JPH10195195A - Oligoimide, resin modifier composition and thermoplastic resin composition containing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a thermoplastic resin composition which has improved moldability and can give a product of excellent quality by adding a resin modifier being a novel oligoimide prepared by the dehydration reaction among a tetracarboxylic acid, a monoamine and a diamine to a thermoplastic resin. SOLUTION: The three compounds of a tetracarboxylic acid, a monoamine and a diamine are subjected to a dehydration reaction to obtain an oligoimide represented by formula I (R<1> and R<2> are each an aliphatic hydrocarbon group; A<1> and A<2> are each a direct bond, phenylene or cyclohexylene; X<1> and X<2> are each -Ph-, -naphthalene-, -Ph-Z<1> -Phor a carboxylic acid residue of formula II; Z<1> is a direct bond, -O-, -CO-, -CH2 -, -CH(CH3 )2 - or -S-; Y<1> is an alkylene, phenylene, -CH2 -(phenylene)-CH2 -, -CH2 (cyclohexylene)-CH2 - or the like; a is 1-10; and R<3> is H or a 1-8C alkyl).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a novel oligoimide, a resin modifier composition containing the same, and a thermoplastic resin composition containing the composition.

[0002]

2. Description of the Related Art Recently, thermoplastic resins having heat resistance have been used as engineering plastics as mechanical materials,
Used in electronic components. In molding the thermoplastic resin, various resin modifiers, for example, fatty acids such as stearic acid, fatty acids, fatty acids such as stearic acid, for the purpose of increasing productivity, lowering melt viscosity, accelerating crystallization, and improving mold releasability. 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 ethylene bisstearamide has been proposed (Japanese Patent Application Laid-Open No. 60-44547, Kaihei 3-250049).

However, thermoplastic resins having heat resistance are excellent in mechanical properties and heat resistance, but are generally inferior in processability such as high melting temperature and low fluidity. In addition, a problem occurs when the filler is mixed. Further, there is a problem in production, such as the necessity of an unnecessarily high temperature in the latter half of the polymerization reaction.

[0004] When the above-mentioned various resin modifiers are blended in order to solve the above-mentioned problems, there have been problems such as thermal decomposition and boiling at the time of melting, contaminating the mold and generating bubbles in the resin. Therefore, development of a resin modifier having heat resistance has been desired.

[0005]

DISCLOSURE OF THE INVENTION The present invention provides a novel oligoimide, a resin modifier composition having excellent heat resistance and not deteriorating the resin properties, and a novel resin composition containing the resin modifier composition. An object is to provide a useful thermoplastic resin composition.

[0006]

Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, a specific oligoimide is a novel compound which has not been described in the literature, has heat resistance itself, and It has been found that it functions as a resin modifier with the desired performance, such as lowering the melt viscosity of the thermoplastic resin and improving the crystallinity or the releasability of the crystalline thermoplastic resin. The present invention has been completed based on such findings.

That is, the oligoimide according to the present invention is characterized by comprising one or more kinds represented by the general formula (1).

[0008]

Embedded image [Wherein, R ¹ and R ² are the same or different and each represents an aliphatic 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 a group -Ph-, a group -naphthalene-, a group -Ph-Z ¹ -Ph-, or a residue from a carboxylic acid of the structural formula (A). Z ¹ is a direct bond, a group —O—, a group —CO—, a group —CH ₂ —, a group —CH (CH ₃ ) ₂ —, a group —
Represents S-. 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 Represents a group -B ¹ -Z ² -B ^2- . B ¹ and B ² are the same or different, and a phenylene group optionally substituted with an alkyl group, a group-(phenylene) -Z
Represents a ^3- (phenylene)-or cyclohexylene group.
Z ² and Z ³ are the same or different and each is a direct bond, a group —S—, a group —SO ₂ —, a group —O—, a group —CH ₂ —, a group —CO—, or a methylene substituted with an alkyl group or an aryl group. Represents a group. a represents an integer of 1 to 10. Incidentally, a number of X ¹ and Y ¹
May be the same or different. ]

[0009]

Embedded image [Wherein, R ³ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. ]

[0010] Among the oligoimides represented by the general formula (1), the oligoimide represented by the general formula (5) is recommended,
Particularly, an oligoimide represented by the general formula (6) is preferable.

[0011]

Embedded image [Wherein, R ⁶ and R ⁷ are the same or different and each have 4 to 30 carbon atoms.
Represents an aliphatic hydrocarbon group. X ^4, X ⁵ are the same or different, group -Ph-, group - naphthalene -, group -Ph-Z ⁷ -
Represents a residue from Ph- or a carboxylic acid of the structural formula (A). Z ⁷ represents a direct bond, a group —O—, a group —CO—, a group —.
CH ₂ —, a group —CH (CH ₃ ) ₂ —, and a group —S—. Y ²
Represents an alkylene group having 4 to 12 carbon atoms 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 —, group — (phenylene) —O
-(Phenylene) -C (CH ₃ ) _2- (phenylene) -O
Represents-(phenylene)-. b represents an integer of 1 to 10. Note that b X ⁴ and Y ² may be the same or different. ]

[0012]

Embedded image [Wherein, R ⁸ and R ⁹ are the same or different and each have 8 to 22 carbon atoms.
Represents an aliphatic hydrocarbon group. X ^6, X ⁷ are the same or different, group -Ph-, group - naphthalene -, group -Ph-Z ⁸ -
Represents a residue from Ph- or a carboxylic acid of the structural formula (A). Z ⁸ represents a direct bond, a group —O—, or a group —CO—. Y ³ represents a group —CH ₂ — (phenylene) —CH ₂ —, a group —CH ₂ — (cyclohexylene) —CH ₂ —, a group — (phenylene) —O— (phenylene) —C (CH ₃ ) ₂ —. Represents (phenylene) -O- (phenylene)-. c is 1 to 10
Represents an integer. Note that c X ⁶ and Y ³ may be the same or different. ]

The oligoimide represented by the general formula (1) is
For example, the compound can be obtained by subjecting the following three kinds of compounds (A) to (C) to a dehydration reaction.

(A) One or more tetracarboxylic acids containing an aromatic ring represented by the general formula (2) or anhydrides thereof. Specifically, an aromatic ring tetracarboxylic acid having 10 to 20 carbon atoms, a tetracarboxylic acid containing an aromatic ring, or an anhydride thereof is exemplified.

