Thermoplastic resin composition and a method of molding the same

This invention provides a thermoplastic resin composition comprising a thermoplastic resin and 0.1 to 100 parts by weight, per 100 parts by weight of the thermoplastic resin, of an imide compound prepared, e.g., by dehydration condensation of 1,2,3,4-butanetetracarboxylic acid or a monoanhydride or a dianhydride thereof with a primary amine, and a method of molding the resin composition.

TECHNICAL FIELD 
The present invention relates to a thermoplastic resin composition and a 
method of molding the composition. 
TECHNICAL BACKGROUND 
Recently heat-resistant thermoplastic resins have been used as engineering 
plastics for machine materials or electronic parts. In molding a 
thermoplastic resin, in order to improve productivity, it has been 
proposed to blend, for the purpose of reducing melt viscosity, promoting 
crystallization and improving mold releasability, various resin modifiers, 
e.g., fatty acids such as stearic acid, metal salts of fatty acids, ester 
derivatives prepared from a fatty acid with a polyhydric alcohol such as 
pentaerythritol, polyethylene glycol or the like, aliphatic amides such as 
ethylenebisstearamide, etc. (Japanese Unexamined Patent Publications 
(Kokai) No. 44547/1985 and No. 250049/1991). 
However, since heat-resistant thermoplastic resins generally have a high 
fusing temperature, said resin additives may thermally decompose or boil 
when melted, thereby tending to stain a mold or form void in the resin. 
For this reason, it has been desired to develop heat-resistant resin 
modifiers. 
In view of the recent increasing need for plastic materials of high 
performance, polyarylene sulfide (PAS) excellent in heat resistance, 
mechanical characteristics and chemical resistance is attracting 
attention, and is now used for extending applications, for example, as 
automotive parts, parts for precision machines, electric and electronic 
parts, etc. 
PAS is a crystalline engineering plastic but has low crystallization rate. 
Therefore, in order to obtain a resin of sufficient mechanical strength by 
injection molding, a high mold temperature of about 130.degree. C. and a 
prolonged cooling time were necessary. This defect posed a serious problem 
in extending the applications of PAS, and it is desired to mold PAS in a 
short time at a mold temperature of not higher than 100.degree. C. which 
is among the molding conditions for resin-molding apparatus commonly used. 
To solve this problem, there have been proposed a method of increasing the 
mold releasability by adding a fatty acid ester (Japanese Unexamined 
Patent Publication No.154867/1992), an aromatic sulfonamide (Japanese 
Unexamined Patent Publication No.59279/1993) or the like, and a method of 
promoting the crystallization by adding a modified polyalkylene glycol 
(Japanese Unexamined Patent Publication No.250049/1991) or an organic 
phosphoric acid metal salt (Japanese Unexamined Patent Publication 
No.142854/1990) or the like. 
However, because of insufficient heat resistance of the resulting resin 
compositions, these methods entail the problem of failing to achieve the 
contemplated results and the problem of exhibiting reduced mechanical 
strength and heat resistance even if the mold releasability or appearance 
of the molded products may be improved. 
DISCLOSURE OF THE INVENTION 
An object of the present invention is to provide a novel and useful 
thermoplastic resin composition containing a resin modifier which is 
excellent in heat resistance. 
Another object of the invention is to provide a novel and useful method of 
molding a thermoplastic resin composition, which method is feasible even 
at a low temperature without deteriorating the inherent mechanical 
characteristics and heat resistance of the thermoplastic resin, 
particularly polyarylene sulfide. 
The inventors of the present invention conducted extensive research to 
solve the foregoing problems, and found that an imide compound having a 
specific structure can function as a resin modifier having the desired 
performance since the imide compound per se has high heat resistance and 
reduces the melt viscosity of thermoplastic resins, increases the 
crystallizability of crystalline thermoplastic resins or enhances the mold 
releasability, etc. The present invention has been accomplished based on 
these novel findings. 
The present inventors further found that when a thermoplastic resin 
composition, particularly a polyarylene sulfide resin composition, 
containing the above specific imide compound is used, a molded article 
which retains the inherent mechanical strength and heat resistance of the 
thermoplastic resins, especially of the polyarylene sulfide, can be 
obtained even at a mold temperature of 100.degree. C. or lower. 
Thus, the thermoplastic resin composition according to the present 
invention is characterized in that the composition comprises a 
thermoplastic resin and 0.1 to 100 parts by weight, per 100 parts by 
weight of said thermoplastic resin, of an imide compound, said imide 
compound being at least one member selected from the group consisting of: 
(1) a bisimide represented by the formula 
##STR1## 
wherein R.sup.1 and R.sup.2 are the same or different and each represents 
an alkyl or alkenyl group having 4 to 22 carbon atoms, a cycloalkyl group 
having 4 to 6 carbon atoms a group represented by the formula 
##STR2## 
or a group represented by the formula 
##STR3## 
in which R.sup.3 and R.sup.5 are the same or different and each represents 
an alkyl group having 1 to 22 carbon atoms, R.sup.4 and R.sup.6 are the 
same or different and each represents a single bond or an alkylene group 
having 1 to 2 carbon atoms, a is an integer of 1 to 2 and b is an integer 
of 0 to 2, and A.sup.1 and A.sup.2 are the same or different and each 
represents a single bond or a phenylene group; 
(2) a monoimide represented by the formula 
##STR4## 
wherein X and Y are the same or different and each represents a group of 
the formula --NH--A.sup.4 --R.sup.8 or a hydroxyl group, R.sup.7 and 
R.sup.8 have the same meaning as R.sup.1 in the formula (1) and may be the 
same or different, and A.sup.3 and A.sup.4 are the same or different and 
each represents a single bond or a phenylene group, and a metal salt 
thereof; and 
(3) a monoimide represented by the formula 
##STR5## 
wherein R.sup.9 and R.sup.10 are the same or different and each represents 
an alkyl or alkenyl group having 4 to 22 carbon atoms, and A.sup.5 and 
A.sup.6 are the same or different and each represents a single bond or a 
phenylene group, and a metal salt thereof. 
The present invention also provides a method of molding a thermoplastic 
resin composition, particularly a polyarylene sulfide resin composition, 
the method being characterized in that the method comprises 
injection-molding or blow-molding a resin composition comprising a 
thermoplastic resin, particularly a polyarylene sulfide resin, and 0.1 to 
100 parts by weight, per 100 parts by weight of said thermoplastic resin, 
of at least one imide compound selected from the group consisting of a 
bisimide of the formula (1), a monoimide of the formula (2) and a metal 
salt thereof and a monoimide of the formula (3) and a metal salt thereof. 
The imide compounds of the formulas (1), (2) and (3) for use in the 
invention can be easily prepared, for example, by dehydration condensation 
of 1,2,3,4-butanetetracarboxylic acid (hereinafter referred to as "BTC") 
or a monoanhydride or dianhydride thereof (BTC and a monoanhydride or 
dianhydride thereof will be hereinafter collectively referred to as "BTC 
compound") with an aliphatic primary amine, an alicyclic primary amine or 
an aromatic primary amine represented by the formula H.sub.2 N--A.sup.1 
--R.sup.1, H.sub.2 N--A.sup.2 --R.sup.2, H.sub.2 N--A.sup.3 --R.sup.7, 
H.sub.2 N--A.sup.4 --R.sup.8, H.sub.2 N--A.sup.5 --R.sup.9 or H.sub.2 
N--A.sup.6 --R.sup.10, or alternatively by decarboxylation reaction of 
said BTC compound with an isocyanate derivative corresponding to said 
amine (stated more specifically, a compound of the formula O=C=N--A.sup.1 
--R.sup.1, O=C=N--A.sup.2 --R.sup.2, O=C=N--A.sup.3 --R.sup.7, 
O=C=N--A.sup.4 --R.sup.8 , O=C=N--A.sup.5 --R.sup.9 or O=C=N-A.sup.6 
--R10). From a commercial viewpoint, the dehydration condensation method, 
particularly dehydration condensation with heating, is desirable. 
The aliphatic primary amine, alicyclic primary amine or aromatic primary 
amine is used in an amount of about 2 to about 6 moles per mole of the BTC 
compound for the preparation of the bisimide of the formula (1), and in an 
amount of about 1 to about 3 moles per mole of the BTC compound for the 
preparation of the monoimide of the formula (2) or formula (3). 
When it is desired to prepare an imide compound wherein groups --A.sup.1 
--R.sup.1 and --A.sup.2 --R.sup.2, or the groups --A.sup.3 --R.sup.7 and 
--A.sup.4 --R.sup.8, or the groups --A.sup.5 --R.sup.9 and --A.sup.6 
--R.sup.10 are different from each other, a mixture of primary amines 
having the respective groups is used in a molar ratio corresponding to the 
number of groups in the desired imide compound. 
In the first half of the dehydration reaction, the neutralization reaction 
and the amidation reaction between the BTC compound and the primary amine 
mainly occur, and in the second half thereof, the dehydration from the 
amic acid formed from the BTC compound and the primary amine mainly takes 
place. 
