JPH059361A - Abs resin composition having improved processability - Google Patents

Abstract

PURPOSE:To provide the subject composition composed of ABS resin and a specified amount of a specified oligoamide compound blended therewith, capable of producing a molding excellent in surface properties, free from lowering of thermal deformation temperature of the resin and capable of blending vinyl chloride resin without a danger of peeling. CONSTITUTION:An objective composition obtained by blending (A) 100 pts.wt. ABS resin with (B) 0.01-20 pts.wt. (preferably 0.05-10 pts.wt.) oligoamide compound represented by formula R1-(-CO-R3-CO-NH-R4-NH-)n-(CO-R5-NH-)n-R2 (R1 is HO-, NH2-R4-NH-, R6-NH- or R7-CO-NH-R4-NH-; R2 is -H, -CO-R7, -CO-R3- OH or -CO-R3-CO-NH-R6; R3-R5 are 1-12C alkylene; R6 and R7 are 1-18C alkyl; m and n are 0-40 and m+n=2-40) and preferably having 60-300 deg.C softening point.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to an ABS resin composition, and more particularly to an ABS resin composition having improved processability by adding a specific oligoamide compound.

[0002]

2. Prior Art and Problems to be Solved by the Invention ABS
Resins have excellent heat resistance, impact resistance, chemical resistance, and good surface gloss, and are used in a wide range of applications such as automobile parts, electric industrial parts, and office machines. .. Further, since ABS resin has good compatibility with other resins, it is often used by blending it with vinyl chloride, polycarbonate, polyurethane, nylon or the like.

However, ABS resin has a drawback that it is inferior in processability such as fluidity, and particularly when blended with other resins, this drawback becomes remarkable, so that it is necessary to further improve the processing performance. It was Conventionally, lubricants such as higher fatty acid metal salts or higher fatty acid amides have been used in order to improve the processability of ABS resin, but these lubricants are not only insufficient in their effect, However, it is not satisfactory in practical use because it is extremely inferior in properties or has a drawback of lowering the heat distortion temperature of the resin.

It has been proposed to add an ester compound in order to improve the processability of the ABS resin (JP-A-2-135248 and JP-A-2-135249), but the effect is not yet satisfactory. In particular, when a vinyl chloride resin or the like is blended with the ABS resin, there is a drawback that peeling (a phenomenon in which peeling occurs in layers when the sheet is bent) occurs. Therefore, the surface properties of the molded product are good, and the heat distortion temperature of the resin is not lowered, and even when blended with a vinyl chloride resin, peeling does not occur and the workability is excellent. It has been sought to find an ABS resin composition.

[0005]

Means for Solving the Problems The inventors of the present invention have made extensive studies in view of the above-mentioned situation, and as a result, by blending the ABS resin with a specific oligoamide compound, the ABS resin having remarkably improved processability was obtained. The inventors have found that a composition can be obtained and have reached the present invention.

That is, the present invention relates to an ABS resin having improved processability, which is obtained by mixing 0.01 to 20 parts by weight of the oligoamide compound represented by the following general formula (I) with 100 parts by weight of the ABS resin. A composition is provided. R ₁ -(-CO-R ₃ -CO-NH-R ₄ -NH-) _m -(-CO-R ₅ -NH-) _n -R ₂ (I) (wherein R ₁ is HO-, NH ₂ -R ₄ -NH-, R ₆ -NH- or R ₇ -CO-NH
-R ₄ -NH-, R ₂ is -H, -CO-R ₇ , -CO-R ₃ -CO-OH or
-CO-R ₃ -CO-NH-R ₆ is shown. R ₃ , R ₄ and R ₅ each have 1 carbon atom
~ 12 are one or more kinds selected from alkylene groups, and R ₆ and R ₇ are each an alkyl group having 1 to 18 carbon atoms. m and n each represent 0 to 40, and m + n is 2
~ 40. )

The present invention having the above gist will be described below in more detail.

In the above general formula (I), the alkylene groups represented by R ₃ , R ₄ and R ₅ include methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, undecylene, Examples of the alkyl group represented by R ₆ and R ₇ include dodecylene and the like. Methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, hexyl, octyl, 2-ethylhexyl, decyl, dodecyl, tridecyl, tetradecyl, Examples include octadecyl, dimethylaminopropyl, methoxyethyl and the like.