[0015]

Embedded image [Wherein X ³ represents a group -Ph-, a group -naphthalene-, a group -P
h-Z ⁴ -Ph- or structural formula represents the residue of a carboxylic acid (i). Z ⁴ is a direct bond, a group —O—, a group —C
O-, group -CH ₂ -, group -CH- (CH _{3) 2} -, group -S
Represents-. ]

More specifically, the tetracarboxylic acids include pyromellitic acid, biphenylenetetracarboxylic acid, diphenylethertetracarboxylic acid, benzophenonetetracarboxylic acid, diphenylsulfidetetracarboxylic acid, naphthalenetetracarboxylic acid, and bis (dicarboxyphenyl). ) Methane, bis (dicarboxyphenyl) propane, 1,3,3a, 4,5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) naphtho [1,2-C] furan- 1,3-dione (hereinafter abbreviated as TDA) is exemplified, and among them, pyromellitic acid, benzophenonetetracarboxylic acid, diphenylethertetracarboxylic acid, and TDA are recommended.

(B) One or more monoamines. Specific examples include an aliphatic primary monoamine having 1 to 30 carbon atoms and an aromatic primary monoamine having 6 to 24 carbon atoms.

Examples of the recommended aliphatic monoamines include aliphatic monoamines represented by the general formula (3) and C6 to C2.
The alicyclic monoamine of No. 4 is exemplified. These may have an aromatic ring.

R ⁵ -A ³ -NH ₂ (3) wherein R ⁵ represents a saturated or unsaturated, linear or branched alkyl group having 1 to 30 carbon atoms. A ³ represents a direct bond, a cyclohexylene group or a phenylene group. ]

As the 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, etc., among which decylamine, dodecylamine, tetradecylamine, hexadecylamine, octadecylamine and the like are recommended.

Furthermore, it is economically possible to use a mixture essentially containing these monoamines, that is, natural amines such as cocoamine, beef min, hydrogenated cocoamine, hydrogenated tallowamine, and hydrogenated fish oil amine. It is significant.

Examples of the alicyclic monoamine include cyclobutylamine, cyclopentylamine, cyclohexylamine, cyclohexylmethylamine, cyclohexylethylamine, methylcyclohexylamine, dimethylcyclohexylamine, and alkylcyclohexylamine having 2 to 18 carbon atoms.

As the aromatic monoamine, C6 to C2 is used.
The aromatic monoamine of No. 4 is exemplified. More specifically, butylaniline, allylaniline, pentylaniline, hexylaniline, heptylaniline, octylaniline, nonylaniline, decylaniline, undecylaniline, dodecylaniline, tridecylaniline, tetradecylaniline, pentadecylaniline, hexadecyl Examples include aniline, heptadecylaniline, octadecylaniline, octadecenylaniline, nonadecylaniline, icosylaniline, heneicosylaniline, docosylaniline, etc., among which decylaniline, dodecylaniline, tetradecylaniline, hexadecylaniline , Octadecylaniline and the like are recommended.

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

Among them, the diamine represented by the general formula (4) is recommended.

H ₂ N—R ⁵ —NH ₂ (4) wherein R ⁵ is an alkylene group having 2 to 15 carbon atoms, a phenylene group, a group —CH ₂ — (phenylene) —CH ₂ —, a group —C
H ₂ - (cyclohexylene) -CH ₂ - or a group -B ³ -Z ⁵
-B ⁴ - represents a. B ³ and B ⁴ are the same or different and each represents a phenylene group, a group-(phenylene) -Z ^6- (phenylene)-or a cyclohexylene group which may be substituted with an alkyl group. Z ⁵ and Z ⁶ may be the same or different, and may be a direct bond;
S-, group -SO ₂ -, group -O-, group -CH ₂ -, group -CO
— Or a methylene group substituted by an alkyl group or an aryl group. ]

As the aliphatic primary diamine, a compound having 2 carbon atoms
Preferred are primary diamines and their geometric isomers linked by a methylene group of ~ 15, specifically ethylenediamine, butylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylene. Diamine, decamethylenediamine, undecamethylenediamine, dodecamethylenediamine and geometric isomers thereof are exemplified.

Specific examples of the alicyclic diamine include 1,3
-Bis (aminomethyl) cyclohexane, isophoronediamine, diaminodicyclohexylmethane and methyl-substituted alicyclic thereof are exemplified.

Examples of the aliphatic primary diamine containing an aromatic ring include m-xylylenediamine and p-xylylenediamine.

Of these aliphatic diamines, ethylenediamine, hexamethylenediamine, 1,3-bis (aminomethyl) cyclohexane, isophoronediamine, m
-Xylylenediamine and p-xylylenediamine are preferred raw materials in view of the performance of lowering the melt viscosity of the oligoimide and the availability of the raw materials.

As the aromatic primary diamine, benzidine, dimethylbenzidine, diaminodiphenylmethane,
Diaminoditolylmethane, diaminodiphenylethane,
Diaminophenoxyphenylpropane, 2,2-bis (aminophenylthioetherphenyl) propane, bis (aminophenoxy) diphenylsulfone, bis (aminophenoxy) diphenylether, bis (aminophenoxy) diphenylsulfide, bis (aminophenylthioether) diphenylsulfone, Bis (aminophenylthioether) diphenylether, bis (aminophenylthioether) diphenylsulfide, bis (aminophenoxy) diphenyl, bis (aminophenoxy) benzophenone, bis (aminophenylthioether) diphenyl, bis (aminophenylthioether) benzophenone, bis (amino) Phenylthioether) benzene, (phenylenediisopropylidene) dianiline, 2,2-bis (Aminophenoxyphenyl) hexafluoropropane, bis (aminophenoxyphenyl) propane, diaminodiphenylether, diaminodiphenylsulfone, diaminobenzophenone, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, bis (aminophenoxy) biphenyl, 9, 10-bis (aminophenyl) anthracene,
Examples thereof include 9,9-bis (aminophenyl) fluorene, tolylenediamine, xylenediamine, and positional isomers thereof.

Of these aromatic diamines, diaminodiphenylmethane, diaminodiphenylether, diaminodiphenylsulfone, diaminobenzophenone, bis (aminophenoxyphenyl) propane, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, tolylenediamine Is a preferable raw material in view of the performance of lowering the melt viscosity of the oligoimide and the availability of the raw material. In particular, 2,2-bis [4- (p-aminophenoxy) phenyl] propane is recommended from the viewpoint of safety.

Isocyanate compounds and diisocyanate compounds corresponding to both the above monoamines and diamines can also be used as raw materials.

The type of the diamine is appropriately selected according to the type of the thermoplastic resin to be applied and the intended effect. In general, 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 its excellent compatibility, and a nonpolar resin is preferably an oligoimide having 8 to 15 carbon atoms. Oligoimides having an alkylene group or an alicyclic group having the following chain length are preferred.

These oligoimides may be used alone or in combination of several oligoimides, depending on the desired physical properties. In some cases, the oligoimide may be added in the form of a mixed imide having different repeating units.