The dehydration reaction may be effected in the absence of a solvent or in 
the presence of a solvent capable of dissolving the BTC compound. Examples 
of useful solvents are dimethylformamide, dimethylacetamide, 
N-methylpyrrolidone, dimethylsulfoxide, dioxane, etc. and polar organic 
solvents such as lower alcohols having 1 to 4 carbon atoms, etc. 
Also effective is a method which comprises reacting the BTC compound with 
the primary amine while dispersing them with stirring in the presence of a 
dispersing solvent. Examples of the dispersing solvents include aromatic 
hydrocarbons such as benzene, toluene, xylene, cumene, tetralin, etc., and 
aliphatic hydrocarbons such as pentane, hexane, heptane, nonane, decane, 
etc. From a commercial viewpoint, the reaction in the absence of a solvent 
is the most desirable, and also effective is the use of a small amount of 
said dispersing solvent as an entrainer. 
Preferably the dehydration reaction is carried out at a temperature of 
0.degree. to about 400.degree. C. In the first half of the reaction, any 
temperature in said range is employable, but in the second half thereof, a 
temperature of 150.degree. to 400.degree. C., preferably 200.degree. to 
300.degree. C., is recommendable. At lower than 150.degree. C., the 
dehydration reaction slowly proceeds and consequently it is improper as a 
commercial method. On the other hand, at a temperature higher than 
400.degree. C., a thermal decomposition reaction tends to occur and thus 
it is undesirable. 
The reaction time is variable depending on the reaction temperature and 
cannot be specified, but is usually in the range of 1 to 50 hours. 
The dehydration reaction may be conducted at atmospheric pressure or 
reduced pressure. It is preferred to carry out the first half of the 
reaction at atmospheric pressure and the second half thereof at reduced 
pressure. The pressure can be reduced to any level in the range of 0.01 to 
760 Torr. A lower pressure of, e.g., 50 Torr or less is desirable in the 
last stage of the reaction. 
The reaction proceeds even in the absence of a catalyst, but if desired, 
catalyst may be used such as hydroxides, oxides, chlorides and organic 
acid salts of sodium, potassium, magnesium, calcium, barium, zinc, 
aluminum, tin, lead and the like. Generally, reaction in the absence of 
such catalyst is preferable, but it is desirable to use the catalyst when 
the reaction is intended to produce a metal salt of the imide represented 
by the formula (2) or (3). 
The same reaction conditions as above can be employed when an isocyanate 
derivative of the primary amine is used as the starting material in place 
of the primary amine. 
The dehydration reaction may be conducted in the presence of a dehydrating 
agent such as acetic anhydride-pyridine, carbodiimide, triphenylphosphite, 
etc. In this case, the dehydrating agent is preferably used in the second 
half of the reaction. A preferred amount of the dehydrating agent to be 
used is 2 to 50 moles per mole of the BTC compound. A desirable reaction 
temperature is in the range of -20.degree. to 200.degree. C. At lower than 
-20.degree. C., the reaction retards. A dehydrating agent requiring a 
temperature of higher than 200.degree. C. gives only a little advantage of 
using such dehydrating agent and in such case the thermal dehydration 
reaction is preferably selected. 
Aliphatic primary amines useful in said reaction include, for example, 
saturated or unsaturated, linear-chain or branched-chain aliphatic amines, 
which may have an aromatic ring. Preferred examples of aliphatic primary 
amines are 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 
them, recommendable to use are decylamine, dodecylamine, tetradecylamine, 
hexadecylamine, octadecylamine, etc. It is economically significant to use 
mixtures containing these amines substantially, namely natural 
material-derived amines, such as coconut oil amine, beef tallow amine, 
fish oil amine, hydrogenated coconut oil amine, hydrogenated beef tallow 
amine, hydrogenated fish oil amine, etc. 
Preferred examples of alicyclic primary amines which are used in said 
reaction are cyclobutylamine, cyclopentylamine, cyclohexylamine, 
cyclohexylmethylamine, cyclohexylethylamine, methylcyclohexylamine, 
dimethylcyclohexylamine, etc. 
Preferred examples of aromatic primary amines which are used in said 
reaction are butylaniline, allylaniline, pentylaniline, hexylaniline, 
heptylaniline, octylaniline, nonylaniline, decylaniline, undecylaniline, 
dodecylaniline, tridecylaniline, tetradecylaniline, pentadecylaniline, 
hexadecylaniline, heptadecylaniline, octadecylaniline, octadecenylaniline, 
nonadecylaniline, eicosylaniline, heneicosylaniline, docosylaniline, etc. 
Among them, more recommendable to use are decylaniline, dodecylaniline, 
tetradecylaniline, hexadecylaniline, octadecylaniline, etc. 
The imide compounds can also be prepared by forming an intermediate partial 
or complete ester (tetraester) from the BTC compound and a lower alcohol 
of 1 to 4 carbon atoms (methyl alcohol, butyl alcohol, etc.), and then 
causing the amine to act on the ester. For example, to an ester formed by 
dissolving the BTC compound in a lower alcohol and if desired heating the 
solution for dehydration is added an primary amine, and then the mixture 
is subjected to a reaction for removing the alcohol at a temperature of 
100.degree. to 400.degree. C., preferably 200.degree. to 300.degree. C., 
whereby the desired imide compound is produced. In this case, although the 
reaction is feasible at any of atmospheric pressure, reduced pressure and 
increased pressure, it is desirable to conduct the reaction at increased 
pressure (0 to 10 kg/cm.sup.2 G) when the primary amine has 4 to 8 carbon 
atoms and at reduced pressure when the primary amine has 16 or more carbon 
atoms. 
The imide compound prepared by the foregoing method via said ester contains 
little or no unreacted acid component, and finds applications wherein the 
inclusion of acid component should be avoided to prevent the decrease of 
polymerization degree. For example, the compound is useful as a resin 
modifier for polyethyleneterephthalate (PET), polyoxymethylene (POM), 
polycarbonate (PC) and the like. 
The desired imide compound can also be prepared by causing the amine to act 
on the BTC compound substantially dehydrated, e.g. by converting the BTC 
compound into an acid chloride by means of a chlorinating reagent such as 
thionyl chloride, phosgene, chlorine, phosphorus trichloride, phosphorus 
pentachloride, etc. The chlorinating reagent is effectively used in the 
second half of the reaction. When the reaction is conducted at a 
temperature of -20.degree. to 200.degree. C. in the presence of 2 to 20 
moles of the chlorinating reagent per mole of the BTC compound in the 
second half of the reaction, the reaction is usually completed in about 1 
to about 10 hours. 
When the imide compound having a carboxyl group, i.e., the compound of the 
formula (2) or formula (3), is used among the above imide compounds, the 
resulting resin composition is imparted a higher affinity for a mold and 
an improved external lubricity. Stated more specifically, the amic acid 
derived from the BTC compound and the aliphatic amine is effective. For 
this purpose, the dehydration reaction of the BTC compound with the 
aliphatic amine may be controlled to leave some of carboxyl groups, when 
so required. In this case, the resulting imide compounds are usually 
obtained in the form of a mixture of the compound of the formula (2) and 
the compound of the formula (3). 
The imide compound retaining the remaining carboxyl may be provided as 
such, or alternatively the imide compound may be provided in the form of a 
metallic soap such as soaps of sodium, potassium, magnesium, calcium, 
barium, zinc, aluminum, tin, lead or the like. 
As a method of preparing such metallic soap, a method comprising melting 
the imide compound containing the remaining free carboxyl group or groups, 
adding to the melt a hydroxide or oxide of said metal or a solution of the 
hydroxide or oxide in water, methanol, ethanol or the like, and stirring 
the mixture is simple and therefore preferable. When the imide compound is 
present as dissolved in the reaction solvent of the foregoing reaction, 
the metallic soap can be produced in a similar manner. The stirring is 
effected at 50.degree. to 130.degree. C. and, 2 to 4 hours later, the 
solvent is removed by topping, whereby the desired metallic soap is 
obtained. The amount of the hydroxide or oxide used is preferably 0.5 to 3 
moles, more preferably 1 to 2 moles, per mole of the remaining carboxyl 
groups. Optionally, when the reaction is performed after adding said 
hydroxide or oxide, the imide compound is obtained in the form of a 
metallic soap on termination of the reaction. 
As is the case with the compound of the formula (2), the carboxyl group may 
be amidated with said amine to convert it into a substituted carbamoyl 
group. In this case, it is recommendable to add 1 to 10 moles of a primary 
amine per mole of the remaining carboxyl group, followed by continuing the 
dehydration reaction at 150.degree. to 300.degree. C. Usually a compound 
of the formula (2) having a substituted carbamoyl group is produced by the 
reaction for 10 minutes to 1 hour, and this compound can be used in the 
invention. 
