JP3467803B2 - Thermoplastic resin composition - Google Patents

Description

Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermoplastic resin composition having excellent heat resistance. [0002] Recently, thermoplastic resins having heat resistance have been used as engineering plastics in mechanical materials and electronic parts. In molding a thermoplastic resin, in order to increase productivity, resin additives for the purpose of lowering melt viscosity, accelerating nucleation, and improving mold release properties, for example, fatty acids such as stearic acid, fatty acid metal salts, etc. It is common practice to knead an ester derivative of a fatty acid with a polyhydric alcohol such as pentaerythritol and polyethylene glycol, and an aliphatic amide such as ethylene bisstearamide (JP-A-60-44547, JP-A-60-44547). 3-
No. 250049). However, a thermoplastic resin having heat resistance has a high melting temperature, and the above-mentioned resin additives may cause thermal decomposition or boiling at the time of melting, thereby contaminating a mold or generating air bubbles in the resin. there were. Therefore, a thermoplastic resin modifier having heat resistance has been desired. [0004] An object of the present invention is to provide a novel and useful thermoplastic resin composition containing a resin modifier having excellent heat resistance. The inventors of the present invention have conducted intensive studies to solve the above problems, and as a result, an imide compound having a specific structure has excellent heat resistance, Lowering the melt viscosity, or improving the crystallinity of the crystalline resin or improving the releasability, etc., has been found to be a resin modifier having desired performance, and the present invention has been made based on such knowledge. completed. That is, the thermoplastic resin composition according to the present invention comprises a diimide represented by the general formula (1), a monoimide represented by the general formula (2) and a monoimide represented by the general formula (2) per 100 parts by weight of the thermoplastic resin. It is characterized by containing 0.1 to 100 parts by weight of one or more imide compounds selected from the group consisting of metal salts (hereinafter collectively referred to as "the present imide compound"). [0007] [Wherein, R ¹ and R ² are the same or different and each have 4 to 28 carbon atoms.
A linear or branched alkyl or alkenyl group, a cycloalkyl group having 4 to 6 carbon atoms, Or Represents R ³ represents an alkyl group having 1 to 22 carbon atoms.
R ⁴ and R ⁶ represent a single bond or an alkylene group having 1 to 2 carbon atoms. R ⁵ represents an alkyl group having 1 to 22 carbon atoms. a is 1
And b represents an integer of 0 to 2. [0008] [Y when in the formula, X is a group NHR ⁷ represents a hydroxyl group, X when Y is a group NHR ⁷ represents a hydroxyl group. R ⁷ and R ⁸ have the same meaning as R ¹ in formula (1), and may be the same or different. The imide compound is diphenylsulfonetetracarboxylic acid or its dianhydride (hereinafter referred to as “the present acid component”).
Collectively. ) And an aliphatic, alicyclic or aromatic primary amine having a predetermined structure by a dehydration reaction. The diphenylsulfonetetracarboxylic acid includes 3,3 ', 4,4'-diphenylsulfonetetracarboxylic acid, 2,2', 3,3'-diphenylsulfonetetracarboxylic acid, 2,3 ', 3 , 4'-diphenylsulfonetetracarboxylic acid alone or in combination with
Mixtures of more than one species. It can also be easily obtained by a decarboxylation reaction between diphenylsulfonetetracarboxylic acid and an isocyanate derived from the primary amine. The dehydration reaction is most preferably industrially performed by heating, but if necessary, a dehydrating reagent such as acetic anhydride-pyridine or carbodiimide can be used. Examples of the aliphatic amine include butylamine, pentylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, and the like.
