JPH08225741A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE: To obtain the subject composition reduced in melt viscosity, high in crystallization rate, moldable over the wide mold temperature range from low to high temperatures, thus useful for electronic parts etc., by blending a thermoplastic resin with a specific oligoimide compound. CONSTITUTION: This thermoplastic resin composition is obtained by incorporating (A) 100 pts.wt. of a thermoplastic resin with (B) 0.1-100 pts.wt. of at least one kind of modifier selected from oligoimides of formula I [R<1> and R<2> are each an aliphatic or aromatic hydrocarbon; A<1> and A<2> are each a direct bond, phenylene or cyclohexylene; X<1> and X<2> are each of formula II, III or IV; Y<1> is an alkylene or geometric isomer thereof, (substituted) phenylene, CH2 - phenylene-CH2 , etc.; (a) is 1-10], the oligoimides bearing carboxyl group and the oligoimides' metal salts. The component B is pref. an oligoimide prepared by dehydrating 1,2,3,4-butanetetracarboxylic acid and/or its anhydride.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a thermoplastic resin composition.

[0002]

2. Description of the Related Art Recently, thermoplastic resins having heat resistance have been used as engineering plastics for mechanical materials and electronic parts. In molding a thermoplastic resin, in order to improve productivity, various resin modifiers for the purpose of decreasing melt viscosity, promoting crystallization, and improving mold releasability, for example, fatty acids such as stearic acid and fatty acids. A method of kneading metal salts, ester derivatives of fatty acids with polyhydric alcohols such as pentaerythritol and polyethylene glycol, and aliphatic amides such as ethylenebisstearamide has been proposed (Japanese Patent Laid-Open No. 60-44547, JP-A-60-44547). Kaihei 3-250049).

However, a thermoplastic resin having heat resistance generally has a high melting temperature, and the above-mentioned resin additives are thermally decomposed or boiled at the time of melting to contaminate the mold or generate bubbles in the resin. There were cases. Therefore, it has been desired to develop a resin modifier having heat resistance.

[0004]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a novel and useful thermoplastic resin composition containing a resin modifier having excellent heat resistance.

[0005]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that a specific oligoimide compound itself has heat resistance and lowers the melt viscosity of a thermoplastic resin. It was found that the crystalline thermoplastic resin functions as a resin modifier having desired performance such as improving the crystallinity or releasing property of the crystalline thermoplastic resin, and the present invention based on such findings. Has been completed.

That is, the thermoplastic resin composition according to the present invention comprises a thermoplastic resin, an oligoimide represented by the general formula (1), a derivative of the oligoimide having a carboxyl group, and 100 parts by weight of the thermoplastic resin. 1 selected from the group consisting of metal salts of the oligoimide derivatives
It is characterized by containing 0.1 to 100 parts by weight of one kind or two or more kinds of compounds (hereinafter referred to as "the present oligoimides").

R ¹ -A ¹ (-X ¹ -Y ¹ ) a -X ² -A ² -R ² (1) [In the formula, R ¹ and R ² are the same or different, and an aliphatic hydrocarbon group or Represents an aromatic hydrocarbon group. A ¹ and A ² are the same or different and represent a direct bond, a phenylene group or a cyclohexylene group. X ¹ and X ² are the same or different and represent structural formula B, structural formula B or structural formula C. Y ¹ is an alkylene group or a geometric isomer thereof, a phenylene group which may be substituted with an alkyl group, a group —CH ₂ — (phenylene) —CH ₂ —, a group —CH ₂ — (cyclohexylene) —CH ₂ —, or Group-B ¹
-Z ¹ -B ² - represents a. B ¹ and B ² are the same or different and each represent a phenylene group which may be substituted with an alkyl group, a group-(phenylene) -Z ^2- (phenylene)-or a cyclohexylene group. Z ¹ and Z ² are the same or different and are a direct bond, —S—, —SO ₂ —, —O—, —CH ₂ —, —CO—.
Alternatively, it represents a methylene group substituted with an alkyl group or an aryl group. a represents the integer of 1-10. The group-(-X
^{In 1} -Y ¹ ) a-, a number of X ^{1 s} and Y ^{1 s} may be the same or different. ]

[0008]

[Chemical 4]

[0009]

Embedded image

[0010]

[Chemical 6]

Among the oligoimides represented by the general formula (1), the oligoimide represented by the general formula (2) is recommended,
The oligoimide represented by the general formula (3) is particularly effective.

R ³ -A ³ (-X ³ -Y ² ) b-X ⁴ -A ⁴ -R ⁴ (2) [In the formula, R ³ and R ⁴ are the same or different and have 8 to 22 carbon atoms.
Represents an alkyl group. A ³ and A ⁴ are the same or different and represent a direct bond, a phenylene group or a cyclohexylene group.
X ³ and X ⁴ are the same or different and represent structural formula B, structural formula B or structural formula C. Y ² is an alkylene group or a geometric isomer thereof, a phenylene group which may be substituted with an alkyl group, a group —CH ₂ — (phenylene) —CH ₂ —, a group —CH ₂
- (cyclohexylene) -CH ₂ - or a group -B ³ -Z ³ -
Represents B ⁴ −. B ^3, B ⁴ are the same or different, an alkyl group which may be substituted with a phenylene group, group - represents a or cyclohexylene group - (phenylene) -Z ⁴ - (phenylene). Z ³ and Z ⁴ are the same or different, and are a direct bond, -S
_{-, - SO 2 -, -} O -, - CH 2 -, - CO- or alkyl or aryl group represents a methylene group substituted. a represents the integer of 1-10. Incidentally, group - (- X ³ -
In Y ² ) b-, b X ³ and Y ² may be the same or different. ]

R ⁵ — (X ⁵ —Y ³ ) c—X ⁶ —R ⁶ (3) [In the formula, R ⁵ and R ⁶ are the same or different, and have 8 to 22 carbon atoms.
Represents an alkyl group. X ⁵ and X ⁶ are the same or different and represent structural formula B, structural formula B or structural formula C. Y ³ is an alkylene group or a geometric isomer thereof, a phenylene group which may be substituted with an alkyl group, and a group —CH ₂ — (phenylene) —
CH ₂ — or a group —B ⁵ —Z ⁵ —B ⁶ —. B ^5, B ⁶ are the same or different, a phenylene group in the alkyl group represented by substituted or group - (phenylene) -Z ⁶ - (phenylene) - represents a. Z ^5, Z ⁶ are the same or different, directly _{bonded, -S -, - SO 2 -} , - O -, - CH 2 -, - CO-
Alternatively, it represents a methylene group substituted with an alkyl group or an aryl group. c represents an integer of 1 to 10. The group-(-X
^{In 5-} Y ³ ) c-, c X ⁵ and Y ³ may be the same or different. ]

The oligoimide represented by the general formula (1) is
For example, it is a compound that can be obtained by dehydration reaction of the following three types of compounds (1) to (3).