The imide compounds of the formula (1), (2) and (3) obtained by said 
techniques without a solvent can be withdrawn as such from a reaction 
vessel or those obtained by said techniques using a solvent, a dispersing 
medium or an entrainer can be withdrawn from a reaction vessel after 
removing the solvent, the dispersing medium or the entrainer, for example, 
by topping. 
The obtained imide compounds of the formulas (1), (2) and (3) are solid in 
many cases, and is pulverized and can be added as such to the 
thermoplastic resin. 
If a purified imide compound is required, purification can be performed by 
filtering off metal salts or like insolubles using a solvent, or by 
adsorption treatment with clay or by recrystallization, using solvents, 
e.g., aromatic nonpolar solvents such as benzene, toluene, xylene, etc., 
aliphatic polar solvents such as acetone, methyl ethyl ketone, methyl 
isobutyl ketone, dioxane, diglime, acetonitrile, alcohols of 1 to 4 carbon 
atoms, etc. and chlorine-containing solvents such as chloroform, 
monochlorobenzene, etc. 
The chain length of alkyl or alkenyl groups represented by R.sup.1, 
R.sup.2, R.sup.7, R.sup.8, R.sup.9 or R.sup.10- or alkyl groups 
represented by R.sup.3 or R.sup.5 is suitably selected according to the 
kind of the thermoplastic resin used and the contemplated effect of the 
composition. Generally, the imide compound having an alkyl group or 
alkenyl group with a chain length of 4 to 18 carbon atoms is useful, in 
most cases, for reducing the melt viscosity or for promoting the 
crystallization. The imide compound having an alkyl group or alkenyl group 
with a chain length of 18 to 22 carbon atoms functions, in most cases, as 
an external lubricant. 
The imide compounds of the present invention is usable singly or at least 
two of them can be used in mixture according to the desired properties. It 
is a matter of course that the imide compounds having the groups --A.sup.1 
--R.sup.1 and --A.sup.2 --R.sup.2, the groups --A.sup.3 --R.sup.7 and 
--A.sup.4 --R.sup.8, or the groups --A.sup.5 --R.sup.9 and --A.sup.6 
--R.sup.10 wherein the groups of each combination differ from each other 
can be used alone or at least two species thereof may be used in 
combination. 
Among the foregoing imide compounds, the bisimides of the formula (1) are 
especially preferred. Of the bisimides of the formula (1), preferred are 
the compounds wherein R.sup.1 and R.sup.2 are the same or different and 
each represents an alkyl group having 4 to 22 carbon atoms, an alkenyl 
group having 4 to 22 carbon atoms, or a group of the formula 
##STR6## 
(wherein R.sup.5 is an alkyl group having 4 to 22 carbon atoms), and 
A.sup.1 and A.sup.2 each represents a single bond or a phenylene group. 
Further, among the bisimides of the formula (1), the compounds represented 
by the formula (A) 
##STR7## 
wherein R.sup.11 and R.sup.12 are the same or different and each 
represents a hydrogen atom or an alkyl group having 1 to 22 carbon atoms 
are novel compounds undisclosed in literature, and possess the advantages 
of having a high thermal decomposition temperature and being excellent in 
heat resistance and in compatibility with a resin depending on the kind of 
the resin. 
The imide compounds of the formulas (1), (2) and (3) are useful as 
modifiers for thermoplastic resins which are required to have heat 
resistance. Such thermoplastic resins include, for example, polyarylene 
sulfides (PAS) such as polyphenylene sulfide (PPS), polysulfone, 
polyphenylene ether (PPE), polyether sulfone (PES), polyether ether ketone 
(PEEK), polyphenylene oxide (PPO), ABS modified with phenylmaleimide, 
.alpha.-methylstyrene and/or maleic anhydride, chlorinated polyvinyl 
chloride, aromatic polyamides prepared from terephthalic acid and an 
aliphatic diamine or from xylylenediamine and an aliphatic dicarboxylic 
acid, aliphatic polyamides such as 6 nylon, 6,6 nylon, 4,6 nylon, 11 
nylon, 12 nylon, etc., polycarbonate (PC), polyacetal, polyethylene 
terephthalate (PET), polybutylene terephthalate, polyoxymethylene (POM), 
polyethylene naphthalene dicarboxylate (PEN), 
poly-1,4-cyclohexanedimethylene terephthalate, polyarylate (e.g. 
polyarylate prepared from bisphenol A and aromatic dicarboxylic acid 
comprising terephthalic acid and/or isophthalic acid, such as products 
commercially available under trademarks "U-Polymer" (product of Unitika 
Ltd.), "Arylon" (product of Du Pont), "NAP" (product of Kanegafuchi 
Chemical Industry Co., Ltd.)), liquid crystal polymers (e.g. liquid 
crystal polymers prepared from p-hydroxybenzoic acid, bisphenol and 
4,4'-diphenyldicarboxylic acid as typical monomers, e.g. products 
commercially available under "Rodrun" (product of Unitika Ltd.), "EPE" 
(product of Mitsubishi Petrochemical Co., Ltd.), "Idemitsu LCP" (product 
of Idemitsu Petrochemical Co., Ltd.), "Ekonol" (product of Sumitomo 
Chemical Co., Ltd.), "Xydar" (product of Nippon Petrochemicals Co., Ltd.), 
"LCP" (product of Tosoh Corporation.), "Vectra" (product of Hoechst 
Celanease Co., Ltd.), "SRP" (product of ICI)), polyamide-imide (e.g. 
polyamide-imide prepared from trimellitic acid and diaminodiphenylmethane, 
diaminodiphenyl ether, m- or p-phenylenediamine or like aromatic diamines, 
etc.), polyimide, polyetherimide (e.g. products commercially available 
under a trade name "ULTEM" (product of General Electric Co.)), 
polymethylpentene, modified products of these resins, polymer alloys, etc. 
The foregoing imide compounds may be added to general-purpose resins other 
than said resins (such as polyvinyl chloride, polyethylene, polypropylene, 
ABS, etc.). 
The foregoing modified resins and polymer alloys include, for example, 
mixtures of PPE/polystyrene, PPE/polyamide, PC/ABS, PC/polyester, 
nylon/modified polyolefin, nylon/modified ABS, nylon/polyarylate, and 
POM/thermoplastic polyurethane. 
Useful polyimides include, for example, those comprising the repeating 
units of the structure represented by the formula (I) given below. Such 
polyimides can be prepared in the conventional manner by reacting a 
tetracarboxylic acid, an anhydride thereof or an ester thereof (especially 
C.sub.1 -C.sub.4 alkyl ester) with a diamine or a diisocyanate. 
##STR8## 
In the formula, R.sup.a is a tetravalent organic group, especially a group 
formed by removing 4 carboxyl groups from a tetracarboxylic acid and 
R.sup.b is a divalent organic group, especially a group formed by removing 
2 amino groups from a diamine. 
Examples of the tetracarboxylic acid are pyromellitic acid, 3,3', 
4,4'-diphenylsulfonetetracarboxylic acid, 3,3', 
4,4'-biphenyltetracarboxylic acid, bis(3,4-dicarboxyphenyl)ether, 3,3', 
4,4'-benzophenonetetracarboxylic acid, 
2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane and the like. The anhydride 
thereof includes monoanhydrides or dianhydrides of said tetracarboxylic 
acids. The ester thereof includes diesters or tetraesters of said 
tetracarboxylic acids. 
Examples of the diamine are aromatic diamines, and the specific examples 
are: 
4,4'-diaminodiphenyl sulfide, 
2,2-bis 4-(p-aminophenoxy)phenyl!propane, 
2,2-bis 3-(p-aminophenoxy)phenyl!propane, 
2,2-bis 4-(p-aminophenylthioether)phenyl!propane, 
2,2-bis 3-(p-aminophenylthioether)phenyl!propane, 
4,4'-bis(p-aminophenoxy)diphenyl sulfone, 
3,3'-bis(p-aminophenoxy)diphenyl sulfone, 
4,4'-bis(p-aminophenoxy)diphenyl ether, 
3,3'-bis(p-aminophenoxy)diphenyl ether, 
4,4'-bis(p-aminophenoxy)diphenyl sulfide, 
3,3'-bis(p-aminophenoxy)diphenyl sulfide, 
4,4'-bis(p-aminophenylthioether)diphenyl sulfone, 
3,3'-bis(p-aminophenylthioether)diphenyl sulfone, 
4,4'-bis(p-aminophenylthioether)diphenyl ether, 
3,3'-bis(p-aminophenylthioether)diphenyl ether, 
4,4'-bis(p-aminophenylthioether)diphenyl sulfide, 
3,3'-bis(p-aminophenylthioether)diphenyl sulfide, 
4,4'-bis(p-aminophenoxy)diphenyl, 
3,3'-bis(p-aminophenoxy)diphenyl, 
4,4'-bis(p-aminophenoxy)benzophenone, 
3,3'-bis(p-aminophenoxy)benzophenone, 
4,4'-bis(p-aminophenylthioether)diphenyl, 
3,3'-bis(p-aminophenylthioether)diphenyl, 
4,4'-bis(p-aminophenylthioether)benzophenone, 
3,3'-bis(p-aminophenylthioether)benzophenone, 
1,4-bis(p-aminophenylthioether)benzene, 
1,3-bis(p-aminophenylthioether)benzene, 
4,4'-(p-phenylenediisopropylidene)dianiline, 
4,4'-(m-phenylenediisopropylidene)dianiline, 
2,2-bis 4-(p-aminophenoxy)phenyl!hexafluoropropane, 
4,4'-diaminodiphenyl ether, 
3,4'-diaminodiphenyl ether, 
3,3'-diaminodiphenyl ether, 
4,4'-diaminodiphenyl sulfone, 
3,4'-diaminodiphenyl sulfone, 
3,3'-diaminodiphenyl sulfone, 
4,4'-diaminobenzophenone, 
3,3'-diaminobenzophenone, 
m-phenylenediamine, 
p-phenylenediamine, 
3,3'-bis(3-aminophenoxy)biphenyl, 
4,4'-bis(3-aminophenoxy)biphenyl, 
9,10-bis(4-aminophenyl)anthracene, 
9,9-bis(4-aminophenyl)fluorene, etc. 