Examples include undecylamine, dodecylamine, tridecylamine, tetradecylamine, pentadecylamine, hexadecylamine, heptadecylamine, octadecylamine, octadecenylamine, nonadecylamine, eicosylamine, heneicosylamine and docosylamine. Among them, decylamine, dodecylamine, tetradecylamine, hexadecylamine, octadecylamine and the like are recommended. Substantially, it is economical to use a mixture containing these amines, for example, natural amines such as cocoamine, tallowamine, fish oil amine, hydrogenated cocoamine, hydrogenated tallowamine, and hydrogenated fish oil amine. Is significant. Specific examples of the alicyclic amine include cyclobutylamine, cyclopentylamine, cyclohexylamine, cyclohexylmethylamine, cyclohexylethylamine, methylcyclohexylamine, and dimethylcyclohexylamine. As the aromatic amine, specifically, allylaniline, hexylaniline, heptylaniline, octylaniline, nonylaniline, decylaniline, undecylaniline, dodecylaniline, tridecylaniline, tetradecylaniline, pentadecylaniline, Hexadecylaniline, heptadecylaniline, octadecylaniline, octadecenylaniline, nonadecylaniline, eicosylaniline, heneicosylaniline,
Examples include docosyl aniline, benzylamine and the like, among which decyl aniline, dodecyl aniline, tetradecyl aniline, hexadecyl aniline, octadecyl aniline and the like are recommended. Further, the present imide compound is obtained by converting the present acid component into a partial ester or a whole ester with a lower alcohol such as methyl alcohol or butyl alcohol, or an acid chloride with a chlorinating reagent such as thionyl chloride, phosgene or chlorine. For example, by reacting the amine in a form in which diphenylsulfonetetracarboxylic acid is substantially dehydrated. In the imide compound prepared by the above method, there is little unreacted acid component, and in order to avoid the decrease in the degree of polymerization, it is desirable to avoid the acid component as much as possible.
For example, polyethylene terephthalate (PET), polyoxymethylene (POM), polycarbonate (PC)
It is useful as a resin modifier. Among the imide compounds, compounds having a carboxyl group have an increased affinity for a mold and an increased external lubrication. Specifically, a carboxyl group of amide acid between diphenylsulfonetetracarboxylic dianhydride and an aliphatic amine is effective. For this reason, the dehydration reaction between diphenylsulfonetetracarboxylic dianhydride and an aliphatic amine may be controlled, if necessary, to leave a carboxyl group. The remaining carboxyl group may be used as it is, or may be in the form of a metal soap such as sodium, potassium, magnesium, barium, zinc, and aluminum. An excess of aliphatic amine can be added to dehydrate amidate to block carboxyl groups. In the imide compound prepared using an aliphatic primary amine as a raw material, the alkyl (or alkenyl) chain length of the raw amine is appropriately selected depending on the type and purpose of the thermoplastic resin to be applied. Specifically, an imide compound having an alkyl (or alkenyl) group having 4 to 18 carbon atoms is generally effective for lowering the melt viscosity and accelerating nucleation, and is generally an alkyl (or alkenyl) having 18 to 28 carbon atoms. ) The imide compound having a group often functions as an external lubricant. The imide compound may be used alone or in combination of two or more compounds depending on desired physical properties. In some cases, it may be added in the form of a mixed imide compound. Examples of the thermoplastic resin according to the present invention include various thermoplastic resins generally known as thermoplastic resins having heat resistance. For example, polyphenylene sulfide (PPS), polyphenylene ether (PP
E), aromatics such as polyethersulfone (PES), polyetheretherketone (PEEK), polyphenylene oxide (PPO), maleimide-modified ABS, chlorinated PVC, terephthalic acid and aliphatic diamine or xylylenediamine and aliphatic dicarboxylic acid Aliphatic polyamides such as aromatic polyamides, 6 nylon, 6,6 nylon, 4,6 nylon, 11 nylon, and 12 nylon, PC, polyacetal, PET, polybutylene terephthalate, PO
M, polyarylate, liquid crystal polymer, polyamide imide, and polyimide can be cited. It can also be added to general-purpose thermoplastic resins other than the resins described above. The amount of the imide compound to be added to the resin is 0.1 to 100 parts by weight, preferably 0.5 to 50 parts by weight, based on 100 parts by weight of the starting resin. To use this imide compound as a low viscosity agent or crystallization accelerator,