The oligoamide compound represented by the above general formula (I) is obtained by reacting, for example, a dibasic acid and a divalent amine or a lactam and, if necessary, a monobasic acid or a monovalent amine as an end-terminating component. It can be easily produced by, and they can be reacted all at once or sequentially.

The oligoamide compound represented by the above general formula (I) may have two or more kinds of dibasic acid components and / or divalent amine components or lactam components. It may be a polymer or a random copolymer.

The dibasic acid used in the synthesis of the oligoamide compound represented by the above general formula (I) includes malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid,
Suberic acid, azelaic acid, sebacic acid and the like, and as the divalent amine, ethylenediamine, propylenediamine, hexamethylenediamine, undecamethylenediamine, dodecamethylenediamine, and the like,
As the monobasic acid, acetic acid, propionic acid, butyric acid, valeric acid, isovaleric acid, caproic acid, heptanoic acid, caprylic acid, 2-ethylhexylic acid, pelargonic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid. Examples of the acid include monoamines such as methylamine, ethylamine, propylamine, butylamine,
Examples thereof include pentylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, undecylamine, dodecylamine, tridecylamine, tetradecylamine, pentadecylamine, hexyldecylamine, heptadecylamine and octadecylamine.

The oligoamide compound represented by the above general formula (I) preferably has a softening point of 60 to 300 ° C.,
It is more preferably in the range of 100 to 250 ° C., and if the softening point is less than 60 ° C., the heat distortion temperature of the resin tends to be lowered, and if it exceeds 300 ° C., insoluble matter may remain during processing. The number average molecular weight thereof is preferably 500 to 10000, more preferably 1000 to 5
It is appropriately selected from the range of 000. The average molecular weight is determined by the degree of polymerization and the type of raw material used, but can be arbitrarily determined by adjusting the molar ratio of each component of the raw material used and the condensation method.

The blending amount of the oligoamide compound represented by the above general formula (I) is 100 parts by weight of ABS resin.
It is 0.01 to 20 parts by weight, preferably 0.05 to 10 parts by weight.

Hereinafter, the oligoamide compound used in the present invention will be described in more detail with reference to synthetic examples, but the present invention is not limited to the following synthetic examples.

[Synthesis Example] Synthesis of oligoamide compound (Sample No. 1) from adipic acid / sebacic acid / ethylenediamine / hexamethylenediamine

Adipic acid 187.1 g, sebacic acid 38
8.3 g, ethylene diamine 76.9 g, hexamethylene diamine 223.1 g and lauric acid 64.1 g were charged all at once and heated to 150 ° C. under a nitrogen stream to melt. The temperature rises gradually with stirring, and finally reaches 250 ° C.
The temperature was raised to. Subsequently, dehydration is performed under reduced pressure, and the theoretical amount of water is 1
After confirming that 15.2 g had been distilled, the reaction was completed. Finally, the reaction was removed from the reaction vessel and cooled to give a pale yellow solid. For synthetic products, heating rate 10 under nitrogen
The softening point was measured by performing differential thermal analysis at ° C / min. Further, the number average molecular weight was measured by the terminal group quantification method.

Softening point: 150 ° C to 165 ° C Number average molecular weight: 2300

By appropriately changing the dibasic acid and the divalent amine or the lactam and the monobasic acid or the monovalent amine as the terminal terminating component, the oligoamide compound shown in the following Table 1 is synthesized by the same operation as in the above Synthesis Example. did.

[0019]

[Table 1]

The ABS resin used in the present invention includes:
AS which is a copolymer with acrylonitrile and styrene
Those produced by a blending method in which a resin and polybutadiene are mechanically blended using a heating mill or mixed in a latex form, in the coexistence of polybutadiene latex, one produced by a grafting method of polymerizing styrene and acrylonitrile, What was manufactured by a conventionally well-known method, such as what was manufactured by the graft blending method which blends the ABS resin latex manufactured by the graft method with the AS resin latex manufactured separately, can be used, and it is limited by the manufacturing method. Not a thing. Further, for improving heat resistance, for example, N-phenylmaleimide, N-cyclohexylmaleimide modified by copolymerization, or heat-resistant ABS in which a part or all of styrene is replaced with α-methylstyrene is used. It may be. Further, for example, in order to improve flame retardancy, it is possible to use it by blending it with a vinyl chloride resin or the like. In this case, a resin containing about 40% by weight or more of ABS resin in all resins is used. be able to.