In preparing the oligoimide, the degree of polymerization can be set by calculating and selecting the molar ratio of each raw material from the theoretical molecular weight. Usually, tetracarboxylic acid / monoamine / diamine (molar ratio) = 2 to 11/2
/ 1 to 10 are preferred.

When 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 tetracarboxylic acid and the monoamine tends to increase. Bisimide of a tetracarboxylic acid and a monoamine also reduces the melt viscosity of the thermoplastic resin by the same kind as in the present invention, promotes crystallization,
It is effective as a release agent, and when a mixture of the bisimide and the oligoimide is desired, a mixture can be obtained by setting the molar ratio of the condensation reaction.

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

There is no particular restriction on the molecular weight distribution of the oligoimide, but generally Mw / Mn (weight average molecular weight / number average molecular weight) is preferably 15 or less, more preferably 6 or less.
Furthermore, among oligoimides having the above-mentioned degree of polymerization, the molecular weight is 8
00 or more, preferably 1000 or more oligoimides,
Excellent heat resistance and recommended. On the other hand, from a manufacturing perspective,
Oligoimides having a molecular weight of 5000 or less, preferably 3000 or less, are recommended as a preferable range in terms of characteristics.

In the first half of the dehydration reaction, the neutralization reaction and the amidation reaction of the tetracarboxylic acid with the primary amine are mainly performed, and in the second half of the reaction, the amide acid of the tetracarboxylic acid and the primary amine is converted. Dehydration reaction is the main.

The dehydration reaction may be performed without a solvent, or a solvent in which tetracarboxylic acid is dissolved may be used.

Examples of the solvent capable of dissolving the tetracarboxylic acid include polar organic solvents such as dimethylformamide (DMF), dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, dioxane, and lower alcohols having 1 to 4 carbon atoms. Can be illustrated.

On the other hand, a method is also effective in which tetraamines are successively added and reacted with a monoamine and a diamine while stirring and dispersing in the presence of a dispersion solvent. 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 the industrial point of view, the reaction without solvent is most preferable, and the method of using a small amount of a dispersing solvent as an entrainer in the above polar solvent is effective.

The dehydration reaction is preferably performed 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, 150 to 400
C., preferably within the range of 200 to 300.degree. Within this range, the occurrence of a thermal decomposition reaction is small, and the reaction proceeds at an industrial rate.

The reaction time depends on the reaction temperature and cannot be determined unconditionally, but is usually 1 to 50 hours.

The dehydration reaction may be performed under normal pressure,
It may be performed under reduced pressure. The first half of the reaction is preferably performed under normal pressure, and the second half of the reaction is preferably performed under reduced pressure. The degree of decompression can be in the range of 0.01 to 760 mmHg.
Hg or less is desirable.

Although the dehydration reaction proceeds without a catalyst, when a catalyst is used, sodium, potassium, magnesium, calcium, barium, zinc, aluminum, tin,
Hydroxides, oxides, chlorides and organic acid salts such as lead can be used.

The oligoimide obtained by the above operation can be obtained by taking it out of the reaction vessel as it is when produced under the condition of no solvent. On the other hand, in the case of producing using a solvent, a dispersion medium or an entrainer, it is obtained by removing the solvent, the dispersion medium or the entrainer by distillation, topping or the like, and then taking out.

The obtained oligoimide is often a solid, and can be used as it is after grinding.

On the other hand, when a purified oligoimide is required, aromatic non-polar solvents such as benzene, toluene, and xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, dioxane, acetonitrile, and carbon atoms of 1
Insolubles such as metal salts are separated by filtration using aliphatic polar solvents such as lower alcohols, etc., and chlorinated solvents such as chloroform and monochlorobenzene, and purified by adsorption treatment such as clay treatment or reprecipitation method. You can do it.

Further, the resin modifier composition according to the present invention comprises:
A hindered phenolic antioxidant can be added in addition to the oligoimide which is an essential component.

The hindered phenolic antioxidants added to the resin modifier composition include 2,6-di-t-butyl-4-ethylphenol and 2,2'-methylenebis (4-methyl-6- t-butylphenol), 4,4 '
-Butylidenebis (6-t-butyl-m-cresol,
3,5-di-t-butyl-4-hydroxybenzylphosphonic acid monoethyl ester calcium, 2,2′-
Ethylidene-bis (4,6-di-t-butylphenol), tetrakis [methylene-3- (3′-5′-di-
t-butyl-4'-hydroxyphenyl) -propionate] methane, 1,3,5-trimethyl-2,4,6-
Tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene and the like are exemplified. One or more of these antioxidants can be blended.

The antioxidant is oligoimide 100
The range is preferably from 0.001 to 200 parts by weight, more preferably from 0.01 to 100 parts by weight based on parts by weight.

By adding a hindered phenolic antioxidant, it is possible to prevent coloring due to oligoimide and to suppress resin deterioration during resin processing.

The method for preparing the resin modifier composition of the present invention is as follows.
Although there is no particular limitation, a raw material such as an oligoimide is dry-blended with a homomixer, a Henschel mixer, or the like, added to a molten oligoimide compound and mixed in a molten state, or added together with the raw material at the time of production of the oligoimide compound to form the oligoimide. A method such as synthesis is exemplified. In particular, if a phenolic antioxidant is added at the stage of synthesizing the oligoimide compound, an oligoimide having a good hue can be obtained, and this is a recommended method.

The resin modifier composition according to the present invention comprises the oligoimide as an essential component and, if necessary, other additives such as an antioxidant other than a hindered phenolic antioxidant, an ultraviolet absorber, Lubricants and the like can be mixed and used in any amount so long as the object of the present invention is not impaired.

Further, the present invention also provides a thermoplastic resin composition comprising a resin modifier composition comprising the oligoimide compound and a thermoplastic resin.