Examples of the isocyanates are diisocyanates having a structure such that 
the amino groups of said diamines are replaced by isocyanate groups. 
The tetracarboxylic acids, anhydrides thereof or esters thereof and the 
diamines or diisocyanates can be used singly or in combination to the 
extent that the polyimide obtained has thermoplastic properties. 
The melt viscosity of the thermoplastic resin to be used in the present 
invention is not specifically limited as far as the resin can be injection 
molded or blow molded. Generally, the melt viscosity is 10-100000 poise, 
preferably about 100-50000 poise, when determined with use of a Koka-type 
flow tester (300.degree. C.; rate of shear: 10.sup.3 /sec.). 
The imide compound is used in an amount of about 0.1-100 parts by weight, 
preferably about 0.5-50 parts by weight, per 100 parts by weight of the 
thermoplastic resin. When used as viscosity-reducing agent or 
crystallization accelerator, the imide compound is preferably added in an 
amount of 1-20 parts by weight per 100 parts by weight of the 
thermoplastic resin. The use of less than 0.1 part by weight of the imide 
compound achieves little improvement in the desired properties, whereas 
the use of more than 100 parts by weight of the imide compound is likely 
to impair the heat resistance necessary to the resin. 
If desired, within the range not contrary to the object of this invention, 
the thermoplastic resin composition of the present invention may contain, 
according to the intended use and purpose, a variety of additives such as 
a crystal nucleating agent, a reinforcing agent, a filler, an antioxidant, 
an ultraviolet ray absorbent, an antistatic agent, a flame retarder, etc. 
When a crystal nucleating agent is used, crystallization is accelerated and 
this brings about better results in many cases. The amount of the crystal 
nucleating agent is not specifically limited. Generally, however, it is 
preferably used in an amount of about 0.001-10 parts by weight relative to 
100 parts by weight of the thermoplastic resin. The crystal nucleating 
agent includes known inorganic or organic nucleating agents. 
Examples of the inorganic nucleating agent are talc, mica, silica, kaolin, 
clay, attapulgite, romeite powder, quartz powder, zinc oxide, diatomaceous 
earth, montmorillonite, vermiculite, amorphous silica, glass powder, 
silica-alumina, wollastonite, carbon black, pyrophyllite, graphite, zinc 
sulfide, boron nitride, silicon resin powder, and silicates, sulfates, 
carbonates, phosphates, aluminates and oxides of calcium, magnesium, 
aluminum, lithium, barium and titanium. 
Examples of the organic nucleating agent are those conventionally used in 
the art, e.g. aliphatic carboxylic acid metal salts, metal salts of 
aromatic carboxylic acids such as benzoic acid and terephthalic acid, 
aromatic phosphonic acids and metal salts thereof, aromatic phosphoric 
acid metal salts, metal salts of aromatic sulfonic acids such as 
benzenesulfonic acid and naphthalenesulfonic acid, metal salts of 
.beta.-diketones, polymeric compound having metal salt of carboxyl groups, 
and fine powders of crystalline polymer such as 4,6 nylon, 
polyphenylenesulfide ketone, and polyester prepared using 
parahydroxybenzoic acid as a monomer. 
A filler may be added as a reinforcing agent or as an extender. The filler 
is not specifically limited and may be one conventionally used in the art. 
Examples of the filler are 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, potassium titanate fiber, etc. The 
amount of the filler is not specifically limited. Generally, it is 
preferably used in an amount of about 10-200 parts by weight relative to 
100 parts by weight of the thermoplastic resin. 
The thermoplastic resin composition of the present invention can be 
prepared by the conventional method. For example, the desired resin 
composition is prepared by mixing the specified amounts of said 
thermoplastic resin, the imide compounds of formulas (1) to (3) and the 
various additives to be used as desired, by means of a V-blender, a ribbon 
blender, Henschel mixer, a tumble blender or the like and kneading the 
mixture by means of a kneading machine such as Banbury's mixer, a kneader, 
an oven roll, a single screw extruder, a twin-screw extruder or a single 
reciprocating screw at a temperature higher than the melting temperature 
of the resin (preferably at a temperature of the melting temperature of 
the resin + (about 20.degree. to 150.degree. C.)). 
The imide compound-containing resin composition thus obtained according to 
the present invention is useful as molding materials for various molded 
articles, and can be molded by the method conventionally used in the art, 
e.g. by injection molding, extrusion molding, blow molding, calender 
molding, or rotational molding. For example, in the case of injection 
molding, it is preferable to employ, depending on the thermoplastic resin 
used, the following conditions: a resin temperature of about 
200.degree.-400.degree. C., a mold temperature of about 
0.degree.-250.degree. C. and an injection pressure of about 500-1300 
kg/cm.sup.2. In the case of blow molding it is preferable to employ, 
depending on the thermoplastic resin used, the following conditions : a 
resin temperature of about 100.degree.-400.degree. C., a mold temperature 
of about 0.degree.-250.degree. C. and a blowing pressure of about 2-10 
kgf/cm.sup.2. The molded articles thus obtained are suitable as a material 
for electric and electronic appliance parts, automobile parts and chemical 
parts. 
The resin composition containing the imide compounds of formulas (1) to (3) 
according to the present invention is also useful as a material for 
fibers, and can be made into fibers by the method conventionally used in 
the art. For example, the resin composition is subjected to spinning in a 
molten state, cooled, stretched and subjected to heat treatment, thereby 
giving fibers. The filaments that are spun may, after cooling, be wound as 
unstretched filaments, and then preheated and stretched, followed by being 
subjected to heat treatment under tension. Alternatively, the filaments 
are not wound but are drawn off by a drawn-off roll and subsequently 
stretched and heat-treated on a heated roller. The stretching and heat 
treatment are carried out in the same manner as in making conventional 
fibers. The preheating temperature for stretching is preferably 
60.degree.-150.degree. C., and the temperature for heat treatment is 
preferably 150.degree.-300.degree. C. Most suitable resins for use as 
materials for fibers are polyethyleneterephthalate, 6-nylon, 6,6-nylon, 
polyarylene sulfide (PAS), etc., and in this case the reduction in the 
melt viscosity thereof is particularly achieved. 
The thermoplastic resin composition of the present invention has the 
following advantages. 
By adding the imide compound(s) to the thermoplastic resin according to the 
present invention, the melt viscosity of the resin is lowered, and in the 
case of crystalline resins the crystallization thereof is accelerated. 
Hence the thermoplastic resin composition of the invention has the 
advantages of increasing productivity and inhibiting thermal deterioration 
due to the lowered molding temperature. 
When the imide compounds of the formulas (1), (2) and (3) according to the 
present invention are added to any of the foregoing thermoplastic resins, 
molding operation can be advantageously carried out to give molded 
articles having excellent properties. 
In particular, the method of molding a thermoplastic resin according to the 
present invention has the advantage that the production of thin-walled 
molded articles or precision molding become possible and that the molding 
cycle can be shortened. 
Particularly, in the case of PAS resin, this resin can be molded at a mold 
temperature of as low as 0.degree.-100.degree. C., and there is 
substantially no deterioration of the inherent properties of the resin, 
especially mechanical strength. Therefore, this leads to the advantage 
that a water cooled mold of the molding machine for general-purpose resins 
can be used. 
When the imide compounds of formulas (1), (2) and (3) according to the 
present invention are blended with polyarylene sulfide (PAS) such as 
polyphenylene sulfide (PPS) among thermoplastic resins, more preferable 
results are achieved. Hereinafter, a resin composition containing 
polyarylene sulfide (PAS) and molding methods thereof will be described 
below. 
The PAS to be used in the present invention is a polymer mainly containing 
at least 70 mole %, preferably at least 90 mole %, of a repeating unit 
represented by (-Ph-S-). In particular, polyphenylene sulfide (PPS) is 
preferably used. 
