 1 to 24 carbon atoms, and R ₂ each independently represents a divalent hydrocarbon group having 1 to 24 carbon atoms. n represents an integer of 0 or more and 20 or less. )