Examples of the type of the thermoplastic resin according to the present invention include polyarylene sulfide (PAS) such as polyphenylene sulfide (PPS), polysulfone, polyphenylene ether (PPE), polypolyether ether ketone (PEEK), phenylmaleimide and α- ABS modified with methylstyrene and / or maleic anhydride,
Chlorinated polyvinyl chloride, aromatic polyamide such as terephthalic acid and aliphatic diamine or aromatic dicarboxylic acid, 6
Nylon, 6,6 nylon, 6,10 nylon, 4,6
Aliphatic polyamides such as nylon, polycarbonate (PC) having bisphenol A in the main skeleton, polyacetal, polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalene dicarboxylate (PEN), poly-1,4- Polyesters and glycols composed of an aromatic dicarboxylic acid such as cyclohexane terephthalate and glycol, and polyarylates (for example, polyarylate of an aromatic dicarboxylic acid composed of terephthalic acid and / or isophthalic acid and bisphenol A, such as trade name "U-Polymer" (Unitika) Company),
"NAP" (manufactured by Kanegafuchi Chemical Co., Ltd.)), liquid crystal polymers (for example, p-hydroxybenzoic acid, biphenol and 4,
Liquid crystal polymer having 4′-diphenyldicarboxylic acid as a representative monomer, for example, trade names “Roadrun” (manufactured by Unitika), “EPE” (manufactured by Mitsubishi Chemical Corporation), “Idemitsu LCP”
(Idemitsu Petrochemical Co., Ltd.), "Econol" (Sumitomo Chemical Co., Ltd.), "Zyder" (Nippon Petrochemical Co., Ltd.), "LCP"
(Manufactured by Tosoh Corporation), "Vectra" (manufactured by Hoechst-Celanese), "SRP" (manufactured by ICI), polyamideimide (for example, trimellitic acid and diaminodiphenylmethane, diaminodiphenylether, m- or p-phenylenediamine, etc.) , Thermoplastic polyimide, polyetherimide (for example, trade name "Ultem" (manufactured by General Electric)), polymethylpentene and modified products of these resins, polymer alloys And the like.

The modified product and the polymer alloy include:
For example, PPE / polystyrene, PPE / polyamide,
A mixture of PC / ABS, PC / polyester, nylon / modified polyolefin, nylon / modified ABS, nylon / polyarylate, POM / thermoplastic polyurethane and the like can be exemplified.

Among the above-mentioned thermoplastic resins, polyarylene sulfide, polyphenylene ether, polycarbonate, polyacetal, polyester and thermoplastic polyimide are particularly recommended.

The amount of the resin modifier composition added to the thermoplastic resin composition according to the present invention depends on the amount of the thermoplastic resin 1 as a raw material.
The amount is about 0.1 to 50 parts by weight, preferably about 0.2 to 20 parts by weight, based on 00 parts by weight. If the amount is less than 0.1 part by weight, the desired properties are not improved, and if the amount exceeds 50 parts by weight, the heat resistance required for the resin may be impaired.

The operation of adding the resin modifier composition to the thermoplastic resin may be performed in any step from the production of the raw material resin to the resin molding. For example, it may be mixed with a raw material resin before molding and then subjected to molding, or may be subjected to molding after adding the resin modifier to the molten resin and melt-mixing.

Alternatively, it is also possible to add a reaction raw material monomer of a thermoplastic resin to a reaction vessel and carry out a polymerization reaction to produce a resin containing the resin modifier. In this case, since the viscosity during the resin polymerization reaction can be reduced, effects such as reduction of the polymerization temperature, prevention of coloring of the resin, reduction of the energy cost, reduction of the reaction time, and improvement of the degree of polymerization of the resin are observed. Can be

The thermoplastic resin composition according to the present invention contains a resin modifier as an essential component, and can further contain a polyolefin and / or an ester compound.

Examples of the polyolefin and / or ester compound include at least one selected from polyolefins containing ethylene as a main component and ester compounds composed of higher fatty acids having 12 to 40 carbon atoms and polyhydric alcohols.

The polyolefin containing ethylene as a main component is a polyolefin having an ethylene content of at least 90 mol%, and specific examples include high-density polyethylene and low-density polyethylene.

Examples of the ester compound composed of a higher fatty acid and a polyhydric alcohol include ethylene glycol, diethylene glycol, trimethylolpropane, glycerin, pentaerythritol, dipentaerythritol and a straight-chain or branched-chain having 12 to 40 carbon atoms. Examples include esters with higher fatty acids.

The total amount of the ester compound of the polyolefin and / or higher fatty acid and the polyhydric alcohol may be 0.0 to 100 parts by weight of the thermoplastic resin.
1 to 25 parts by weight is preferable, and particularly 0.05 to 10 parts by weight is recommended as a preferable range.

The addition of the polyolein and / or ester compound is effective in shortening the molding cycle such as improving the releasability of the thermoplastic resin composition from the mold.

The thermoplastic resin composition according to the present invention may contain a nucleating agent, a reinforcing agent, a filler, an antioxidant, an ultraviolet absorber, and the like, as long as the object of the present invention is not impaired, depending on the use and purpose. Various additives such as an antistatic agent, a flame retardant, a lubricant, a release agent, a pigment and a dye can be added.

Examples of the crystal nucleating agent include known inorganic and organic nucleating agents. The amount used is usually 10
About 0.001 to 10 parts by weight is used per 0 parts by weight.

Examples of the inorganic nucleating agent include talc, mica, silica, kaolin, clay, attapullite, 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 fatty salts, aromatic phosphonic acids and metal salts, aromatic metal phosphates, benzenesulfonic acid, and naphthalenesulfonic acid. Crystallinity of aromatic sulfonic acid metal salt, β-diketone metal salt, polymer compound having carboxyl group metal salt, 4,6 nylon, polyester using polyphenylene sulfide ketone or parahydroxybenzoic acid as a monomer Examples thereof include polymer fine powder.

A filler may be added as a reinforcing agent or for increasing the amount. Such a 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. These can be used alone or in combination of two or more. The amount of the filler is not particularly limited, but is usually 10 to 4 per 100 parts by weight of the thermoplastic resin.
00 parts by weight, especially 30 to 300 parts by weight, are used.

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

Examples of the antioxidant include phenolic compounds having a relatively large molecular weight, such as bisphenol A or trade name "Irganox 1010".

Examples of the ultraviolet absorber and light stabilizer include hindered amine compounds, benzophenone compounds, and benzotriazole compounds.

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

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

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

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

The above-mentioned predetermined polybasic acid may have 4 to 4 carbon atoms.
26 aliphatic tribasic acids such as aliphatic dibasic acid, tricarballylic acid, aconitic acid, and methylcyclohexentricarboxylic acid, 1,2,3,4-butanetetracarboxylic acid, cyclopentanetetracarboxylic acid, and methyltetrahydrophthalic acid Tetraphthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, biphenyltetracarboxylic acid, benzophenonetetracarboxylic acid, 3,3 ', 4,4'-diphenyl Aromatic polycarboxylic acids such as sulfonetetracarboxylic acid are exemplified.

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

[0085]

BEST MODE FOR CARRYING OUT THE INVENTION The thermoplastic resin composition according to the present invention is prepared by an ordinary method by a master batch method or a direct one-stage blending method. For example, the thermoplastic resin, the present oligoimides, each required amount of various additive components appropriately used as needed, V-blender, ribbon blender, Henschel mixer, tumbler blender and the like, mixed, Banbury mixer, kneader, Using a kneader such as an oven roll, a single-screw extruder, a twin-screw extruder, or a single-screw reciprocating screw, a temperature exceeding the melting temperature of the resin (preferably, the melting temperature of the resin +
(At a temperature of about 20 to 150 ° C.) to obtain the desired resin composition.