There is no restriction on PPS as far as it is produced by the conventional 
method. For example, there can be used a comparatively low molecular 
weight polymer described in Japanese Unexamined Patent Publication (Kokai) 
No. 3368/1970, a high molecular weight polymer prepared by heating said 
low molecular weight polymer in an atmosphere of oxygen or by crosslinking 
the polymer using peroxide, and an essentially linear and comparatively 
high molecular weight polymer produced by the method of Japanese 
Unexamined Patent Publication (Kokai) No. 12240/1977. 
Also usable are the PAS copolymers which contain other repeating unit as a 
copolymer component in an amount of more than 0 but not more than 30 mole 
%, preferably not more than 10 mole %. 
Examples of the other repeating unit are ortho-phenylenesulfide, 
methaphenylenesulfide, diphenylsulfide ether, diphenylsulfide sulfone, 
diphenylenesulfide ketone, biphenylenesulfide, naphthalenesulfide, 
diphenylenesulfide methane, diphenylenesulfide propane, trifunctional 
phenylenesulfide, substituted phenylenesulfide (having one or two 
substituents selected from the group consisting of an alkyl group 
(particularly C.sub.1 -C.sub.4 alkyl group), nitro group, phenyl group, a 
carboxylic acid group, an alkoxy group (particularly C.sub.1 -C.sub.4 
alkoxy group), amino group and the like). 
The melt viscosity of the PAS or PAS copolymer is not particularly limited 
as far as the PAS or PAS copolymer can be injection molded. However, it is 
recommended that the viscosity is generally 10-100000 poise, preferably 
about 100-50000 poise as determined by a Koka-type flow tester 
(300.degree. C.; rate of shear: 10.sup.3 /sec.). 
The imide compound is used in an amount of 0.1-100 parts by weight, 
preferably 0.5-50 parts by weight, relative to 100 parts by weight of the 
PAS or PAS copolymer. When used as a viscosity-reducing agent or 
crystallization accelerator, the imide compound is preferably used in an 
amount of 1-20 parts by weight relative to 100 parts by weight of the PAS 
or PAS copolymer. The use of less than 0.1 part by weight of the imide 
compound achieves little improvement in the desired properties, whereas 
the use of more than 100 parts by weight of the imide compound is likely 
to impair the heat resistance necessary to the resin. 
If desired, the resin composition of the present invention may incorporate 
therein a crystal nucleating agent, a reinforcing agent, a filler, an 
antioxidant, an ultraviolet ray absorbent, an antistatic agent, a flame 
retarder, a modifier, a lubricant or the like. 
When a crystal nucleating agent is used, crystallization is accelerated, 
and this brings about better results in many cases. The amount of the 
crystal nucleating agent is not specifically limited. Generally, it is 
preferably used in an amount of about 0.001-10 parts by weight relative to 
100 parts by weight of the thermoplastic resin. The crystal nucleating 
agent includes known inorganic nucleating agents and organic nucleating 
agents. 
Examples of the inorganic nucleating agent are talc, mica, silica, kaolin, 
clay, attapulgite, romeite powder, quartz powder, zinc oxide, diatomaceous 
earth, montmorillonite, vermiculite, amorphous silica, glass powder, 
silica-alumina, wollastonite, carbon black, pyrophyllite, graphite, zinc 
sulfide, boron nitride, silicon resin powder, and silicates, sulfates, 
carbonates, phosphates, aluminates and oxides of calcium, magnesium, 
aluminum, lithium, barium and titanium. 
Examples of the organic nucleating agent are aliphatic carboxylic acid 
metal salts, metal salts of aromatic carboxylic acids such as benzoic acid 
and terephthalic acid, aromatic phosphonic acids and metal salts thereof, 
aromatic phosphoric acid metal salts, metal salts of aromatic sulfonic 
acids such as benzenesulfonic acid and naphthalenesulfonic acid, metal 
salts of .beta.-diketones, polymeric compound having metal salt of 
carboxyl groups, and fine powders of crystalline polymer such as polyester 
prepared using parahydroxybenzoic acid as a monomer, 4,6. nylon and 
polyphenylenesulfide ketone. 
A filler can be added as a reinforcing agent or as an extender. The filler 
is not specifically limited. Examples of useful fillers as reinforcing 
agent are carbon black, calcium carbonate, magnesium carbonate, barium 
sulfate, kaolin, calcined clay, talc, aluminum silicate, calcium silicate, 
silicic acid, carbon fiber, glass fiber, asbestos fiber, silica fiber, 
zirconia fiber, aramid fiber, potassium titanate fiber, and metal fiber. 
The amount of the filler is not specifically limited. Generally, the 
filler is preferably used in an amount of about 10-200 parts by weight 
relative to 100 parts by weight of the PAS or PAS copolymer. 
In using these fillers, it is preferable to use a surface treating agent or 
a sizing agent if so desired. Examples of such surface treating agent and 
sizing agent are silane compounds epoxy compounds and isocyanate 
compounds. 
If desired, it is also possible to add additives such as an antioxidant 
such as hindered amine compounds, benzophenone compounds and benzotriazole 
compounds, a pigment, a dye, an antistatic agent, a lubricant and a mold 
releasing agent. 
Within the range not contrary to the object of this invention, it is 
possible to add other thermoplastic resin such as polyethylene, 
polypropylene, polybutene, polystyrene, polyphenylene ether, polyether 
sulfone, polyetherether ketone, polyphenylene oxide, poly-oxymethylene, 
PTFE, maleimide modified ABS, chlorinated PVC, aromatic polyamides 
prepared from terephthalic acid and an aliphatic diamine or from 
xylylenediamine and an aliphatic dicarboxylic acid, aliphatic polyamides 
such as 6 nylon, 6,6 nylon, 4,6 nylon, 11 nylon and 12 nylon, 
polycarbonate, polyethyleneterephthalate, polybutyleneterephthalate, 
polyarylate, liquid-crystal polymer, polyamide-imide, polyetherimide, 
polyimide, and the like. 
Generally, said other thermoplastic resin is preferably used in an amount 
of about 10-200 parts by weight relative to 100 parts by weight of the PAS 
or PAS copolymer. 
The PAS resin composition of the present invention can be prepared by the 
known method. For example, there can be mentioned a method comprising 
adding the imide compound of formula (1), (2) or (3) as such to PAS resin 
powder, a method comprising the steps of dissolving the imide compound in 
xylene, dimethylformamide or the like, mixing PAS resin powder with the 
solution and drying the mixture, a method comprising adding the imide 
compound to the slurry after polymerization of PAS, a method comprising 
homogeneously blending the imide compound and PAS resin with a reinforcing 
agent such as glass fiber, a filler such as calcium carbonate or other 
optionally usable additives by V-blender, ribbon blender, Henschel mixer, 
tumbler blender or the like, heating, melting and kneading the mixture 
using Banbury's mixer, a kneader, an oven roll, a single screw extruder, a 
twin-screw extruder, a single reciprocating screw or the like and 
pelletizing the resulting composition. The method comprising melting, 
kneading and pelletizing the composition is recommendable among them. In 
this case, it is possible to knead only the necessary components to 
prepare a masterbatch. 
The kneading temperature is set at a temperature not lower than the melting 
point of the PAS resin to be used. For example, PPS resin is preferably 
kneaded at 280.degree.-400.degree. C. If the temperature is 280.degree. C. 
or lower, the resin is insufficiently dissolved, whereas if the 
temperature is 400.degree. C. or higher, smoke is emitted due to the 
decomposition of additives, hence undesirable. 
The method of molding the PAS resin composition prepared by the above 
method can be conducted by known method. 
Injection molding machine can be any of the screw-in-line type or plunger 
type. In order to avoid unnecessary heat history, it is preferable to use 
a molding machine in which the capacity of the molding machine is equal to 
the amount of injection. It is preferable that the screw is made of wear 
resistant material. 
The resin pellets to be subjected to the molding are preferably pre-dried 
at 120.degree.-160.degree. C. for 2 to 6 hours, whereby insufficient 
appearance such as silver streak, haze or the like is unlikely to occur. 
The resin temperature in injection molding is preferably 
280.degree.-400.degree. C., in particular about 290.degree.-360.degree. C. 
The mold temperature is generally 0.degree.-100.degree. C., and 
particularly 40.degree.-80.degree. C. is recommended. However, it is also 
possible to conduct injection molding at a mold temperature of 100.degree. 
C. or higher (e.g., about 130.degree. C.). When the heat resistance of the 
molded article is important, a high mold temperature is preferable and 
gives better results, whereas when dimensional accuracy is considered to 
be important, a low mold temperature brings about better results. 
The injection pressure is preferably 500-1300 kg/cm.sup.2. Generally, 
molded articles having uniform and lustrous surface are obtained when the 
injection is conducted at a high pressure and a high speed, whereas molded 
articles having less warping and flash are obtained when the injection is 
carried out at a low pressure and a low speed. 
The rotation speed of the screw is 10-300 rpm, preferably about 40-200 rpm. 