(1) 1,2,3,4-butanetetracarboxylic acid (hereinafter referred to as "BTC") and / or its anhydride (both monoanhydride and dianhydride are applicable) (hereinafter referred to as " BTCs ").

(2) One or more monoamines. Specific examples thereof include an aliphatic primary monoamine having 4 to 22 carbon atoms and an aromatic primary monoamine having 6 to 24 carbon atoms.

Examples of recommended aliphatic primary monoamines include aliphatic monoamines represented by the general formula (4) and alicyclic monoamines having 6 to 24 carbon atoms. These may have an aromatic ring.

R ⁷ —A ⁵ —NH ₂ (4) [In the formula, R ⁷ represents a saturated or unsaturated linear or branched alkyl group having 4 to 22 carbon atoms. A ⁵ represents a direct bond or a phenylene group. ]

As the above aliphatic monoamine, more specifically, butylamine, pentylamine, hexylamine,
Heptylamine, octylamine, 2-ethylhexylamine, nonylamine, decylamine, undecylamine, dodecylamine, tridecylamine, tetradecylamine, pentadecylamine, hexadecylamine, heptadecylamine, octadecylamine, nonadecylamine, eicosylamine. , Heneicosylamine, docosylamine, octadecenylamine, benzylamine and the like are exemplified, and among them, decylamine, dodecylamine, tetradecylamine, hexadecylamine, octadecylamine and the like are recommended.

Further, it is practical to use a mixture containing these monoamines, that is, a natural amine such as palm amine, tallow amine, fish oil amine, hydrogenated palm amine, hydrogenated tallow amine, hydrogenated fish oil amine. It is economically meaningful.

Examples of the alicyclic monoamine include cyclobutylamine, cyclopentylamine, cyclohexylamine, cyclohexylmethylamine, cyclohexylethylamine, methylcyclohexylamine, dimethylcyclohexylamine, and alkyl (C2-18) cyclohexylamine.

The aromatic monoamine has 6 to 2 carbon atoms.
The aromatic monoamine of 4 is exemplified. More specifically, butylaniline, allylaniline, pentylaniline, hexylaniline, heptylaniline, octylaniline, nonylaniline, decylaniline, undecylaniline, dodecylaniline, tridecylaniline, tetradecylaniline, pentadecylaniline, hexadecyl. Aniline, heptadecylaniline, octadecylaniline, octadecenylaniline, nonadecylaniline, eicosylaniline, heneicosylaniline, docosylaniline and the like are exemplified, and among them, decylaniline, dodecylaniline, tetradecylaniline, hexadecylaniline. , Octadecylaniline, etc. are recommended.

(3) One or more diamines.
Specifically, an aliphatic primary diamine having 2 to 15 carbon atoms,
Alicyclic primary diamine having 6 to 30 carbon atoms and 6 to 3 carbon atoms
An aromatic primary diamine of 0 is illustrated.

Among them, the diamine represented by the general formula (5) is recommended. ^{_{H 2 N-R 8 -NH 2}} (5) [ wherein, the alkylene group of R ⁸ is 2 to 15 carbon atoms, a phenylene group, group -CH ₂ - (phenylene) -CH ₂ - or a group -
B ⁷ -Z ⁷ -B ⁸ - represents a. B ^7, B ⁸ are the same or different, a phenylene group or a group that the alkyl group is substituted - (phenylene) -Z ⁸ - (phenylene) - represents a.
Z ⁷ and Z ⁸ are the same or different and are a direct bond, -S-, -S.
It represents a methylene group substituted with O ₂ —, —O—, —CH ₂ —, —CO—, an alkyl group or an aryl group. ]

The aliphatic primary diamine has 1 carbon atom.
Primary diamines and their geometrical isomers bound by methylene groups of ˜12 are recommended, specifically ethylenediamine, trimethylenediamine, tetramethylenediamine,
Examples include pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, undecamethylenediamine, dodecamethylenediamine and geometric isomers thereof.

Further, as the alicyclic primary diamine,
Examples thereof include 1,3-bis (aminomethyl) cyclohexane, isophoronediamine, diaminodicyclohexylmethane and their alicyclic methyl-substituted products.

As the aliphatic primary diamine containing an aromatic ring, m-xylylenediamine is exemplified.

Among these aliphatic diamines, ethylenediamine, hexamethylenediamine, 1,3-bis (aminomethyl) cyclohexane, isophoronediamine, m-
Xylylenediamine is a preferable raw material because of its ability to reduce the melt viscosity of oligoimide and the availability of raw materials.

As the aromatic primary diamine, benzidine, dimethylbenzidine, diaminodiphenylmethane,
Diaminoditolylmethane, diaminodiphenylethane,
Diaminodiphenylpropane, diaminodiphenylbutane, diaminodiphenyl sulfide, 2,2-bis (aminophenoxyphenyl) propane, 2,2-bis (aminophenylthioetherphenyl) propane, bis (aminophenoxy) diphenyl sulfone, bis (aminophenoxy) Diphenyl ether, bis (aminophenoxy) diphenyl sulfide, bis (aminophenylthioether) diphenyl sulfone, bis (aminophenylthioether) diphenyl ether, bis (aminophenylthioether) diphenyl sulfide, bis (aminophenoxy) diphenyl, bis (aminophenoxy) benzophenone, Bis (aminophenyl thioether) diphenyl, bis (aminophenyl thioether) benzophenone, bi (Aminophenyl thioether) benzene, (phenylenediisopropylidene) dianiline, 2,2-bis (aminophenoxy phenyl) hexafluoropropane, diaminodiphenyl ether, diaminodiphenyl sulfone, diaminobenzophenone,
o-phenylenediamine, m-phenylenediamine, p
-Phenylenediamine, bis (aminophenoxy) biphenyl, 9,10-bis (aminophenyl) anthracene, 9,9-bis (aminophenyl) fluorene, tolylenediamine, xylenediamine and positional isomers thereof. it can.

Among these aromatic diamines, diaminodiphenylmethane, diaminodiphenyl ether, diaminodiphenyl sulfone, diaminobenzophenone, o-
Phenylenediamine, m-phenylenediamine, p-phenylenediamine, and tolylenediamine are selected from the viewpoint of the melt viscosity reduction performance of oligoimide and the availability of raw materials.
It is a preferred raw material.

The corresponding isocyanate compounds and diisocyanate compounds of the above monoamines and diamines can also be used as raw materials.

The type of diamine is appropriately selected depending on the type of thermoplastic resin to be applied and the intended effect. Generally, for a highly polar resin, an oligoimide using a diamine having an alkylene group or an aromatic group having a chain length of 2 to 8 carbon atoms is preferable because of excellent compatibility, and for a non-polar resin, a carbon number of 8 to 15 carbon atoms is preferable. An oligoimide having an alkylene group or an alicyclic group having a chain length of is preferable.

These oligoimides may be used alone or in an appropriate mixture depending on the desired physical properties. In some cases, it may be added in the form of a mixed radical imide.