The thermoplastic resin composition thus obtained comprises:
It is useful as a material for various molded products, and is molded by methods such as injection molding, extrusion molding, blow molding, calender molding, and rotational molding according to a method commonly used in this field, and the form of the molded product is a molded product. , Films, sheets, fibers, nonwoven fabrics, etc.

For example, in the case of injection molding, the injection conditions are appropriately selected according to the type of the thermoplastic resin to be used, but usually, the resin temperature is about 200 to 400 ° C., the mold temperature is about 0 to 250 ° C., A condition of a pressure of about 10 to 1300 kg / cm ² is employed.

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

Further, in the case of extrusion molding, the molding conditions can be appropriately selected according to the type of the thermoplastic resin to be used. However, the resin is extruded and cooled from a slit-shaped or nozzle-shaped die at a melting temperature of about 200 to 400 ° C. It can be obtained in the form of an undrawn thread or sheet. Next, the fiber or film can be drawn by heating with a heating roller or a tenter. The preferred temperature during stretching is 50 to 200 ° C.
The preferred stretching ratio is 3 to 7 times.

The molded articles prepared as described above include, for example, electric and electronic parts such as coil bobbins, connectors, relays, switches, capacitor cases, motor parts, distributors, carburetors, intake manifolds, ignition coils, pipes, and the like. Automotive parts, gears, cams, bearings and other mechanical parts, CDs and DVs
Optical disks such as D, FDD chassis, and O
A, home appliances, clothing made of fibers, fabrics, knitting, etc.,
It is suitable for household fabrics such as curtains, adhesive tape reinforcing materials, tent fabrics, base films for magnetic tapes, and fabrics for industrial materials such as domes and fences as building materials.

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

[0092]

The present invention will be described below in detail with reference to examples. The properties of the resin composition were measured by the following methods.

Melt flow rate (MFR) The melt flow rate (MFR) was measured at a predetermined temperature and a predetermined pressure using a Koka type flow tester under the conditions of a die diameter of 1 mm and a length of 10 mm. still,
MFR is an index indicating the fluidity of a resin, and the larger the value, the better the fluidity.

Intrinsic Viscosity The sample after MFR measurement was dissolved in a predetermined solvent at a concentration of 0.5 g / dl, and the intrinsic viscosity [η] was measured at a predetermined temperature. The intrinsic viscosity [η] is an index indicating the molecular weight of the resin. If there is no change in the intrinsic viscosity, it indicates that there is no decrease in the molecular weight of the resin.

Example 1 400 g of N-methyl-2-pyrrolidone (hereinafter abbreviated as NMP) was obtained by mixing 43.6 g (0.2 mol) of pyromellitic anhydride and 27.2 g (0.1 mol) of xylylenediamine.
And mixed in a mixed solvent of 50 g of xylene and heated. While removing generated water, the reaction was continued until the distillate disappeared, and then 53.8 g (0.2 mol) of stearylamine was added dropwise. While separating and removing the generated water, the solvent was also distilled off, and the mixture was heated until the reaction temperature finally reached 260 ° C., and the reaction was continued under reduced pressure of 10 mmHg or less until no distillate disappeared, and oligoimide (oligoimide 1) was obtained. It was created.

As a result of infrared absorption spectrum analysis of “oligoimide 1,” the characteristic absorption (νN-
H) 1560 cm ^-1 was not observed, and the characteristic absorption (νC = 0) due to the imide group was 1775 cm ^-1 , 1703 cm
^-1 was recognized. Also, as a result of measuring the molecular weight distribution by GPC,
Since the weight average molecular weight was 1360, the compound represented by the general formula (5) (R ⁶ = R ⁷ = alkyl group of X 18, X ⁴ = X ⁵ = group- (phenyl)-, Y ² = group -CH _2- (phenylene) )-
It was confirmed to be an oligoimide represented by CH ₂ —, b (average value) = 2).

Example 2 65.4 g (0.3 mol) of pyromellitic anhydride and 2,2
82.0 g (0.2 mol) of -bis [4- (p-aminophenoxy) phenyl) propane was mixed and stirred in a mixed solvent of 400 g of NMP and 50 g of xylene and heated. The reaction was continued until the distillate disappeared while removing generated water, followed by 53.8 g (0.2 mol) of stearylamine.
Was added dropwise. While separating and removing the generated water, the solvent was also distilled off, and the mixture was heated until the reaction temperature finally reached 260 ° C.
The reaction was continued under reduced pressure of not more than mmHg until no distillate was left to produce an oligoimide (oligoimide 2).

As a result of infrared absorption spectrum analysis of "oligoimide 2", the same characteristic absorption as in Example 1 was recognized.
In addition, as a result of measuring the molecular weight distribution by GPC, it was found that the weight average molecular weight was 1900, so that the general formula (5) (R ⁶ = R ⁷
= C18 alkyl group, X ⁴ = X ⁵ = group - (phenyl)
—, Y ² = group — (phenylene) —O— (phenylene) —
C (CH ₃ ) _2- (phenylene) -O- (phenylene)
−, B (average value) = 2).

Example 3 76.2 g (0.3 mol) of pyromellitic acid and 23.2 g (0.2 mol) of 1,6-hexanediamine were mixed and stirred in a mixed solvent of 400 g of ion-exchanged water and 100 g of anisole. Then, the temperature was raised. The reaction was continued while distilling off the distillate out of the system until distillate was no longer present, and then 52.2 g (0.2 mol) of p-dodecylaniline was added dropwise. While separating and removing the generated water, the solvent was also distilled off, and the temperature was finally raised to 260 ° C., and the reaction was continued under reduced pressure of 10 mmHg or less until no distillate was generated, thereby preparing oligoimide 3.

As a result of infrared absorption spectrum analysis of "oligoimide 3", the same characteristic absorption as in Example 1 was recognized.
Further, as a result of measuring the molecular weight distribution by GPC, it was found that the weight average molecular weight was 1300, so that the general formula (1) (R ¹ = R ²
= C12 alkyl group, A ¹ = A ² = phenylene group, X ¹
= X ² = group- (phenyl)-, Y ¹ = alkylene group of C6, and an oligoimide represented by a (average value) = 2.

On the other hand, 52.2 g (0.2 mol) of p-dodecylaniline was dropped into the reaction solution at the time of producing the oligoimide 3, and then tetrakis [methylene-3- (3'-
5'-di-t-butyl-4'-hydroxyphenyl)-
Propionate] methane (trade name “Irganox 10
10 ") 0.1 g was added, and then the solvent was distilled off while separating and removing the produced water. Finally, the temperature was raised to 260 ° C., and the distillate was eliminated under reduced pressure of 10 mmHg or less. By continuing the reaction, a resin modifier composition containing oligoimide 3 containing a hindered phenolic antioxidant and having good hue was obtained.