When the molding cycle is desired to be quickened, it is preferable to 
increase the rotation speed. However, excessive increase in rotational 
frequency is unfavorable because it causes severance of glass fiber and 
generation of heat from the resin. 
The PAS resin composition according to the present invention has a high 
crystallization speed, can be molded at a mold temperature ranging from 
low to high temperature, and the molded articles obtained have good 
appearance and few flash and are low in dimension shrinkage percentage and 
excellent in mechanical strength. Therefore, the composition is suitable 
for molding materials for various molded articles such as electric and 
electronic appliance parts, automobile parts and chemical parts. 
The present invention will be described in greater detail with reference to 
Production Examples which illustrate the preparation of the imide 
compounds or PPS resin and Examples which illustrate the resin 
compositions prepared by incorporating the imide compounds into 
thermoplastic resins. 
The imide compounds prepared in Production Examples were identified by NMR 
and IR analyses.

PRODUCTION EXAMPLE 1 
A 19.8 g quantity (0.1 mole) of BTC dianhydride and 53.8 g (0.2 mole) of 
stearylamine were mixed with stirring in 500 ml of xylene and the 
temperature was raised to 130.degree. C. While water that generated and 
xylene were removed and separated by cooling a distilled water-xylene 
azeotropic mixture by means of a cooler, the reaction mixture was heated 
until the reaction temperature reached 260.degree. C. The reaction was 
continued until 3.6 g of the generated water was removed from the reaction 
system. After completion of the reaction, the reaction mixture was 
neutralized with a 10% aqueous solution of sodium hydroxide, treated with 
clay and filtered, and the remaining xylene was removed by topping, thus 
giving the desired imide compound (imide A). 
Said imide A is a bisimide of the formula (1) wherein R.sup.1 and R.sup.2 
each represent a C.sub.18 alkyl group and A.sup.1 and A.sup.2 each 
represent a single bond. 
PRODUCTION EXAMPLE 2 
The same procedure as in Preparation Example 1 was repeated using 23.4 g 
(0.1 mole) of BTC, 51.8 g (0.2 mole) of tallow amine and 500 ml of xylene. 
The reaction was terminated when 6.6 g of the generated water was 
distilled off. After completion of the reaction, and the remaining xylene 
was removed by topping, thus giving the desired imide compound (imide B) 
having a residual carboxyl group. 
This imide B is a mixture which comprises, as a main component, a bisimide 
of the formula (1) wherein R.sup.1 and R.sup.2 each represent a C.sub.8 
-C.sub.22 alkyl or alkenyl group and A.sup.1 and A.sup.2 each represent a 
single bond, and which further comprises 
a monoimide of the formula (2) wherein R.sup.7 represents a C.sub.8 
-C.sub.22 alkyl or alkenyl group, A.sup.3 represents a single bond, X 
represents --NH--R.sup.8 (wherein R.sup.8 represents a C.sub.8 -C.sub.22 
alkyl or alkenyl group) and Y represents --OH, and 
a monoimide of the formula (3) wherein R.sup.9 and R.sup.10 each represent 
a C.sub.8 -C.sub.22 alkyl or alkenyl group and A.sup.5 and A.sup.6 each 
represent a single bond. 
PRODUCTION EXAMPLE 3 
The same procedure as in Preparation Example 1 was repeated using 23.4 g 
(0.1 mole) of BTC, 51.8 g (0.2 mole) of tallow amine and 500 ml of xylene. 
The reaction was terminated when 6.6 g of the generated water was 
distilled off. After completion of the reaction, the reaction mixture was 
neutralized with addition of 1.2 g of calcium hydroxide, and the remaining 
xylene was removed by topping, thus giving the desired imide compound 
(imide C) containing a carboxylic acid calcium salt. 
This imide C is a mixture which comprises, as a main component, a bisimide 
of the formula (1) wherein R.sup.1 and R.sup.2 each represent a C.sub.8 
-C.sub.22 alkyl or alkenyl group and A.sup.1 and A.sup.2 each represent a 
single bond, and which further comprises 
a calcium salt of a monoimide of the formula (2) wherein R.sup.7 represents 
a C.sub.8 -C.sub.22 alkyl or alkenyl group, A.sup.3 represents a single 
bond, X represents --NH--R.sup.8 (wherein R.sup.8 represents a C.sub.8 
-C.sub.22 alkyl or alkenyl group) and Y represents --OH, and 
a calcium salt of a monoimide of the formula (3) wherein R.sup.9 and 
R.sup.10 each represent a C.sub.8 -C.sub.22 alkyl or alkenyl group and 
A.sup.5 and A.sup.6 each represent a single bond. 
PRODUCTION EXAMPLE 4 
The same procedure as in Preparation Example 1 was repeated using 23.4 g 
(0.1 mole) of BTC, 52.2 g (0.2 mole) of p-dodecylaniline and 500 ml of 
xylene. The reaction was terminated when 6.6 g of the formed water was 
distilled off. After completion of the reaction, the reaction mixture was 
neutralized with a 10% aqueous solution of potassium hydroxide, treated 
with clay and filtered, and the remaining xylene was removed by topping, 
thus giving the desired imide compound (imide D). 
This imide D is a mixture which comprises, as a main component, a bisimide 
of the formula (1) wherein R.sup.1 and R.sup.2 each represent a C.sub.12 
alkyl group and A.sup.1 and A.sup.2 each represent a phenylene group, and 
which further comprises 
a monoimide of the formula (2) wherein R.sup.7 represents a C.sub.12 alkyl 
group, A.sup.3 represents a phenylene group, X represents a group 
--NH--A.sup.4 --R.sup.8 (wherein A.sup.4 represents a phenylene group, 
R.sup.8 represents a C.sub.12 alkyl group) and Y represents --OH, and 
a monoimide of the formula (3) wherein R.sup.9 and R.sup.10 each represent 
a C.sub.12 alkyl group and A.sup.5 and A.sup.6 each represent a phenylene 
group. 
PRODUCTION EXAMPLE 5 
The same procedure as in Preparation Example 1 was repeated using 20.4 g 
(0.1 mole) of BTC monoanhydride, 41.0 g (0.2 mole) of p-butylaniline and 
500 ml of xylene. The reaction was terminated when 3.3 g of the formed 
water was distilled off. After completion of the reaction, and the 
remaining xylene was removed by topping, thus giving the desired imide 
compound (imide E) having a residual carboxylic group. 
This imide E is a mixture which comprises, as a main component, a bisimide 
of the formula (1) wherein R.sup.1 and R.sup.2 each represent a C.sub.4 
alkyl group and A.sup.1 and A.sup.2 each represent a phenylene group, and 
which further comprises 
a monoimide of the formula (2) wherein R.sup.7 represents a C.sub.4 alkyl 
group, represents a phenylene group, X represents a group --NH--A.sup.4 
--R.sup.8 (wherein A.sup.4 represents a phenylene group, R.sup.8 
represents a C.sub.4 alkyl group) and Y represents --OH, and 
a monoimide of the formula (3) wherein R.sup.9 and R.sup.10 each represent 
a C.sub.4 alkyl group and A.sup.5 and A.sup.6 each represent a phenylene 
group. 
PRODUCTION EXAMPLE 6 
The same procedure as in Preparation Example 1 was repeated using 19.8 g 
(0.1 mole) of BTC dianhydride, 46.6 g (0.2 mole) of p-decylaniline and 500 
ml of xylene. The reaction was terminated when 3.3 g of the formed water 
was distilled off. After completion of the reaction, the reaction mixture 
was neutralized with calcium hydroxide and the remaining xylene was 
removed by topping, thus giving the desired imide compound (imide F) 
containing a carboxylic acid salt. 
This imide F is a mixture which comprises, as a main component, a bisimide 
of the formula (1) wherein R.sup.1 and R.sup.2 each represent a C.sub.10 
alkyl group and A.sup.1 and A.sup.2 each represent a phenylene group, and 
which further comprises 
a calcium salt of a monoimide of the formula (2) wherein R.sup.7 represents 
a C.sub.10 alkyl group, A.sup.3 represents a phenylene group, X 
represents a group --NH--A.sup.4 --R.sup.8 (wherein A.sup.4 represents a 
phenylene group and R.sup.8 represents a C.sub.10 alkyl group) and Y 
represents --OH, and 
a calcium salt of a monoimide of the formula (3) wherein R.sup.9 and 
R.sup.10 each represent a C.sub.10 alkyl group and A.sup.5 and A.sup.6 
each represent a phenylene group. 
EXAMPLE 1 
Five parts by weight of "imide A" was added to 100 parts by weight of PET 
resin, and the mixture was melted and mixed at 260.degree. C. in an 
extruder. The extruded strand was cooled with water and cut to prepare a 
specimen. 
The melt flow index (MFI) of the specimen was determined as the amount of 
molten resin extruded from an orifice (2 mm in diameter, 8 mm in length) 
for 10 minutes at a temperature of 275.degree. C. and under a load of 2 
kg. The obtained value was 31 cm.sup.3 /10 min. 