In the preparation of the oligoimide, the degree of polymerization can be set by selecting the molar ratio of each raw material. Usually, BTCs / monoamine / diamine (molar ratio) = 2 to 11/2/1 to 10 is preferable.

If the molar ratio of the diamine is less than 1 with respect to 2 moles of the monoamine, the amount of bisimide formed between the BTCs and the monoamine tends to increase. The bisimides of BTCs and monoamines are also effective as a melt viscosity lowering agent, a crystallization promoting agent, and a mold releasing agent of the thermoplastic resin depending on the kind as in the present invention. When a mixture of the bisimide and oligoimide is desired, the condensation reaction molar ratio is A mixture can be obtained by setting

When the molar ratio of the diamine exceeds 10 relative to 2 mol of the monoamine, the degree of polymerization becomes too large,
There is a tendency that the characteristics of the oligoimide of the present invention do not appear,
Not preferred.

In the first half of the dehydration reaction, the neutralization reaction and amidation reaction between BTCs and primary amines are the main part, and in the latter half of the reaction, dehydration of BTCs and primary amines from amic acid. The reaction is central.

The dehydration reaction may be carried out without a solvent,
You may use the solvent which can melt | dissolve BTCs. Examples of the solvent include polar organic solvents such as dimethylformamide (DMF), dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, dioxane, and lower alcohols having 1 to 4 carbon atoms.

On the other hand, a method in which monoamine and diamine are sequentially added and reacted while stirring and dispersing BTCs in the presence of a dispersion solvent is also effective. Examples of these solvents include aromatic hydrocarbons such as benzene, toluene, xylene, cumene and tetralin, and aliphatic hydrocarbons such as pentane, hexane, heptane, nonane and decane. From an industrial viewpoint, the solvent-free reaction is most preferable, and the method of using a small amount of the above dispersion solvent as an entrainer is also effective.

The dehydration reaction is preferably carried out at about 0 to 400 ° C. In the first half of the reaction, any temperature range is possible, but in the second half of the reaction, it is 150 to 40
It is recommended that the temperature is 0 ° C, preferably 200 to 300 ° C. Within this range, the thermal decomposition reaction rarely occurs, and the reaction proceeds at an industrial rate.

The reaction time depends on the reaction temperature and cannot be generally stated, but it is usually 1 to 50 hours.

The dehydration reaction may be carried out under normal pressure,
It may be performed under reduced pressure. The first half of the reaction is preferably carried out under normal pressure, and the second half of the reaction is preferably carried out under reduced pressure. The degree of reduced pressure may be in the range of 0.01 to 760 Torr, but especially at the end of the reaction, a low pressure such as 50
Toll or less is desirable.

The dehydration reaction proceeds without a catalyst, but when a catalyst is used, sodium, potassium, magnesium, calcium, barium, zinc, aluminum, tin,
Hydroxides such as lead, oxides, chlorides, and organic acid salts can be used. Usually, a non-catalytic reaction is preferable, but when the purpose is to produce a metal salt of these catalytic imides, it is preferable to use these catalysts.

When the isocyanate derivative is used as a raw material instead of the primary amine, the same reaction conditions as above can be applied.

The dehydration reaction according to the present invention may be carried out in the presence of a dehydrating agent such as acetic anhydride-pyridine and triphenyl carbodiimide phosphite, in which case the dehydrating agent is used in the latter half of the reaction. It is preferable to use 2 to 50 mol per mol of BTCs. At this time, the reaction temperature is preferably in the range of -20 ° C to 200 ° C.
If the temperature is lower than -20 ° C, the reaction is slow, and for a dehydrating agent that requires a temperature of higher than 200 ° C, the advantage of using the dehydrating agent is small and it is preferable to select the heating dehydration reaction.

Further, BTCs are thionyl chloride, phosgene,
The target oligoimide can also be prepared by reacting the above amine with BTCs in a substantially dehydrated form such as forming an acid chloride with a chlorinating reagent such as chlorine, phosphorus trichloride, phosphorus pentachloride and the like. The chlorinating reagent is effectively used in the latter stage of the reaction. In the latter stage of the reaction, BTCs 1
If 2 to 20 mol of chlorinating reagent is added to the mol and the reaction is carried out at a reaction temperature of -20 to 200 ° C, it is usually 1 to 10
The reaction is completed in about an hour.

The target oligoimide is also prepared by preliminarily reacting the BTCs with a lower alcohol (such as methyl alcohol or butyl alcohol) having about 1 to 4 carbon atoms as a partial ester or a total ester, and reacting with the above amine. To be done. That is, for example, lower alcohol to BT
A primary amine is added to the ester obtained by dissolving the C compound and, if necessary, dehydrating by heating, and carrying out a dealcoholation reaction at 100 to 400 ° C., preferably 200 to 300 ° C. An imide compound can be produced. In this case, the reaction can be carried out under any conditions of normal pressure, reduced pressure and pressurization, but when the primary amine has about 4 to 8 carbon atoms, pressurization (0 to 10 kg / cm ² G) is preferable, When the primary amine has 12 or more carbon atoms, the reaction under reduced pressure is preferable.

When the derivative of the oligoimide in which the carboxyl group remains is used, the affinity with the mold is increased and the external lubricity is increased. Specifically, an amic acid obtained from BTCs and an amine is effective. Therefore, the dehydration reaction between the BTCs and the amine may be controlled as necessary to leave the carboxyl group.

The remaining carboxyl group may be used as it is or in the form of a metal salt of sodium, potassium, magnesium, calcium, barium, zinc, aluminum, tin, lead or the like.

As a method for producing such a metal salt, an oligoimide in which the carboxyl group remains in a free form is melted, and a hydroxide or oxide of the above metal, or these are dissolved in water, methanol, ethanol or the like. The method of adding a solution and stirring is simple and preferable. Oligoimide
Even when it is dissolved in the reaction solvent of the above reaction, the above metal salt can be obtained in the same manner. Agitation is 50 to 130
The reaction is carried out at ℃ for 2 to 4 hours, and then the solvent is removed by topping to obtain the desired product. The amount of the hydroxide or oxide used is preferably 0.5 to 3 mol, and more preferably 1 to 2 mol, based on 1 mol of the residual carboxyl group. If the hydroxide or oxide is added and the reaction is carried out in advance, the desired imide compound in the form of a metal salt is obtained at the end of the reaction.

Further, the residual carboxyl group may be amidated with the above amine to form a substituted carbamoyl group. In that case, 1 to 10 mol of a primary amine is added to 1 mol of the residual carboxyl group to obtain 150 to 300. The method of continuing the dehydration reaction at ° C is recommended. Generally, a compound having a substituted carbamoyl group can be produced in 10 minutes to 1 hour, and this can be used in the present invention.

The oligoimide obtained by the above operation can be taken out from the reaction vessel as it is when it is produced in the absence of solvent, while the operation such as topping is performed when it is produced using a solvent, a dispersion medium or an entrainer. After removing the solvent, the dispersion medium or the entrainer with, the product is taken out.