Example 4 88.2 g of biphenyltetracarboxylic dianhydride (0.
3 mol) and 28.4 g (0.2 mol) of 1,3-bis (aminomethyl) cyclohexane were mixed and stirred in 500 g of anisole, and the temperature was raised. While removing generated water from the system, the reaction was continued until no distillate was generated, and then 37.0 g (0.2 mol) of laurylamine was added dropwise. While removing the generated water, the solvent was also distilled off, and finally 260 ° C.
The reaction was continued under reduced pressure of 10 mmHg or less until the distillate disappeared to prepare an oligoimide (oligoimide 4).

As a result of infrared absorption spectrum analysis of "oligoimide 4", the same characteristic absorption as in Example 1 was recognized.
Also, as a result of measuring the molecular weight by GPC, the weight average molecular weight was 1
400, the general formula (5) (R ⁶ = R ⁷ = C
12 alkyl group, X ⁴ = X ⁵ = group - (phenyl) - (phenyl) -, Y ² = group -CH ₂ - (cyclohexylene) -
It was confirmed to be an oligoimide represented by CH ₂ —, b (average value) = 2).

Example 5 The procedure of Example 4 was repeated, except that 40.0 g (0.2 mol) of 4,4′-oxydianiline was used instead of 1,3-bis (aminomethyl) cyclohexane. An oligoimide (oligoimide 5) was prepared. In addition, as a result of infrared absorption spectrum analysis of "oligoimide 5," the same characteristic absorption as in Example 1 was recognized. As a result of molecular weight measurement by GPC, since a weight average molecular weight 1400, the general formula (5) (the alkyl group of ^{R 6 = R 7 = C12,} X 4 = X 5
= Group - (phenyl) - (phenyl) -, Y ² = group -CH ₂
-(Phenylene))-CH _2- , b (average value) = 2).

Example 6 An oligoimide (oligoimide 6) was prepared in the same manner as in Example 1 except that 64.4 g (0.2 mol) of benzophenonetetracarboxylic dianhydride was used instead of pyromellitic anhydride. . In addition, as a result of infrared absorption spectrum analysis of "oligoimide 6," the same characteristic absorption as in Example 1 was recognized. As a result of molecular weight measurement by GPC, since a weight average molecular weight 1240, the general formula (5) (R ⁶
= Alkyl group ^{R 7 = C18, X 4 =} X 5 = group - (phenyl) -CO- (phenyl) -, Y ² = group -CH ₂ - (phenylene) -CH ₂ -, b (average value) = It was confirmed to be the oligoimide represented by 1).

Example 7 Benzophenone tetracarboxylic dianhydride 64.4 g
(0.2 mol) and 1,12-dodecanediamine 30.1
g (0.15 mole) in 400 g of NMP at 50 ° C.
The mixture was stirred for hours. Next, 50 g of xylene was added, followed by 12.9 g (0.1 mol) of 2-ethylhexylamine.
Was added dropwise, and the temperature was raised. The solvent was also gradually distilled off while removing generated water out of the reaction system, and the temperature was finally raised to 260 ° C. The reaction was continued under reduced pressure of 10 mmHg or less until no distillate was generated, to prepare an oligoimide (oligoimide 7).

As a result of infrared absorption spectrum analysis of "oligoimide 7", the same characteristic absorption as in Example 1 was recognized.
In addition, as a result of the molecular weight measurement by GPC, the weight average molecular weight 2
000, the general formula (5) (R ⁶ = R ⁷ = C
8 branched alkyl groups, X ⁴ = X ⁵ = group- (phenyl) -C
O- (phenyl)-, an alkylene group of Y ² ＣC12, b
(Average value) = 3) It was confirmed that this was an oligoimide.

Example 8 93.0 diphenylethertetracarboxylic dianhydride
g (0.3 mol) and 4,4′-oxodianiline 40.0
g (0.2 mol) with NMP 500 g and xylene 50 g
After stirring and mixing at 50 ° C. for 3 hours in a mixed solvent with 53.8 g, 53.8 g of stearylamine was added dropwise and the temperature was raised. While removing the generated water out of the system, the solvent was also gradually distilled off, and finally 2
The temperature was raised to 60 ° C. The reaction was continued under reduced pressure of 10 mmHg or less until no distillate disappeared to prepare an oligoimide (oligoimide 8).

As a result of infrared absorption spectrum analysis of "oligoimide 8," the same characteristic absorption as in Example 1 was recognized.
Also, as a result of measuring the molecular weight by GPC, the weight average molecular weight was 1
750, the general formula (5) (R ⁶ = R ⁷ = C
18 alkyl group, X ⁴ = X ⁵ = group - (phenyl) -O-
It was confirmed that this was an oligoimide represented by (phenyl)-, Y ² = group- (phenylene) -O- (phenylene), b (average value) = 3.

Example 9 82.0 g of 2,2-bis (4-aminophenoxyphenyl) propane was used instead of 4,4'-oxydianiline
An oligoimide (oligoimide 9) was prepared in the same manner as in Example 8 except that (0.2 mol) was used. In addition, as a result of infrared absorption spectrum analysis of "oligoimide 9," the same characteristic absorption as in Example 1 was recognized. Further, as a result of measuring the molecular weight by GPC, it was found that the weight average molecular weight was 2180, so that the alkyl group represented by the general formula (5) (R ⁶ = R ⁷ = C18,
X ⁴ = X ⁵ = group- (phenyl) -O- (phenyl)-, Y
² = group- (phenylene) -O- (phenylene) -C (C
H _{3) 2} - (phenylene) -O- (phenylene), b (it was confirmed that the oligoimide represented by an average value) = 3).

Example 10 63.5 g (0.25 mol) of pyromellitic anhydride was added to NM
The mixture was stirred and heated in a mixed solvent of 300 g of P and 50 g of xylene. When the temperature reached 80 ° C., 27.0 g (0.1 mol) of stearylamine was added dropwise. After stirring for 2 hours, m-xylylenediamine 27.2 g (0.2
Mol) was added dropwise. After continuing the reaction for another 2 hours, the temperature was raised to evaporate the generated water out of the system, the solvent was also distilled off, and finally the temperature was raised to 260 ° C., and the distillate was removed under reduced pressure of 10 mmHg or less. The reaction was continued until it disappeared, and an oligoimide (oligoimide 10) was prepared.

As a result of infrared absorption spectrum analysis of "oligoimide 10," the same characteristic absorption as in Example 1 was recognized.
In addition, as a result of the molecular weight measurement by GPC, the weight average molecular weight 2
Since it was 150, general formula (5) (R ⁶ = R ⁷ = C
18 alkyl groups, X ⁴ = X ⁵ = group- (phenyl)-, Y
² = group -CH ₂ - (phenylene) -CH ₂ -, b was confirmed that the oligoimide represented by (average) = 4).