COMATIVE EXAMPLE 1 
The MFI of the PET resin per se used in Example 1 was determined following 
the procedure of Example 1. The obtained value was 18 cm.sup.3 /10 min. 
EXAMPLE 2 
One hundred parts by weight of PET resin, 5 parts by weight of "imide C" 
and 3 parts by weight of talc as a crystallization nucleating agent were 
mixed at 50.degree. C. with a Henschel mixer. The mixture was then melted 
and mixed at 260.degree. C. in an extruder, and the extruded strand was 
cooled with water and cut to prepare a specimen. 
Fifteen mg of the specimen was placed in a differential scanning 
calorimeter (DSC), heated at a rate of 10.degree. C./min., melted at 
300.degree. C. for 3 minutes and cooled at a rate of 10.degree. C./min. 
The difference (.increment.t) between the crystallization temperature 
measured during heating and the melting point measured during cooling 
(crystallization temperature measured during cooling) was 124.degree. C., 
and the crystallization temperature was 84.degree. C. 
The difference (.increment.t) between the crystallization temperature 
measured during heating and the melting point measured during cooling 
(crystallization temperature measured during cooling) is an index of the 
crystallization rate. The greater the difference, the higher the 
crystallization rate of the resin composition. 
Further, the lower crystallization temperature is indicative of the 
promoted crystallization of the resin composition. 
COMATIVE EXAMPLE 2 
The difference in crystallization temperatures (.increment.t) of the PET 
resin per se used in Example 2 was determined following the procedure of 
Example 2. The obtained value was 90.degree. C. and the crystallization 
temperature was 117.degree. C. 
EXAMPLE 3 
One hundred parts by weight of 12 nylon resin and 5 parts by weight of 
"imide B" were kneaded on an oven roll at 180.degree. C. to prepare a 
specimen. 
The MFI of the specimen was determined as the amount of molten resin 
extruded from an orifice having a diameter of 1 mm and the length of 10 mm 
for 10 minutes at a temperature of 240.degree. C. under a load of 20 kg. 
The obtained value was 12.4 cm.sup.3 /10 min. 
COMATIVE EXAMPLE 3 
The MFI of the nylon resin per se used in Example 3 was determined 
following the procedure of Example 3. The obtained value was 5.6 cm.sup.3 
/10 min. 
EXAMPLE 4 
One hundred parts by weight of PPS resin and 5 parts by weight of "imide A" 
were melted, mixed and kneaded at 290.degree. C. with a labo plastomixer 
to prepare a specimen. 
According to the DSC measurement (conditions: sample 15 mg, heated at a 
rate of 10.degree. C./min., melted at 330.degree. C. for 3 minutes and 
cooled at a rate of 10.degree. C./min), the temperature difference 
(.increment.t) was 165.degree. C. and the crystallization temperature was 
117.degree. C. 
EXAMPLE 5 
A specimen was prepared in the same manner as in Example 4 with the 
exception of using 5 parts by weight of "imide F". 
According to the DSC measurement (conditions: the same as in Example 4), 
the temperature difference (.increment.t) was 175.degree. C. and the 
crystallization temperature was 109.degree. C. 
COMATIVE EXAMPLE 4 
The temperature difference (.increment.t) of the PPS resin per se used in 
Example 4 was determined following the procedure of Example 4. The 
obtained value was 156.degree. C. and the crystallization temperature was 
128.degree. C. 
EXAMPLE 6 
One hundred parts by weight of chlorinated vinyl chloride resin with a 
chlorination degree of about 65%, 5 parts by weight of "imide B", 1.5 
parts by weight of dibutyltin maleate, 1.5 parts by weight of dibutyltin 
sulfide, 0.4% of butyl stearate and 0.4% of stearyl alcohol were mixed 
using a Henschel mixer, and the mixture was melted and mixed on a roll at 
190.degree. C. to prepare a specimen. 
The MFI of the specimen was determined as the amount of the molten resin 
extruded from an orifice having a diameter of 1 mm and a length of 10 mm 
for 10 minutes at a temperature of 190.degree. C. under a load of 160 kg. 
The obtained value was 520 cm.sup.3 /10 min. 
COMATIVE EXAMPLE 5 
The MFI of a chlorinated vinyl chloride resin composition was determined 
following the procedure of Example 6, the resin composition having the 
same formulation as the one used in Example 6 with the exception that 
"imide B" was not added. The obtained value was 270 cm.sup.3 /10 min. 
EXAMPLE 7 
Five parts by weight of "imide D" was dry-blended with 100 parts by weight 
of POM resin. The mixture was melted and kneaded at 230.degree. C. in a 
twin-screw extruder and extruded into water and cut to prepare a specimen. 
The MFI (190.degree. C., under a load of 2.19 kg) of this specimen was 
determined, and the obtained value was 15.8 cm.sup.3 /10 min. 
COMATIVE EXAMPLE 6 
The MFI of the POM resin per se used in Example 7 was determined following 
the procedure of Example 7. The obtained value was 7.0 cm.sup.3 /10 min. 
EXAMPLE 8 
Two parts by weight of "imide E" was thoroughly mixed with 100 parts by 
weight of ABS resin with a Henschel mixer, and the mixture was kneaded in 
a single-screw extruder to prepare pellets. 
The flow length of the pellets was determined at 260.degree. C. by means of 
an injection molding machine using a spiral mold. The obtained value was 
63.5 cm. 
Longer flow length is indicative of lower melt viscosity of the resin 
composition. 
COMATIVE EXAMPLE 7 
The flow length of the ABS resin per se used in Example 8 was determined 
following the procedure of Example 8. The obtained value was 47.9 cm. 
EXAMPLE 9 
Two parts by weight of "imide A" was added to 100 parts by weight of 
powdery thermoplastic polyimide obtained by dehydration condensation of 
3,3', 4,4'-diphenylsulfontetracarboxylic acid dianhydride and 
2,2-bis 4-p-aminophenoxy)phenyl!propane at 170.degree. C., and the mixture 
was mixed by means of an extruder until-it became homogeneous. The 
extruded strand was cooled with water and cut to prepare a specimen. 
Subsequently, according to JIS K7210 (flow test method (reference test)), 
the melt viscosity of the specimen at 360.degree. C. was determined 
(apparatus: "CFT-500C" manufactured by Shimadzu Seisakusho Ltd., test 
pressure: 100 kgf/cm.sup.2, die: 1.times.10 mm). As a result, the melt 
viscosity of the specimen was found to be 20,600 poise. 
The melt viscosity of the above powdery thermoplastic polyimide per se, as 
determined in the same manner as above, was 68,000 poise. 
Therefore, it was observed that addition of imide A of the present 
invention results in a remarkable decrease in melt viscosity. 
Further, neither void nor coloring due to decomposition were recognized on 
the obtained strands. 
As apparent from the Examples and Comparative Examples, addition of the 
imide compound of the present invention to a thermoplastic resin can 
decrease the melt viscosity of the resin, and promote the crystallization 
of the resin if the resin is crystalline. 
A resin composition prepared by adding the imide compound of the present 
invention to polyphenylene sulfide (PPS) is illustrated below. 
PRODUCTION EXAMPLE 7 
A 650 g (5.0 moles), quantity of sodium sulfide.2.9 hydrate and 1800 g of 
N-methylpyrrolidone (NMP) were placed in an autoclave. The mixture was 
heated to 205.degree. C., and about 150 g of distilled water was removed 
therefrom. Subsequently, 720 g (4.85 moles) of p-dichlorobenzene and 400 g 
of N-methylpyrrolidone (NMP) were added and a reaction was carried out at 
250.degree. C. for 4 hours. 
After completion of the reaction, the reaction mixture was cooled to room 
temperature and filtered to collect the product. The product was 
repeatedly washed with warm water and dried at 100.degree. C. for twenty 
four hours to obtain a PPS resin (PPS-1) having a melt viscosity of 300 
poise (determined with a Koka type flow tester, the same applies 
hereinafter). 
PRODUCTION EXAMPLE 8 
"PPS-1" was thermally crosslinked by subjecting the resin to heat treatment 
in the air at 260.degree. C. for 5 hours, giving a PPS resin (PPS-2) 
having a melt viscosity of 2500 poise. 
PRODUCTION EXAMPLE 9 
A 650 g (5.0 moles) quantity of sodium sulfide.multidot.2.9 hydrate, 210 g 
(5.0 moles) of lithium chloride and 1800 g of MNP were placed in an 
autoclave and the mixture was heated to 205.degree. C. to remove about 140 
g of the water that was distilled. Subsequently, 720 g (4.85 moles) of 
p-dichlorobenzene and 400 g of NMP were added and a reaction was carried 
out at 250.degree. C. for 4 hours. 
On completion of the reaction, the reaction mixture was cooled to room 
temperature and filtered to collect the product. The product was 
repeatedly washed with warm water and dried at 100.degree. C. for twenty 
four hours to obtain a PPS resin (PPS-3) having a melt viscosity of 1800 
poise. 