The obtained oligoimide is often a solid and can be pulverized and added to the thermoplastic resin as it is.

When a purified oligoimide is required, an aromatic non-polar solvent such as benzene, toluene, xylene, or acetone, methyl ethyl ketone, methyl isobutyl ketone, dioxane, diglyme, acetonitrile, a lower alcohol having 1 to 4 carbon atoms, etc. Insoluble substances such as metal salts can be filtered out using an aliphatic polar solvent such as, chlorine-based solvents such as chloroform and monochlorobenzene, and purification can be performed by adsorption treatment such as clay treatment or reprecipitation method. it can.

The oligoimides are useful as a modifier for thermoplastic resins which are particularly required to have heat resistance.

As the kind of the thermoplastic resin, polyarylene sulfide (PAS) such as polyphenylene sulfide (PPS), polysulfone, polyphenylene ether (PPE), polyether sulfone (PES),
Aroma such as polyetheretherketone (PEEK), phenylmaleimide, ABS modified with α-methylstyrene and / or maleic anhydride, chlorinated polyvinyl chloride, terephthalic acid and aliphatic diamine, or xylylenediamine and aliphatic dicarboxylic acid. Group polyamide, 6 nylon,
6,6 nylon, 4,6 nylon, 11 nylon, 12
Aliphatic polyamide such as nylon, polycarbonate (P
C), polyacetal, polyethylene terephthalate (PET), polybutylene terephthalate, polyethylene naphthalene dicarboxylate (PEN), poly-
1,4-cyclohexane dimethylene terephthalate, polyarylate (for example, aromatic dicarboxylic acid consisting of terephthalic acid and / or isophthalic acid and bisphenol A)
With polyarylate, for example, trade name "U-Polymer"
(Manufactured by Unitika), "Ariron" (manufactured by DuPont),
"NAP" (manufactured by Kaneka Corporation), liquid crystal polymer (for example, p-hydroxybenzoic acid, biphenol and 4,
Liquid crystal polymer having 4'-diphenyldicarboxylic acid as a representative monomer, for example, trade name "Rhodolan" (manufactured by Unitika Ltd.), "EPE" (manufactured by Mitsubishi Chemical Corporation), "Idemitsu LCP"
(Made by Idemitsu Petrochemical Co., Ltd.), "Econol" (made by Sumitomo Chemical Co., Ltd.), "Zider" (made by Nippon Petrochemical Co., Ltd.), "LCP"
(Manufactured by Tosoh Co., Ltd.), “Vectra” (manufactured by Hoechst-Celanies Co., Ltd.), “SRP” (manufactured by ICI Co.), polyamideimide (for example, trimellitic acid and diaminodiphenylmethane, diaminodiphenylether, m- or p-phenylenediamine). Polyamide imides obtained from the aromatic diamines, etc.), thermoplastic polyimides, polyether imides (for example, trade name "Ultem" (manufactured by General Electric Co.)), polymethylpentene and modified products of these resins, polymer alloys. Etc. can be illustrated.

As the thermoplastic polyimide, a resin obtained by dehydrating a tetracarboxylic acid or its anhydride and a diamine by a conventional method is exemplified.

Examples of the tetracarboxylic acid include pyromellitic acid, diphenylsulfone tetracarboxylic acid, biphenyl tetracarboxylic acid, diphenyl ether tetracarboxylic acid, benzophenone tetracarboxylic acid and 2,2-bis (dicarboxyphenyl) hexafluoropropane. Examples of the anhydrides include monoanhydrides and dianhydrides of the above-mentioned tetracarboxylic acids.

Examples of the diamine include aromatic diamines, and more specifically, diaminodiphenyl ether, diaminodiphenyl sulfide, diaminodiphenyl sulfone, diaminobenzophenone, diaminodiphenylmethane, 2,2-bis (aminophenoxy). Phenyl) propane, 2,2-bis (aminophenylthioetherphenyl) propane, bis (aminophenoxy) diphenyl sulfone, bis (aminophenoxy) diphenyl ether, bis (aminophenoxy) diphenyl sulfide, bis (aminophenylthioether) diphenyl sulfone, bis (Aminophenyl thioether) diphenyl ether, bis (aminophenyl thioether) diphenyl sulfide, bis (aminophenoxy) diphenyl, bi (Aminophenoxy) benzophenone, bis (aminophenyl thioether) diphenyl, bis (aminophenyl thioether) benzophenone, bis (aminophenyl thioether) benzene,
Examples include 4,4′-bis (phenylenediisopropylidene) dianiline, 2,2-bis (aminophenoxyphenyl) hexafluoropropane, bis (aminophenyl) anthracene, bis (aminophenyl) fluorene and phenylenediamine.

A diisocyanate having a structure in which the amino group of the above diamine is replaced with an isocyanate group can be used as well.

These tetracarboxylic acids or their anhydrides and diamines or diisocyanates can be used either alone or in combination of two or more, as long as the resulting polyimide exhibits thermoplasticity.

The above-mentioned modified products and polymer alloys include
For example, PPE / polystyrene, PPE / polyamide,
Examples include PC / ABS, PC / polyester, nylon / modified polyolefin, nylon / modified ABS, nylon / polyarylate, and POM / thermoplastic polyurethane.

Further, the present oligoimides can be added to general-purpose thermoplastic resins other than the above resins (for example, polyvinyl chloride, polyethylene, polypropylene, ABS, etc.).

The thermoplastic resin according to the present invention can be used alone or in admixture of two or more as long as the characteristics are not impaired.

The melt viscosity of the thermoplastic resin used in the present invention is not particularly limited as long as it can be injection-molded or blow-molded.
When measured using 00 ° C. and a shear rate of 10 ³ / sec), it is usually 10 to 100,000 poise, preferably 1
It is recommended to be about 00 to 50,000 poise.

The amount of this oligoimide compounded is about 0.1 to 100 parts by weight, based on 100 parts by weight of the thermoplastic resin.
It is preferably about 0.5 to 50 parts by weight. Furthermore, when the oligoimide is used as a low-viscosity agent or a crystallization accelerator, it is 1 to 20 parts with respect to 100 parts by weight of the thermoplastic resin.
It is desirable to add so that it may be added by weight. If the addition amount is less than 0.1 parts by weight, the desired properties are not improved so much, and if it is added in excess of 100 parts by weight, the heat resistance required for the resin may be impaired.

The thermoplastic resin composition according to the present invention has a crystal nucleating agent, a reinforcing agent, a filler, an antioxidant, an ultraviolet absorber, and Various additives such as antistatic agents, flame retardants, lubricants, release agents, pigments and dyes can be added.

The use of a crystal nucleating agent often gives favorable results because the crystallization rate becomes faster. Although the amount of the crystal nucleating agent used is not particularly limited, it is usually preferable to use about 0.001 to 10 parts by weight per 100 parts by weight of the thermoplastic resin. Examples of the crystal nucleating agent include known inorganic nucleating agents and organic nucleating agents.