Example 11 1,3,3a, 4,5,9b-Hexahydro-5- (tetrahydro-2,5-dioxo-3-fusenyl) naphtho [1,2-C] furan-1,3-dione 60.0g
(0.2 mol) and 13.6 g of m-xylylenediamine
(0.1 mol) was stirred and mixed at 50 ° C. for 3 hours in a mixed solvent of 500 g of NMP and 50 g of xylene, and then 53.8 g (0.2 mol) of stearylamine was added dropwise and the temperature was raised. While removing the generated water out of the system, the solvent was also gradually distilled off, and finally the temperature was raised to 260 ° C. The reaction was continued under reduced pressure of 10 mmHg or less until no distillate disappeared to prepare an oligoimide (oligoimide 11).

As a result of infrared absorption spectrum analysis of "oligoimide 11," the same characteristic absorption as in Example 1 was recognized.
Also, as a result of measuring the molecular weight by GPC, the weight average molecular weight was 9
Since it was 50, general formula (5) (R ⁶ = R ⁷ = C1
An alkyl group of 8, X ⁴ = X ⁵ = R ³ = H in the structural formula (A),
Y ² = oligoimide represented by group —CH ₂ (phenylene) —CH ₂ —, b (average value) = 1).

Example 12 1,3,3a, 4,5,9b-Hexahydro-5- (tetrahydro-2,5-dioxo-3-fusenyl) naphtho [1,2-C] furan-1,3-dione 90.0g
(0.30 mol) and 102.5 g (0.25 mol) of 2,2-bis [4- (p-aminophenoxy) phenyl) in a mixed solvent of 800 g of NMP and 80 g of xylene.
After stirring and mixing at 0 ° C. for 3 hours, stearylamine
9 g (0.1 mol) was added dropwise, and the temperature was raised. While removing the generated water out of the system, the solvent was also gradually distilled off and finally 260
The temperature was raised to ° C. The reaction was continued under reduced pressure of 10 mmHg or less until no distillate disappeared, and oligoimide (oligoimide 1
1) was created.

As a result of infrared absorption spectrum analysis of "oligoimide 11," the same characteristic absorption as in Example 1 was recognized.
Also, as a result of measuring the molecular weight by GPC, the weight average molecular weight was 4
Since R was 100, the general formula (5) (R ⁶ = R ⁷ = C
An alkyl group of 18, X ⁴ = X ⁵ = R ^{3 of the} structural formula (A) =
H, Y ² = group- (phenylene) -O- (phenylene)-
CH (CH _{3) 2} - (phenylene) -O- (phenylene)
−, B (average value) = 5).

Example 13 "Oligoimide 1" was added as a resin modifier composition to 100 parts by weight of a polyethylene terephthalate resin.
After adding 5 parts by weight, the mixture was melt-mixed at 260 ° C. using an extruder, and the obtained strand was cooled with water and cut to obtain a sample. Using this sample, 265 ° C, 10 kgf / cm ² ,
The melt flow rate (MFR) was measured under the conditions of a die diameter of 1 mm and a length of 10 mm. Further, the intrinsic viscosity [η] is
It was measured at 25 ° C. in a phenol / tetrachloroethane = 60/40 (weight ratio) solution. Table 1 shows the obtained results.

Examples 14 to 20 Resin compositions were prepared in the same manner as in Example 13 except that a predetermined amount of "oligoimide" described in Table 1 was used as the resin modifier composition. The MFR and intrinsic viscosity [η] were measured. Table 1 shows the obtained results.

Comparative Example 1 A resin composition was prepared in the same manner as in Example 13 except that "oligoimide 1" was not used, and its MFR and intrinsic viscosity [η] were measured. Table 1 shows the obtained results.

[0120]

[Table 1]

Example 21 "Oligimide 1" was used as a resin modifier composition with respect to 100 parts by weight of a bisphenol A type polycarbonate resin.
M of resin composition prepared by dry blending 3 parts by weight
FR was measured under the conditions of a resin temperature of 280 ° C., a pressure of 40 kgf / cm ² , a die diameter of 1.0 mm and a length of 10 mm. The sample after melt viscosity measurement was dissolved in dichloromethane at a concentration of 0.5 g / dl, and the intrinsic viscosity [η] at 20 ° C. was measured. Table 2 shows the obtained results.

Examples 22 to 27 "Oligoimides" listed in Table 2 were used as resin modifiers.
Was prepared in the same manner as in Example 21 except that a predetermined amount of was used, and the MFR and intrinsic viscosity [η] of the resin composition were measured. The results are shown in Table 2.

Comparative Example 2 A resin composition was prepared in the same manner as in Example 21 except that "oligoimide 1" was not used, and its MFR and intrinsic viscosity [η] were measured. Table 1 shows the obtained results.

[0124]

[Table 2]

Example 28 3,3'-4,4'-Diphenylsulfonetetracarboxylic dianhydride (1.02 mol) and 2,2-bis [4-
(P-aminophenoxy) phenyl) propane (1.0
0 mol) and 170 parts by weight of a thermoplastic polyimide powder obtained by dehydration condensation at 170 ° C., 5 parts by weight of “oligoimide 2” as a resin modifier was added, and the mixture was uniformly mixed with an extruder. The resulting strands were melt-mixed until the temperature became as small as possible, and the obtained strands were cooled with water and cut to obtain samples. The melt viscosity of this sample was measured at a temperature of 360 ° C., a pressure of 100 kgf / cm ² , and a die diameter of 1.
The measurement was performed under the conditions of 0 mm and a length of 10 mm. Further, discoloration and foaming of the obtained strand were visually observed and evaluated in two stages (（: no change, x: change). Table 3 shows the obtained results.

Examples 29 to 32 A resin composition was prepared in the same manner as in Example 28 except that a predetermined amount of "oligoimide" shown in Table 3 was used as a resin modifier, and the melt viscosity of the resin composition was measured. The strand was measured, and the obtained strand was visually evaluated. Table 3 shows the obtained results.

Comparative Example 3 A resin composition was prepared in the same manner as in Example 28 except that "oligoimide 2" was not used, and the melt viscosity was measured and the strand was visually evaluated. The obtained result is the third
It is shown in the table.