It is desirable to add so as to be 20 parts by weight. If the addition amount is 0.1 parts by weight or less, the characteristics do not improve much,
If the amount is more than 100 parts by weight, the heat resistance required for the resin may be impaired. Further, a nucleating agent according to its use and purpose,
Various additives such as a reinforcing agent, a filler, an antioxidant, an ultraviolet absorber, an antistatic agent, and a flame retardant can be appropriately added. Examples of the crystal nucleating agent include known inorganic and organic nucleating agents. Examples of the inorganic nucleating agent include talc, mica, silica, kaolin, clay, attapulgite, romite powder, quartz powder, zinc white, diatomaceous earth, montmorillonite,
Permiculite, amorphous silica, glass powder, silica-alumina, wollastonite, hytron, boron,
Nitrite, carbon black, pyroferrite, graphite, zinc sulfide, boron nitride, silicon resin powder, silicates such as calcium, magnesium, aluminum, lithium, barium, titanium, etc., sulfates, carbonates, phosphates, aluminates , Oxides and the like. Examples of the organic nucleating agent include metal salts of aliphatic carboxylic acids, metal salts of aromatic carboxylic acids such as benzoic acid and terephthalic acid, aromatic phosphonic acids and metal salts, metal salts of aromatic phosphates, benzenesulfonic acid, and naphthalene. Metal salts of aromatic sulfonic acids such as sulfonic acid, metal salts of β-diketones, polymer compounds having metal salts of carboxyl groups, fine powders of crystalline polymers such as 4,6 nylon and parahydroxylbenzoate, etc. Is exemplified. A filler may be added as a reinforcing agent or for increasing the volume. Such fillers are not particularly limited, and as fillers for reinforcement, carbon black, calcium carbonate, magnesium carbonate, kaolin, calcined clay, talc, aluminum silicate, calcium silicate, silicic acid, carbon fiber, glass Fiber, asbestos fiber, aramid fiber, potassium titanate fiber and the like. To add the resin modifier according to the present invention,
An ordinary method for preparing a resin composition is used. For example, predetermined additives used as necessary are mixed with a V-blender, a ribbon blender, a Henschel mixer, a tumbler blender, etc., and a Banbury mixer, a kneader, an oven roll, a single screw extruder, a twin screw extruder are used. The desired resin composition can be obtained by mixing with a kneader such as a single-axis reciprocating screw. The thermoplastic resin composition to which the diimide compound is added as described above is suitable for various molded article materials, for example, electric, electronic equipment parts, automobile equipment parts, and chemical parts materials. . The present invention will be described below in detail with reference to examples. In addition, the identification of the imide compound prepared in each Production Example was performed using NMR and IR. Production Example 1 3,3'-4,4'-diphenylsulfonetetracarboxylic dianhydride (hereinafter abbreviated as "DSDA")
8 g (0.1 mol) and 37.0 g of laurylamine (0.
2 mol) was mixed and stirred in xylene, and the temperature was raised. While separating and removing generated water and xylene, the mixture was heated until the temperature finally reached 230 ° C., and the reaction was continued until the generated water reached 3.6 g. After completion of the reaction, the mixture is neutralized with a 10% aqueous sodium hydroxide solution, treated with clay, filtered, and the remaining xylene is topped to obtain the desired imide compound (imide A).
66.4 g were obtained (96% yield). Production Example 2 The reaction and post-treatment were carried out in the same manner as in Production Example 1 except that 35.8 g (0.1 mol) of DSDA and 52.2 g (0.2 mol) of paradodecylaniline were used. 77.6 g of the imide compound (the present imide B) was obtained (yield: 92%). Production Example 3 39.4 g of 3,3′-4,4′-diphenylsulfonetetracarboxylic acid (hereinafter abbreviated as “DSTC”)
(0.1 mol) and 54.2 g (0.2
Mol) was mixed and stirred in xylene, and the temperature was raised. Production Example 1
The reaction was continued in the same manner as described above until the amount of produced water became 5.6 g. After completion of the reaction, xylene is topped as it is, and the desired imide compound (the present imide C) is 86.2.
g was obtained (96% yield). Production Example 4 39.4 g (0.1 mol) of DSTC and tallowamine 5
4.2 g (0.2 mol) was mixed and stirred in xylene, and the temperature was raised. The produced water was 5.1 while reacting in the same manner as in Production Example 1.