As the inorganic nucleating agent, talc, mica, silica, kaolin, clay, attapulgite, romite powder, quartz powder, zinc white, diatomaceous earth, montmorillonite,
Vermiculite, amorphous silica, glass powder, silica-alumina, wollastonite, carbon black, pyroferrite, graphite, zinc sulfide, boron nitride,
Examples include silicon resin powder, silicates such as calcium, magnesium, aluminum, lithium, barium, and titanium, sulfates, carbonates, phosphates, aluminates, and oxides.

As the organic nucleating agent, those commonly used in this field can be used. Examples thereof include metal salts of aliphatic carboxylic acids, metal salts of aromatic carboxylic acids such as benzoic acid and terephthalic acid, aromatic phosphonic acids and Polymer compounds having metal salts, metal salts of aromatic phosphoric acid, metal salts of aromatic sulfonic acids such as benzenesulfonic acid and naphthalenesulfonic acid, metal salts of β-diketones, metal salts of carboxyl groups, 4,6 nylon Examples thereof include fine powders of crystalline polymers such as polyphenylene sulfide ketone and polyester having para-hydroxybenzoic acid as a monomer.

Fillers may be added as reinforcing agents or for bulking purposes. The filler is not particularly limited, and those commonly used in this field can be used. Specifically, carbon black, calcium carbonate, magnesium carbonate, kaolin, calcined clay, talc, aluminum silicate, calcium silicate, silicic acid, carbon fiber, glass fiber, asbestos fiber, silica fiber, zirconia fiber, aramid fiber, Examples include potassium titanate fibers and the like. These can be used alone or in combination of two or more. The amount of the filler used is not particularly limited, but is usually 10 to 4 per 100 parts by weight of the thermoplastic resin.
It is preferred to use 00 parts by weight, especially 30 to 300 parts by weight.

When using these fillers, it is desirable to use a surface treatment agent and a sizing agent if necessary. As such a surface treatment agent and a sizing agent, a silane compound,
Epoxy compounds and isocyanate compounds are used.

Examples of the antioxidant include phenolic compounds such as bisphenol A or trade name "Irganox 1010".

Examples of ultraviolet absorbers and light stabilizers include hindered amine compounds, benzophenone compounds and benzotriazole compounds.

Examples of the antistatic agent include sodium alkane sulfonate and polymers having a poly (oxyalkylene) segment and a polyamide segment.

As the lubricant and release agent, those commonly used in this field can be used as long as the characteristics of the present invention are not impaired. Specific examples include wax esters, esters of polyhydric alcohols and higher fatty acids, esters of higher alcohols and polyhydric carboxylic acids, polyolefins and the like.

Examples of the wax ester include rice bran wax, carnauba wax, candelilla wax and beeswax.

Examples of esters of polyhydric alcohols and higher fatty acids include esters of ethylene glycol, diethylene glycol, trimethylolpropane, pentaerythritol, dipentaerythritol and aliphatic monocarboxylic acids having 12 to 36 carbon atoms. It

Examples of the ester of higher alcohol and polycarboxylic acid include esters obtained from a higher alcohol having 12 to 36 carbon atoms and a predetermined polybasic acid or an anhydride thereof.

The predetermined polybasic acid has 4 to 4 carbon atoms.
26 aliphatic dibasic acids, tricarballylic acid, aconitic acid, aliphatic cyclobasic acids such as methylcyclohexene tricarboxylic acid, 1,2,3,4-butanetetracarboxylic acid, cyclopentanetetracarboxylic acid, methyltetrahydrophthalic acid And an aliphatic tetrabasic acid such as an ene adduct of maleic acid,
Phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, biphenyltetracarboxylic acid, benzophenonetetracarboxylic acid, 3,3 ', 4,4'-
Aromatic polycarboxylic acids such as diphenyl sulfone tetracarboxylic acid are exemplified.

Examples of the polyolefin include polyethylene and poly (4-methyl-1-pentene).

[0082]

BEST MODE FOR CARRYING OUT THE INVENTION The thermoplastic resin composition according to the present invention is prepared by a usual method. For example, the required amount of each of the above-mentioned thermoplastic resin, the present oligoimides, and various additive components which are appropriately used as necessary are mixed by a V-blender, a ribbon blender, a Henschel mixer, a tumbler blender, etc. Using a kneader such as an oven roll, a single-screw extruder, a twin-screw extruder, and a single-screw reciprocating screw, a temperature exceeding the melting temperature of the resin (preferably the melting temperature of the resin + (about 20 to 150 ° C)) The desired resin composition is obtained by mixing at a certain temperature).

The thermoplastic resin composition thus obtained is
It is useful as a material for various molded articles, and is molded by a method commonly used in this field, for example, injection molding, extrusion molding, blow molding, calender molding, rotational molding or the like.

For example, in the case of injection molding, the injection conditions are appropriately selected according to the type of thermoplastic resin used, but usually the resin temperature is about 200 to 400 ° C., the mold temperature is about 0 to 250 ° C., and the injection is performed. It is preferable to adopt a condition of a pressure of about 500 to 1300 kg / cm ² .

In the case of blow molding, the molding conditions can be appropriately selected according to the type of thermoplastic resin used, but usually the resin temperature is about 100 to 400 ° C. and the mold temperature is 0.
It is preferable to employ conditions of about 250 ° C. and a blowing pressure of about ² to 10 kgf / cm ² .

The obtained molded product is suitable for use in, for example, electrical and electronic equipment parts, automobile equipment parts and chemical part materials.

The thermoplastic resin composition of the present invention has the following advantages. That is, by blending the oligoimides with a thermoplastic resin, the melt viscosity of the resin can be reduced and the crystallization of the crystalline resin can be promoted. Therefore, there are advantages such as improvement in productivity and suppression of thermal deterioration due to a decrease in molding temperature.

When the present oligoimides are blended with any of the above-mentioned thermoplastic resins, molding can be advantageously carried out, and moldings having excellent properties can be obtained. Particularly, according to the thermoplastic resin molding method of the present invention,
There are advantages that the molded product can be made thinner, precision molding can be performed, and the molding cycle can be shortened.

[0089]

EXAMPLES The present invention will be described in detail below with reference to examples.

Production Example 1 46.8 g (0.2 mol) of BTC and 5 stearylamine
4.0 g (0.2 mol) and 6.0 g of ethylenediamine
(0.1 mol) and DMF 200 g and xylene 200 g
The mixture was mixed and stirred in a mixed solvent, and the temperature was raised. The solvent was also distilled off while removing the produced water, and finally heated to 260 ° C., and the reaction was continued under a reduced pressure condition of 10 mmHg until no distillate was consumed to prepare oligoimide (oligoimide 1). . In addition, as a result of infrared absorption analysis of "oligoimide 1",
Characteristic absorption (ν (C = O)) due to imide group is 1775cm
^-1 and 1703 cm ^-1 .