By adding a phenolic antioxidant to the ABS resin composition of the present invention, thermal oxidative deterioration is remarkably improved.

Examples of the phenolic antioxidant used in the present invention include 2,6-di-tert-butyl-p-
Cresol, 4,4'-thiobis (6-tert-butyl-m
-Cresol), 4,4'-butylidene bis (6-tert-butyl-m-cresol), 4,4'-isopropylidene bis (2-tert-butylphenol), 4,4'-methylenebis (2,6-di) Tert-butylphenol), 2,
2'-methylenebis (4-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-ethyl-6-
Tert-butylphenol), 2,2'-ethylidenebis (4,6-di-tert-butylphenol), 2,2'-ethylidenebis (4-tert-butyl-6-tert-butylphenol), 2-tert-butyl- 4-methyl-6- (2-acryloyloxy-3-tert-butyl-5-methylbenzyl)
Phenol, stearyl-β- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 1,6-
Hexamethylene bis [β- (3,5-di-tert-butyl-4]
-Hydroxyphenyl) propionate], 3-thia-
1,5-Pentanebis [β- (3,5-di-tert-butyl-
4-hydroxyphenyl) propionate], 2,2-
Bis [4- {2- (β- (3,5-di-tert-butyl-4-
Hydroxyphenyl) propionyloxy) ethyl} phenyl] propane, 3,7-dioxa-1,8-octanebis [β- (3-tert-butyl-4-hydroxy-5-
Methylphenyl) propionate], 3,9-bis [1,1-dimethyl-2- (β- (3-tert-butyl-4)
-Hydroxy-5-methylphenyl) propionyloxy) ethyl-2,4,8,10-tetraoxaspiro [5,5] undecane, pentaerythritol tetrakis [β- (3,5-di-tert-butyl-4-hydroxy) Phenyl) propionate], 1,3,5-tris (2,6
-Dimethyl-3-hydroxy-4-tert-butylbenzyl) isocyanurate, 1,3,5-tris (3,5-
Di-tert-butyl-4-hydroxybenzyl) isocyanurate, 2-octylthio-4,6-di (3,5-di-tert-butyl-4-hydroxyphenoxy) -s-triazine, bis [2-tert-butyl- 4-Methyl-6- (2-hydroxy-3-tert-butyl-5-methylbenzyl) phenyl] terephthalate, 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane , 1,3,5-Tris (3,5-di-tert-butyl-4hydroxybenzyl) -2,4,6-trimethylbenzene, 1,2-ethanebis [3,3-bis (4-hydroxy-3-) Tert-butylphenyl) butyrate] and the like.

Among the above phenolic antioxidants,
Since a compound having a molecular weight of less than 500 tends to foam during molding, it is preferable to use a compound having a molecular weight of 500 or more. In particular, β- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid monovalent An ester of a tetrahydric alcohol and / or a 1,3,5-tris (alkylated hydroxybenzyl) isocyanurate compound is preferable because it has an extremely large stabilizing effect on thermal oxidation.

The amount of the above-mentioned phenolic antioxidant added is
It is preferably 0.01 to 100 parts by weight of ABS resin.
5 parts by weight, more preferably 0.05 to 3 parts by weight.

The composition of the present invention also includes tris (nonylphenyl) phosphite, octyldiphenylphosphite, distearyl pentaerythritol diphosphite, bis (2,4-ditertiary butylphenyl) pentaerythritol diphosphite. Fight, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,4,6-tri-tert-butylphenyl) pentaerythritol diphosphite, 2,2'-
Methylenebis (4,6-di-tert-butylphenyl) ・ 2-
Organic phosphite compounds such as ethylhexyl phosphite: phthalate ester-based plasticizers, ester-based plasticizers such as adipic acid ester-based plasticizers, polyester-based plasticizers,
Plasticizers such as epoxy plasticizers, phosphate ester plasticizers, chlorine plasticizers; lithium, sodium, magnesium,
Metal-containing compounds such as organic carboxylates of metals such as calcium, barium, zinc, cadmium, aluminum, tin, organotin, lead, organic phenol salts, organic phosphates, organic phosphites and organic mercaptides; dehydroacetic acid , Dibenzoylmethane, stearoylbenzoylmethane, etc.
Diketone compounds; benzophenone-based, benzotriazole-based, salicylate-based, hindered amine-based, substituted acrylonitrile-based light stabilizers and the like can be appropriately used depending on the application.