[0128]

[Table 3]

Example 33 100 parts by weight of a semi-crosslinked polyphenylene sulfide resin was dry-blended with 3 parts by weight of "oligoimide 3" as a resin modifier, and then melt-kneaded at 300 ° C. using an extruder. The obtained strand was cooled and pelletized.
The MFR of the pellet was adjusted to a temperature of 280 ° C, a pressure of 10 kgf / cm ²
The measurement was performed under the conditions of a die diameter of 1.0 mm and a length of 10 mm. or,
The pellets were injection molded at a cylinder temperature of 300 ° C. and a mold temperature of 70 ° C. to form a sample piece, and the releasability was visually checked.
Visual confirmation was performed on a three-point scale (◎: particularly excellent,
：: excellent, △: not very good). Further, the heat of recrystallization of this sample at the time of temperature rise was measured using DSC.
Table 4 shows the obtained results. The value of the heat of recrystallization is an index of the degree of crystallinity of the molded article, and the smaller the value, the higher the crystallization promoting effect.

Examples 34 to 37 A resin composition was prepared in the same manner as in Example 33, except that a predetermined amount of "oligoimide" shown in Table 3 was used as a resin modifier. Was visually confirmed. Furthermore,
The MFR of the resin composition was measured, and the D
SC measurements were made. Table 4 shows the obtained results.

Example 38 With the exception that 2.5 parts by weight of "oligoimide 3" and 2.5 parts by weight of ethylene glycol dimontanate were dry-blended as resin modifiers with respect to 100 parts by weight of a semi-crosslinked polyphenylene sulfide resin. A resin composition was prepared in the same manner as in Example 33, and the releasability of the resin composition was visually confirmed. Further, the MFR of the resin composition was measured, and the DSC measurement of the injection-molded test piece was performed. Table 4 shows the obtained results.

Comparative Example 4 The mold release property and MFR of the semi-crosslinked polyphenylene sulfide resin used in Example 33 without using “oligoimide 3”
And DSC measurement were performed in the same manner as in Example 33. Table 4 shows the obtained results.

[0133]

[Table 4]

[0134]

The oligoimide of the present invention can be advantageously molded, and can be obtained with excellent properties, when it is mixed with any of thermoplastic resins as a resin modifier. In particular, according to the thermoplastic resin molding method of the present invention, there are advantages that a molded article can be thinned, precision molded, and the like, and a molding cycle can be shortened.

Claims (10)

[Claims] 1. One or more oligoimides represented by the general formula (1). Embedded image [Wherein, R ¹ and R ² are the same or different and each represents an aliphatic 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 a group -Ph-, a group -naphthalene-, a group -Ph-Z ¹ -Ph-, or a residue from a carboxylic acid of the structural formula (A). Z ¹ is a direct bond, a group —O—, a group —CO—, a group —CH ₂ —, a group —CH (CH ₃ ) ₂ —, a group —
Represents S-. 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 Represents a group -B ¹ -Z ² -B ^2- . B ¹ and B ² are the same or different, and a phenylene group optionally substituted with an alkyl group, a group-(phenylene) -Z
Represents a ^3- (phenylene)-or cyclohexylene group.
Z ² and Z ³ are the same or different and each is a direct bond, a group —S—, a group —SO ₂ —, a group —O—, a group —CH ₂ —, a group —CO—, or a methylene substituted with an alkyl group or an aryl group. Represents a group. a represents an integer of 1 to 10. Incidentally, a number of X ¹ and Y ¹
May be the same or different. ] [Wherein, R ³ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. ] 2. The oligoimide according to claim 1, wherein the oligoimide is prepared by dehydrating the following three compounds (A) to (C). (A) One or more kinds of tetracarboxylic acids represented by the general formula (2) or anhydrides thereof. Embedded image [Wherein X ³ represents a group -Ph-, a group -naphthalene-, a group -P
h-Z ⁴ -Ph- or structural formula represents the residue of a carboxylic acid (i). Z ⁴ is a direct bond, a group —O—, a group —C
O-, group -CH ₂ -, group -CH (CH _{3) 2} -, the group -S-
Represents (B) One or more monoamines represented by the general formula (3). R ⁴ —A ³ —NH ₂ (3) wherein R ⁴ represents an alkyl group having 1 to 30 carbon atoms. A ³
Represents a direct bond or a phenylene group. (C) One or more diamines represented by the general formula (4). H ₂ N—R ⁵ —NH ₂ (4) wherein R ⁵ is an alkylene group having 2 to 15 carbon atoms, a phenylene group, a group —CH ₂ — (phenylene) —CH ₂ —, a group —C
H ₂ - (cyclohexylene) -CH ₂ - or a group -B ³ -Z ⁵
-B ⁴ - represents a. B ³ and B ⁴ are the same or different and each represents a phenylene group, a group-(phenylene) -Z ^6- (phenylene)-or a cyclohexylene group which may be substituted with an alkyl group. Z ⁵ and Z ⁶ may be the same or different, and may be a direct bond;
S-, group -SO ₂ -, group -O-, group -CH ₂ -, group -CO
— Or a methylene group substituted by an alkyl group or an aryl group. ] 3. The tetracarboxylic acid represented by the general formula (2) is pyromellitic acid, biphenyltetracarboxylic acid,
Benzophenone tetracarboxylic acid, diphenyl ether tetracarboxylic acid, 1,3,3a, 4,5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3
The oligoimide according to claim 2, wherein the oligoimide is one or two or more tetracarboxylic acids selected from the group consisting of -furanyl) naphtho [1,2-C] furan-1,3-dione. 4. A diamine represented by the general formula (4):
1,4-butanediamine, 1,6-hexanediamine,
One or more diamines selected from the group consisting of xylylenediamine, 1,3-bis (aminomethyl) cyclohexane, 2,2, -bis [4- (p-aminophenoxy) phenyl] propane, and phenylenediamine 4. The oligoimide according to claim 2 or claim 3. 5. A resin modifier composition comprising the oligoimide according to any one of claims 1 to 4. 6. The resin modifier composition comprising an oligoimide 10
The resin modifier composition according to claim 5, wherein 0.001 to 200 parts by weight of at least one kind of a hindered phenolic antioxidant is added to 0 parts by weight. 7. A thermoplastic resin composition comprising a thermoplastic resin and the resin modifier composition according to any one of claims 5 to 6. 8. A thermoplastic resin composition comprising at least one selected from a resin modifier composition, a polyolefin containing ethylene as a main component and / or an ester compound comprising a higher fatty acid and a polyhydric alcohol. The thermoplastic resin composition according to claim 7, comprising an additive and a thermoplastic resin. 9. The method according to claim 7, wherein the amount of the resin modifier composition is 0.1 to 50 parts by weight based on 100 parts by weight of the thermoplastic resin. Thermoplastic resin composition. 10. A thermoplastic resin comprising: polyarylene sulfide, polyphenylene ether, polycarbonate,
The thermoplastic resin composition according to any one of claims 7 to 9, wherein the thermoplastic resin composition is one or more thermoplastic resins selected from the group consisting of polyacetal, polyester, nylon, and thermoplastic polyimide.