Production Example 2 As raw materials, 46.8 g (0.2 mol) of BTC, 53.8 g (0.2 mol) of hydrogenated tallow amine and 11.6 g (0.1 mol) of 1,6-hexanediamine were used. Except for this, the same procedure as in Production Example 1 was carried out to prepare an oligoimide (oligoimide 2). As a result of infrared absorption analysis of "oligoimide 2", the same characteristic absorption as "oligoimide 1" was observed.

Production Example 3 46.8 g (0.2 mol) of BTC, 5 stearylamine
4.0 g (0.2 mol) and m-xylylenediamine 1
3.6 g (0.1 mol) was mixed and stirred in a mixed solvent of 80 g of ion-exchanged water and 80 g of xylene, and the temperature was raised. The solvent was also distilled off while removing the produced water, and finally heated to 260 ° C., and the reaction was continued under a reduced pressure of 10 mmHg until no distillate was produced to prepare oligoimide (oligoimide 3). . As a result of infrared absorption analysis of "oligoimide 3", the same characteristic absorption as "oligoimide 1" was observed.

Production Example 4 As raw materials, 46.8 g (0.2 mol) of BTC, 53.8 g (0.2 mol) of hydrogenated tallow amine and 14.2 g (0.1 mol) of 1,3-bis (aminomethyl) cyclohexane. In the same manner as in Production Example 2 except that was used, an oligoimide (oligoimide 4) was prepared. In addition, as a result of infrared absorption analysis of "oligoimide 4", "oligoimide 1"
Similar characteristic absorption was observed.

Production Example 5 46.8 g (0.2 mol) of BTC, laurylamine 3
7.0 g (0.2 mol) and 4,4'-diaminodiphenylmethane (19.8 g, 0.1 mol) were dispersed in xylene and heated under reflux to remove xylene while removing water produced by distillation. It was distilled off gradually and the reaction was continued until the reaction temperature reached 260 ° C. After the reaction, the remaining xylene was topped under reduced pressure to prepare oligoimide (oligoimide 5). As a result of infrared absorption analysis of "oligoimide 5", the same characteristic absorption as "oligoimide 1" was observed.

Production Example 6 Instead of laurylamine, hydrogenated tallow amine 53.8
An oligoimide (oligoimide 6) was produced in the same manner as in Production Example 5 except that g (0.2 mol) was used.
As a result of infrared absorption analysis of "oligoimide 6", the same characteristic absorption as "oligoimide 1" was observed.

Production Example 7 39.6 g (0.2 mol) of BTC dianhydride and 4,4 '
-20.0 g (0.1 mol) of oxydianiline was mixed and stirred in 200 g of N-methylpyrrolidone (NMP) at 50 ° C for 2 hours. Then 54.0 g of stearylamine
(0.2 mol) was added and the temperature was raised. The solvent was also distilled off while removing the produced water, and finally heated to 260 ° C., and the reaction was continued under a reduced pressure condition of 10 mmHg until no distillate was produced to prepare an oligoimide (oligoimide 7). . As a result of infrared absorption analysis of "oligoimide 7",
The same characteristic absorption as "oligoimide 1" was observed.

Production Example 8 39.6 g (0.2 mol) of BTC dianhydride as a raw material,
An oligoimide (oligoimide 8) was prepared in the same manner as in Production Example 8 except that 21.2 g (0.1 mol) of m-phenylenediamine and 52.2 g (0.2 mol) of p-dodecylaniline were used. As a result of infrared absorption analysis of "oligoimide 8", the same characteristic absorption as "oligoimide 1" was observed.

Production Example 9 BTC (70.2 g, 0.3 mol) and m-xylylenediamine (27.2 g, 0.2 mol) were added to water (120 g) and NMP.
The mixture was stirred in 60 g and xylene 60 g, and the temperature was raised.
While heating and refluxing, distilled water was distilled out of the system, and the reaction was continued until the distilled water disappeared. Then, 54.0 g (0.2 mol) of stearylamine was added. Xylene and NMP were also distilled off, and the mixture was finally heated to 260 ° C., and the reaction was continued under a reduced pressure of 10 mmHg until no distillate was left, to prepare oligoimide (oligoimide 9). In addition, as a result of infrared absorption analysis of "oligoimide 9",
The same characteristic absorption as "oligoimide 1" was observed.

Production Example 10 54.0 g (0.2 mol) of stearylamine was mixed and stirred in 50 g of xylene, and the temperature was raised. Under heating under reflux, a separately prepared BTC aqueous solution containing 70.2 g (0.3 mol) of BTC and 150 g of ion-exchanged water was added dropwise. While distilling the distilled product out of the system, the reaction is continued until the distilled water is exhausted, and then hexamethylenediamine 23.2
g (0.2 mol) was added dropwise. Xylene is also distilled off, and the reaction temperature is finally heated to 260 ° C., 10 mmHg
The reaction was continued under reduced pressure conditions until the distillate was exhausted to prepare oligoimide (oligoimide 10). As a result of infrared absorption analysis of "oligoimide 10", the same characteristic absorption as "oligoimide 1" was observed.

Example 1 "Oligoimide 1" 2 per 100 parts by weight of PET resin
After adding parts by weight, the mixture was melt-mixed at 260 ° C. in an extruder, and the obtained strand was water-cooled and cut to prepare a sample. The melt viscosity of this sample is 265 ° C and the pressure is 10 kg.
It was measured under the conditions of f / cm ² , die diameter of 1 mm, and length of 10 mm. The sample after melt viscosity measurement was dissolved in a phenol / tetrachloroethane = 60/40 (weight ratio) solution, and the intrinsic viscosity [η] at 25 ° C. was measured. The obtained results are first
Shown in the table. The melt viscosity is an index for evaluating the fluidity of the resin, and the larger the value, the better the fluidity. The intrinsic viscosity [η] is an index of the molecular weight of the resin, and the additive-free resin When the same as, it means that the molecular weight of the resin does not decrease.

Examples 2 to 6 A resin composition was prepared in the same manner as in Example 1 except that a predetermined oligoimide was used as a resin modifier, and the melt viscosity and the intrinsic viscosity of the resin composition were measured. The results obtained are shown in Table 1.

Comparative Example 1 The melt viscosity and intrinsic viscosity of the PET resin used in Example 1 were measured in the same manner as in Example 1. The results obtained are shown in Table 1.

[0103]

[Table 1]

Example 7 The melt viscosity of a resin composition prepared by dry blending 3 parts by weight of "oligoimide 7" with 100 parts by weight of a bisphenol A type polycarbonate resin was measured at a resin temperature of 280.
℃, pressure 40kgf / cm ² , die diameter 1.0mm, length 10mm
It was measured under the conditions of. The sample after the melt viscosity measurement was dissolved in dichloromethane to measure the intrinsic viscosity at 20 ° C.
The results obtained are shown in Table 2.