In addition, if necessary, the composition of the present invention contains a crosslinking agent, a filler, a pigment, a foaming agent, an antistatic agent, an antifogging agent, an antiplateout agent, a surface treatment agent, a flame retardant, and a fluorescent agent. , An antifungal agent, a bactericidal agent, a photodegradation agent, a release agent and the like can be included.

[0027]

EXAMPLES Next, the present invention will be specifically described by way of examples. However, the invention is not limited by these examples.

Example 1 Styrene 2 was added in the presence of 70 parts by weight of polybutadiene rubber.
Graft polymer obtained by polymerizing 2.5 parts of acrylonitrile and 7.5 parts of a-methylstyrene 50% by weight, methyl methacrylate 35% by weight and acrylonitrile 15
% Of the copolymer was mixed at a ratio of 25:75 by weight, and heat resistance A with an α-methylstyrene content of 37.5% by weight was used.
BS resin was obtained.

100 parts by weight of this heat-resistant ABS resin was mixed with pentaerythritol tetrakis [β- (3,5-ditert-butyl-4-hydroxyphenyl) propionate] 0.
15 parts by weight, 0.25 parts by weight of bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, 0.4 parts by weight of magnesium stearate and the sample compound were added (the addition amount is shown in Table 2). And mixed well.
Using this mixture, the cylinder temperature was 260 ° C and the rotation speed was 2
Pellets were prepared using a 5 rpm twin-screw extruder, and the surface condition was observed.

Using the pellets obtained by the above-mentioned operation, a spiral flow was conducted with a melt indexer under a load of 2160 g, a melt index (MI: g / 10 min) under the conditions of 265 ° C. and a condition of 260 ° C. and 6 Kg · f / cm. (Cm) was measured. In addition, this pellet was heated at 260 ° C, 6
Injection molded under the condition of Kg · f / cm, 127 × 12.7 ×
A 6.4 mm square rod-shaped test piece was prepared and conformed to JIS K-68.
According to No. 71, the heat distortion temperature (° C.) was measured.

Further, a test piece injection-molded after being retained in the injection molding machine for 10 minutes was prepared, and the color difference (ΔE) from the non-retained test piece was measured.

As the sample compound, in this example, the oligoamide compound (Sample N) used in the present invention was used.
o.1 to No. 5), and ethylene bisstearic acid amide (comparative compound) in Comparative Examples.

The results are shown in Table 2.

[0034]

Example 2 50 parts by weight of ABS resin (Brendex 111), 50 parts by weight of vinyl chloride resin (Geon 103 EP-8), 1.0 part by weight of dibutyltin-β-mercaptopropionate, 3 parts of dibutyltin-maleate. 0.0 parts by weight and the sample compound (addition amount shown in Table 3) were thoroughly mixed. Using this mixture, pellets were prepared using a twin-screw extruder having a cylinder temperature of 200 ° C. and a rotation speed of 25 rpm, and the surface state was observed.

Using the pellets obtained by the above-mentioned operation, a melt index (MI: g / 10 minutes) under a load of 2160 g and a temperature of 200 ° C. and a spiral flow under the conditions of 200 ° C. and 6 Kg · f / cm were used. (Cm) was measured. In addition, this pellet at
Injection molding under conditions of kgf / cm 127 x 12.7 x
A 6.4 mm square rod-shaped test piece was prepared and conformed to JIS K-68.
According to No. 71, the heat distortion temperature (° C.) was measured. The peeled state when the test piece was bent was observed.

As the sample compound, in this example, the oligoamide compound used in the present invention (Sample N
o.1 to No. 5), and ethylene bisstearic acid amide (comparative compound) in Comparative Examples.

The results are shown in Table 3.