The reaction was continued until it reached 6 g. After completion of the reaction, the mixture is neutralized by adding 1.2 g of calcium hydroxide, and topped with xylene as it is to obtain the desired imide compound (the present imide D).
86.7 g were obtained (98% yield). Example 1 A sample was prepared by blending 5 parts by weight of "the present imide A" with 100 parts by weight of a PPS resin in a Labo Plast mixer, then melt-kneading at 290 ° C and molding at 100 ° C. The heat of recrystallization of this sample by DSC measurement was 0.2 mW / mg. Comparative Example 1 The heat of recrystallization of the PPS resin itself used in Example 1 was measured according to Example 1, and was found to be 7.4 mW / mg. Example 2 A mixture of 5 parts by weight of "the present imide B" and 3 parts by weight of talc as a crystallization nucleating agent in a Henschel mixer with respect to 100 parts by weight of a PET resin was melt-mixed with an extruder to obtain a mixture. The stelland was cooled with water and cut to obtain a sample. According to DSC measurement of this sample, the difference between the melting point when the temperature was raised and the crystallization temperature when the temperature was lowered was 129 ° C., and the crystallization temperature was 89 ° C. Comparative Example 2 The temperature difference of the PET resin used in Example 2 was measured according to Example 2, and it was 90 ° C., and the crystallization temperature was 1
17 ° C. Example 3 "The present imide C" was added to 100 parts by weight of a polystyrene resin.
2.5 parts by weight were added and kneaded at 200 ° C. with a Labo Plastomill to obtain a sample. The melt flow rate (MFR) of this sample was 1 mm in diameter at 200 ° C. under a load of 5 kg.
The amount of the molten resin extruded from the orifice having a length of 10 mm in 10 minutes was 5.1 g / 10 minutes. Comparative Example 3 The MFR of the polystyrene resin used in Example 3 was measured and found to be 2.6 g / 10 minutes. Example 4 "Non-imide D" 5 per 100 parts by weight of 12 nylon resin
A sample in which parts by weight were kneaded at 185 ° C. on an oven roll was used as a sample. The MFR of this sample was measured at a temperature of 240 ° C and a load of 2
The amount of the molten resin extruded from an orifice having a diameter of 1 mm and a length of 10 mm at 0 kg in 10 minutes was 23.2 g / 10 minutes. Comparative Example 4 The MFR of the nylon 12 resin used in Example 4 was measured in Example 3.
It was 6.5 g / 10 minutes when measured according to. The imide compound according to the present invention is excellent in heat resistance and can be mixed with a thermoplastic resin to lower the melt viscosity of the target resin and promote crystallization. .

──────────────────────────────────────────────────続 き Continued on front page (58) Field surveyed (Int.Cl. ⁷ , DB name) C08L 1/00-101/16

Claims (1)

(57) [Claim 1] A diimide represented by the general formula (1), a monoimide represented by the general formula (2), and a metal salt of the monoimide with respect to 100 parts by weight of the thermoplastic resin. A thermoplastic resin composition comprising 0.1 to 100 parts by weight of one or more imide compounds selected from the group consisting of: Embedded image [Wherein, R ¹ and R ² are the same or different and each have 4 to 28 carbon atoms.
A linear or branched alkyl or alkenyl group, a cycloalkyl group having 4 to 6 carbon atoms, Or Represents R ³ represents an alkyl group having 1 to 22 carbon atoms.
R ⁴ and R ⁶ represent a single bond or an alkylene group having 1 to 2 carbon atoms. R ⁵ represents an alkyl group having 1 to 22 carbon atoms. a is 1
And b represents an integer of 0 to 2. ] [Y when in the formula, X is a group NHR ⁷ represents a hydroxyl group, X when Y is a group NHR ⁷ represents a hydroxyl group. R ⁷ and R ⁸ have the same meaning as R ¹ in formula (1), and may be the same or different. ]