Examples 8 to 10 A resin composition was prepared in the same manner as in Example 7 except that a predetermined oligoimide was used as a resin modifier, and the melt viscosity and the intrinsic viscosity of this sample were measured. The results obtained are shown in Table 2.

Comparative Example 2 The melt viscosity and intrinsic viscosity of the polycarbonate resin used in Example 7 were measured in the same manner as in Example 7. The results obtained are shown in Table 2.

[0107]

[Table 2]

Example 11 3,3 ′, 4,4′-diphenylsulfone tetracarboxylic acid dianhydride (1.02 mol) and 2,2-bis [4-
(P-Aminophenoxy) phenyl] propane (1.0
0 mol) and 5 parts by weight of “oligoimide 6” are added to 100 parts by weight of the thermoplastic polyimide powder obtained by dehydration condensation at 170 ° C., and the mixture is homogenized at 360 ° C. using an extruder. After mixing, the resulting strand was cooled with water and cut to prepare a sample. The melt viscosity of this sample was measured at a temperature of 360 ° C., a pressure of 100 kgf / cm ² , a die diameter of 1.0 mm, and a length of 10 mm. Further, the discoloration and foaming of the obtained strand were visually confirmed. The obtained result is the third
Shown in the table.

Examples 12 to 14 A resin composition was prepared in the same manner as in Example 11 except that a predetermined oligoimide was applied as a resin modifier, the melt viscosity of the resin composition was measured, and the obtained strands were visually evaluated. did. The results obtained are shown in Table 3.

Comparative Example 3 The melt viscosity of the thermoplastic polyimide resin powder used in Example 11 was measured in the same manner as in Example 11, and the obtained strand was visually evaluated. The results obtained are shown in Table 3.

[0111]

[Table 3]

Example 15 To 100 parts by weight of PEEK resin containing 30% by weight of glass fiber, 5 parts by weight of "oligoimide 6" was added and mixed using an extruder at 380 ° C until uniform. The obtained strand was cooled with water and cut to obtain a sample.
The flow distance of this sample was measured using a 1.2 mm-thick spiral die, with a cylinder temperature of 380 ° C. and a pressure of 850 kgf / c.
The measurement was performed under the conditions of m ² and a mold temperature of 170 ° C. The results obtained are shown in Table 4.

Examples 16 to 18 A resin composition was prepared in the same manner as in Example 15 except that a predetermined oligoimide was used as a resin modifier, and the flow distance of this was measured. The results obtained are shown in Table 4.

Comparative Example 4 The flow distance of the PEEK resin used in Example 15 was changed to that of Example 1.
Measurement was carried out in the same manner as 5. The results obtained are shown in Table 4.

[0115]

[Table 4]

Example 19 3 parts by weight of "oligoimide 3" was dry blended with 100 parts by weight of a semi-crosslinked polyphenylene sulfide resin, and the mixture was melt-kneaded at 300 ° C using an extruder and pelletized. Cylinder temperature 300 ℃, the obtained pellets,
A sample was obtained by injection molding at a mold temperature of 70 ° C. The heat quantity of recrystallization of this sample at the time of temperature rise was measured using DSC. or,
Pellet MFR, temperature 280 ℃, pressure 10kgf / cm ² ,
It was measured under the conditions of a die diameter of 1.0 mm and a length of 10 mm. The results are shown in Table 5. The smaller the amount of heat of crystallization at the time of temperature rise, the higher the degree of crystallinity, which is an index showing the effect of promoting crystallization in a low temperature mold.

Examples 20 to 23 A resin composition was prepared in the same manner as in Example 19 except that a predetermined oligoimide was applied as a resin modifier, and DSC measurement of this sample was carried out. The results obtained are shown in Table 5.

Comparative Example 5 The DSC measurement of the semi-crosslinked polyphenylene sulfide resin used in Example 19 was carried out in the same manner as in Example 19. The results obtained are shown in Table 5.

[0119]

[Table 5]

Example 24 100 parts by weight of a 30% by weight glass fiber-containing resin of polyamide resin (nylon MXD6) of m-xylylenediamine and adipic acid was mixed with 5 parts by weight of "oligoimide 3", and a cylinder temperature was 260 ° C. The appearance (in particular, the presence or absence of glass fiber protrusion) and the surface gloss of a sample piece obtained by injection molding at a mold temperature of 100 ° C. were observed. The protrusion of the glass fiber of the test piece is influenced by the fluidity of the resin in the mold, and when the fluidity is poor, the protrusion tends to increase. Further, the surface gloss of the sample piece is shown that the oligoimide of the present invention has the effect of promoting the crystallization of the resin and produces dense crystal grains on the surface of the molded sample by the low temperature mold.

Examples 25 and 26 A resin composition was prepared in the same manner as in Example 24 except that a predetermined oligoimide was applied as a resin modifier, and the appearance and surface gloss of this sample were observed. The results obtained are shown in Table 6.

Comparative Example 6 The appearance and surface gloss of the glass fiber-containing polyamide resin used in Example 24 were observed in the same manner as in Example 24. The results obtained are shown in Table 6.

[0123]

[Table 6]

Example 27 Poly (2,6) modified with high impact polystyrene (A)
-Dimethyl-1,4-phenylene ether (hereinafter "PP
It is abbreviated as "E resin". ) (B) (mixing ratio: A / B = 1
(1/1, weight basis) 5 parts by weight of “oligoimide 1” to 100 parts by weight, and melt-mixed with an extruder at 270 ° C. until uniform and pelletized. The melt flow rate (MFR) of this resin composition was measured at a temperature of 250.
℃, load 10kgf, die diameter 2.095mm, length 8.0m
It was measured under the condition of m. The results obtained are shown in Table 7.

Examples 28 to 31 A resin composition was prepared in the same manner as in Example 27 except that a predetermined oligoimide was applied as a resin modifier, and the MFR of this was measured. The results obtained are shown in Table 7.

Comparative Example 7 The MFR of the high impact polystyrene / PPE resin used in Example 27 was measured in the same manner as in Example 27. The results obtained are shown in Table 7.

[0127]

[Table 7]

Example 32 PPE resin modified with amorphous nylon (mixing ratio = 1
(1/1, weight basis) 5 parts by weight of “oligoimide 1” was added to 100 parts by weight, and the mixture was melt-mixed at 270 ° C. using an extruder until uniform, and then pelletized. The melt flow rate (MFR) of this resin composition was measured at a temperature of 280 ° C.
It was measured under a load of 5 kgf, a die diameter of 2.095 mm, and a length of 8.0 mm. The results obtained are shown in Table 8.

Examples 33 to 35 A resin composition was prepared in the same manner as in Example 32 except that a predetermined oligoimide was used as a resin modifier, and the MFR of this was measured. The results obtained are shown in Table 8.

Comparative Example 8 MFR of 6-nylon / PPE resin used in Example 32
Was measured in the same manner as in Example 32. The results obtained are shown in Table 8.