[0039]

Example 3 50 parts by weight of the heat-resistant ABS resin of Example 1, 50 parts by weight of vinyl chloride resin (Geon 103 EP-8), 1.0 part by weight of dibutyltin-β-mercaptopropionate, dibutyltin-maleate. 3.0 parts by weight, 1,1,3-tris (2-methyl-
4-hydroxy-5-tert-butylphenyl) butane 0.
5 parts by weight and 2.0 parts by weight of the sample compound were thoroughly mixed. Using this mixture, pellets were prepared using a twin-screw extruder with a cylinder temperature of 200 ° C. and a rotation speed of 25 rpm,
The surface condition was observed.

Using the pellets obtained by the above operation, a melt index (MI: g / 10 minutes) under a load of 2160 g and a temperature of 200 ° C. and a spiral flow under the conditions of 200 ° C. and 6 kg · f / cm were used with a melt indexer. (Cm) was measured. In addition, this pellet at
Injection molding under conditions of kgf / cm 127 x 12.7 x
A 6.4 mm square rod-shaped test piece was prepared and conformed to JIS K-68.
According to No. 71, the heat distortion temperature (° C.) was measured. The peeled state when the test piece was bent was observed.

As a sample compound, in this example, the oligoamide compound used in the present invention (Sample N
o.1 to No. 5), and ethylene bisstearic acid amide (comparative compound) in Comparative Examples.

The results are shown in Table 4.

[0044]

Example 4 N-phenylmaleimide-modified ABS resin (heat distortion temperature 1
30 ° C.) 100 parts by weight, 1,3,5-tris (3-ditertiarybutyl-4-hydroxybenzyl) isocyanurate 0.25 parts by weight, calcium stearate 0.5 parts by weight, and sample compound (addition amount is shown in Table 1). (Shown in -5),
Pellets were prepared using a twin-screw extruder having a rotation speed of 200 rpm and a cylinder temperature of 250 ° C.

Using the pellets, an injection molding machine (cylinder temperature 280 ° C. and 300 ° C., nozzle temperature 300
A test piece having a thickness of 2 mm was prepared at (° C.), and a silver streak on the surface of the test piece was observed at 280 ° C. when not retained and at 300 ° C. for 5 minutes. The generation state of the silver streak is displayed in 10 stages, and 1 (none) ← →→ 10 (large) is shown. At the same time, the yellowness of the test piece was measured using a Hunter colorimeter, and the test piece was measured at 300 ° C. for 5 minutes at 280 ° C.
The color difference (ΔE) after the retention for a minute was measured.

As the sample compound, in the present example, the oligoamide compound used in the present invention (Sample N
o.1 to No. 5), and ethylene bisstearic acid amide (comparative compound) in Comparative Examples. The results are shown in Table-5.

[0048]

As is clear from each example, when ethylenebisstearic acid amide is used, not only the heat distortion temperature of the resin is significantly lowered, but also the surface of the molded article which is considered to be caused by thermal decomposition or volatilization. The deterioration of the state is also recognized, and the deterioration of the hue due to being left in a high temperature molten state is remarkable.

On the other hand, when the oligoamide compound used in the present invention is used, not only the processability (MI, spiral flow) and the surface condition of the molded product are good, but also
It is clear that the heat distortion temperature is hardly lowered, and that the deterioration of the hue is extremely small even if the heat distortion temperature is left as it is.

[0051]

EFFECTS OF THE INVENTION The ABS resin composition of the present invention has good surface properties of the molded product, does not lower the heat distortion temperature of the resin, and peels even when blended with vinyl chloride resin. It has excellent workability and does not cause

Claims (1)

Claims: 1. An oligoamide compound represented by the following general formula (I) 0.01-2 based on 100 parts by weight of an ABS resin.
An ABS resin composition having an improved processability, which comprises 0 part by weight. R ₁ -(-CO-R ₃ -CO-NH-R ₄ -NH-) _m -(-CO-R ₅ -NH-) _n -R ₂ (I) (wherein R ₁ is HO-, NH ₂ -R ₄ -NH-, R ₆ -NH- or R ₇ -CO-NH
-R ₄ -NH-, R ₂ is -H, -CO-R ₇ , -CO-R ₃ -CO-OH or
-CO-R ₃ -CO-NH-R ₆ is shown. R ₃ , R ₄ and R ₅ each have 1 carbon atom
~ 12 are one or more kinds selected from alkylene groups, and R ₆ and R ₇ are each an alkyl group having 1 to 18 carbon atoms. m and n each represent 0 to 40, and m + n is 2
~ 40. )