PRODUCTION EXAMPLE 10 
A 19.8 g (0.1 mole) of BTC dianhydride and 53.8 g (0.2 mole) of tallow 
amine were mixed and stirred in 500 ml of xylene and heated to 130.degree. 
C. The mixture was further heated to the final temperature of 260.degree. 
C. while separating and removing the generated water and xylene by cooling 
the distilled xylene-water azeotropic mixture with a condenser. The 
reaction was continued until 3.6 g of the generated water was removed from 
the reaction system. 
On completion of the reaction, the reaction mixture was neutralized with an 
aqueous solution of potassium hydroxide, treated with clay and filtered, 
and the remaining xylene was removed by topping. Thus, an imide compound 
(imide G) was obtained. 
This imide G is a bisimide represented by the formula (1) wherein R.sup.1 
and R.sup.2 each represent C.sub.8 -C.sub.22 alkyl or alkenyl group and 
A.sup.1 and A.sup.2 each represent a single bond. 
PRODUCTION EXAMPLE 11 
The procedure of Production Example 10 was repeated using 19.8 g (0.1 mole) 
of BTC dianhydride, 34.0 g (0.2 mole) of laurylamine and xylene, and the 
reaction was completed when 3.0 g of the generated water was distilled 
off. On completion of the reaction, the reaction mixture as such was 
subjected to topping to remove xylene. Thus, a monoimide compound (imide 
H) was obtained wherein the carboxyl groups partially remained. 
This imide H is a mixture which comprises, as the main component, a 
bisimide of the formula (1) wherein R.sup.1 and R.sup.2 each represent a 
C.sub.12 alkyl group and A.sup.1 and A.sup.2 each represent a single bond, 
and which further comprises 
a monoimide of the formula (2) wherein R.sup.7 is a C.sub.12 alkyl group, 
A.sup.3 is a single bond, X is a group --NH--A.sup.4 --R.sup.8 (wherein 
A.sup.4 is a single bond and R.sup.8 is a C.sub.12 alkyl group) and Y is 
--OH, and 
a monoimide of the formula (3) wherein R.sup.9 and R.sup.10 each represent 
a C.sub.12 alkyl group and A.sup.5 and A.sup.6 each represent a single 
bond. 
PRODUCTION EXAMPLE 12 
The procedure of Production Example 10 was repeated using 23.4 g (0.1 mole) 
of BTC, 34.0 g (0.2 mole) of laurylamine and xylene, and the reaction was 
terminated when 5.4 g of the generated water was distilled off. On 
completion of the reaction, the reaction mixture was neutralized with 
sodium hydroxide and the neutralized mixture as such was subjected to 
topping to remove xylene. Thus, an imide compound (imide I) containing 
carboxylic acid sodium salt was obtained. 
This imide I is a mixture which comprises, as the main component, a 
bisimide of the formula (1) wherein R.sup.1 and R.sup.2 each represent a 
C.sub.12 alkyl group and A.sup.1 and A.sup.2 each represent a single bond, 
and which further comprises 
a sodium salt of a monoimide of the formula (2) wherein R.sup.7 is a 
C.sub.12 alkyl group, A.sup.3 is a single bond, X is a group --NH--A.sup.4 
--R.sup.8 (wherein A.sup.4 is a single bond and R.sup.8 is a C.sub.12 
alkyl group) and Y is --OH, and 
a sodium salt of a monoimide of the formula (3) wherein R.sup.9 and 
R.sup.10 each represent a C.sub.12 alkyl group and A.sup.5 and A.sup.6 
each represent a single bond. 
PRODUCTION EXAMPLE 13 
The procedure of Production Example 10 was repeated using 23.4 g (0.1 mole) 
of BTC, 52.2 g (0.2 mole) of paradodecylaniline and xylene, and the 
reaction was terminated when 7.2 g of the generated water was distilled 
off. After completion of the reaction, the reaction mixture was 
neutralized with calcium hydroxide and the neutralized mixture as such was 
subjected to topping to remove xylene. Thus, an imide compound (imide J) 
was obtained. 
Imide J is a mixture which comprises, as the main component, a bisimide of 
the formula (1) wherein R.sup.1 and R.sup.2 each represent a C.sub.12 
alkyl group and A.sup.1 and A.sup.2 each represent a phenylene group, and 
which further comprises 
a calcium salt of a monoimide of the formula (2) wherein R.sup.7 is a 
C.sub.12 alkyl group, A.sup.3 is a phenylene group, X is a group 
--NH-A.sup.4 --R.sup.8 (wherein A.sup.4 is a phenylene group and R.sup.8 
is a C.sub.12 alkyl group) and Y is --OH, and 
a calcium salt of a monoimide of the formula (3) wherein R.sup.9 and 
R.sup.10 each represent a C.sub.12 alkyl group and A.sup.5 and A.sup.6 
each represent a phenylene group. 
EXAMPLES 10-14 
A PPS resin, an imide compound and, where necessary, talc as shown in the 
following Table 1 were preliminarily mixed using a Henschel mixer, and 65 
parts by weight of a commercially available glass fiber was added to 100 
parts by weight of the PPS resin. The mixture thus obtained was melted and 
kneaded in an extruder having a cylinder temperature of 310.degree. C. to 
obtain pellets of a PPS resin composition. The pellets were then 
injection-molded at a cylinder temperature of 310.degree. C. and a mold 
temperature of 70.degree. C. 
The tensile strength, flexural strength and Izod impact strength of the 
thus-obtained test pieces were respectively determined by the following 
methods. 
(a) Tensile strength 
Determined based on ASTM-D68. 
(b) Flexural strength of the molded product 
Determined based on ASTM-D790. 
(c) Izod impact strength of the molded product 
Determined based on ASTM-D256 
The obtained results are shown in Table 1. 
COMATIVE EXAMPLE 8 
The tensile strength, flexural strength and Izod impact strength of a 
molded product prepared from PPS-1 alone were determined. The obtained 
results are shown in Table 1. 
COMATIVE EXAMPLE 9 
A PPS resin composition was prepared in the same manner as in Example 11 
with the exception of using ethylenebisstearamide (EBS) in lieu of "imide 
H". The tensile strength, flexural strength and Izod impact strength of 
the molded product of the composition were determined. The obtained 
results are shown in Table 1. 
COMATIVE EXAMPLE 10 
A PPS resin composition was prepared in the same manner as in Example 12 
except that "imide G" was not used. The tensile strength, flexural 
strength and Izod impact strength of the molded product of the composition 
were determined. The obtained results are shown in Table 1. 
As apparent from Table 1, according to the method of the present invention, 
molding can be conducted even at a low temperature without impairing the 
inherent mechanical properties and heat resistance of polyarylene sulfide. 
TABLE 1 
______________________________________ 
Examples Comp. Ex 
10 11 12 13 14 8 9 10 
______________________________________ 
PPS resin 
PPS-1 100 100 
PPS-2 100 100 
PPS-3 100 100 100 100 
Imide 
compound 
Present imide 
3 3 
Present imide 3 
H 
Present imide 3 
I 
Present imide 5 
J 
Resin reform- 
ing agent 
Talc 3 3 
EBS 3 
Tensile 1350 1750 1790 1750 1780 1180 1680 1670 
strength 
(kg/cm.sup.2) 
Flexural 1900 2440 2480 2450 2480 1760 2320 2320 
strength 
(kg/cm.sup.2) 
Izod impact 
8.6 9.8 14.5 12.8 14.2 4.8 6.5 9.9 
strength 
(kg.cm/cm) 
______________________________________ 
PRODUCTION EXAMPLE 14 
A 23.4 g quantity (0.1 mole) of BTC and 52.2 g (0.2 mole) of 
p-dodecylaniline were mixed and stirred in 500 ml of xylene. The mixture 
was heated until the reaction temperature finally reached 260.degree. C., 
while removing and separating the generated water and xylene by cooling 
the distilled xylene-water azeotropic mixture with a condenser. The 
reaction was continued until 6.9 g of water was separated and removed from 
the reaction system. 
For purification by recrystallization, after the reaction, the reaction 
mixture was dissolved in 250 g of toluene/methyl ethyl 
ketone/dimethylformamide solvent mixture (weight ratio: 3/1/1) with 
heating. Then, 3 g of calcium oxide was added, dispersed and stirred. The 
dispersion was filtered to remove insoluble matters. The filtrate was 
cooled to obtain 41 g of a bisimide of BTC and p-dodecylaniline. 
The obtained compound was a solid having a melting point of 203.degree. C. 
The characteristic absorption of the infrared absorption was as follows. 
.upsilon. (C=)) 1778, 1703 cm.sup.-1 (characteristic absorption of imido 
group) 
The structure of the obtained bisimide 
##STR9## 
The results of elementary analysis were as follows. 
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C H O N 
______________________________________ 
Found (%) 77.5 9.4 9.1 4.0 
Calcd. (%) 77.2 9.4 9.3 4.1 
______________________________________