[0131]

[Table 8]

[0132]

By blending the oligoimides according to the present invention with a thermoplastic resin, the melt viscosity of the resin can be reduced and the crystallization of the crystalline resin can be promoted. That is, the resin composition according to the present invention has a high crystallization rate and can be molded at a wide range of mold temperatures from low temperature to high temperature, and the obtained molded product has a good appearance, few burrs, and dimensions. Low shrinkage and excellent mechanical strength.

Claims (5)

[Claims] 1. A thermoplastic resin and the thermoplastic resin 1
To 100 parts by weight, one or more modifiers selected from the group consisting of the oligoimide represented by the general formula (1), a derivative of the oligoimide having a carboxyl group, and a metal salt of the derivative of the oligoimide are added. 0.1-10
A thermoplastic resin composition containing 0 part by weight. R ¹ -A ¹ (-X ¹ -Y ¹ ) a-X ² -A ² -R ² (1) [wherein R ¹ and R ² are the same or different, and are an aliphatic hydrocarbon group or an aromatic carbon group] Represents a hydrogen group. A ¹ and A ² are the same or different and represent a direct bond, a phenylene group or a cyclohexylene group. X ¹ and X ² are the same or different and represent structural formula B, structural formula B or structural formula C. Y ¹ is an alkylene group or a geometric isomer thereof, a phenylene group which may be substituted with an alkyl group, a group —CH ₂ — (phenylene) —CH ₂ —, a group —CH ₂ — (cyclohexylene) —CH ₂ —, or Group-B ¹
-Z ¹ -B ² - represents a. B ¹ and B ² are the same or different and each represent a phenylene group which may be substituted with an alkyl group, a group-(phenylene) -Z ^2- (phenylene)-or a cyclohexylene group. Z ¹ and Z ² are the same or different and are a direct bond, —S—, —SO ₂ —, —O—, —CH ₂ —, —CO—.
Alternatively, it represents a methylene group substituted with an alkyl group or an aryl group. a represents the integer of 1-10. The group-(-X
^{In 1} -Y ¹ ) a-, a number of X ^{1 s} and Y ^{1 s} may be the same or different. ] [Chemical 1] Embedded image Embedded image 2. The thermoplastic resin composition according to claim 1, wherein the modifier is an oligoimide represented by the general formula (2). ^{R 3 -A 3 (-X 3 -Y} 2) b-X 4 -A 4 -R 4 (2) [ wherein, R ^3, R ⁴ are the same or different, carbon atoms from 8 to 22
Represents an alkyl group. A ³ and A ⁴ are the same or different and represent a direct bond, a phenylene group or a cyclohexylene group.
X ³ and X ⁴ are the same or different and represent structural formula B, structural formula B or structural formula C. Y ² is an alkylene group or a geometric isomer thereof, a phenylene group which may be substituted with an alkyl group, a group —CH ₂ — (phenylene) —CH ₂ —, a group —CH ₂
- (cyclohexylene) -CH ₂ - or a group -B ³ -Z ³ -
Represents B ⁴ −. B ^3, B ⁴ are the same or different, an alkyl group which may be substituted with a phenylene group, group - represents a or cyclohexylene group - (phenylene) -Z ⁴ - (phenylene). Z ³ and Z ⁴ are the same or different, and are a direct bond, -S
_{-, - SO 2 -, -} O -, - CH 2 -, - CO- or alkyl or aryl group represents a methylene group substituted. a represents the integer of 1-10. Incidentally, group - (- X ³ -
In Y ² ) b-, b X ³ and Y ² may be the same or different. ] 3. The thermoplastic resin composition according to claim 1, wherein the modifier is an oligoimide represented by the general formula (3). ^{R 5 - (X 5 -Y 3} ) c-X 6 -R 6 (3) [ wherein, R ^5, R ⁶ are the same or different, having from 8 to 22 carbon atoms
Represents an alkyl group. X ⁵ and X ⁶ are the same or different and represent structural formula B, structural formula B or structural formula C. Y ³ is an alkylene group or a geometric isomer thereof, a phenylene group which may be substituted with an alkyl group, and a group —CH ₂ — (phenylene) —
CH ₂ — or a group —B ⁵ —Z ⁵ —B ⁶ —. B ^5, B ⁶ are the same or different, a phenylene group in the alkyl group represented by substituted or group - (phenylene) -Z ⁶ - (phenylene) - represents a. Z ^5, Z ⁶ are the same or different, directly _{bonded, -S -, - SO 2 -} , - O -, - CH 2 -, - CO-
Alternatively, it represents a methylene group substituted with an alkyl group or an aryl group. c represents an integer of 1 to 10. The group-(-X
^{In 5-} Y ³ ) c-, c X ⁵ and Y ³ may be the same or different. ] 4. The thermoplastic resin composition according to claim 1, wherein the modifier is an oligoimide prepared by dehydration reaction of the following three kinds of compounds (1) to (3). (1) 1,2,3,4-butanetetracarboxylic acid and /
Or its anhydride (2) 1 represented by the general formula (4)
Species or two or more monoamines. _{^{R 7 -A 5 -NH 2 (4}} ) [ wherein, R ⁷ represents an alkyl group having 4 to 22 carbon atoms. A ⁵
Represents a direct bond or a phenylene group. ] (3) 1 type (s) or 2 or more types of diamine represented by General formula (5). _{^{H 2 N-R 8 -NH 2}} (5) [ wherein, the alkylene group of R ⁸ is 2 to 15 carbon atoms, a phenylene group, group -CH ₂ - (phenylene) -CH ₂ - or a group -
B ⁷ -Z ⁷ -B ⁸ - represents a. B ^7, B ⁸ are the same or different, a phenylene group or a group that the alkyl group is substituted - (phenylene) -Z ⁸ - (phenylene) - represents a.
Z ⁷ and Z ⁸ are the same or different and are a direct bond, -S-, -S.
It represents a methylene group substituted with O ₂ —, —O—, —CH ₂ —, —CO—, an alkyl group or an aryl group. ] 5. The thermoplastic resin is polyarylene sulfide, polysulfone, polyphenylene ether, polyether sulfone, polyether ether ketone, phenylmaleimide, ABS modified with α-methylstyrene and / or maleic anhydride, or chlorinated poly (vinyl chloride). Aromatic polyamides of vinyl chloride, terephthalic acid and aliphatic diamines or xylylenediamine and aliphatic dicarboxylic acids, 6 nylon, 6,6 nylon, 4,6 nylon, 11 nylon,
12 nylon, polycarbonate, polyacetal, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalene dicarboxylate, poly-1,4-cyclohexane dimethylene terephthalate,
1. One or more resins selected from the group consisting of polyarylate, liquid crystal polymer, polyamideimide, thermoplastic polyimide, polyetherimide, polymethylpentene, modified products of these resins, and polymer alloys. The thermoplastic resin composition according to claim 4.