JPH032255A - Heat-resistant abs resin composition - Google Patents

Abstract

PURPOSE:To provide a resin composition having excellent heat resistance, excellent weather resistance and improved processability by compounding maleimide or alpha-methylstyrene-modified ABS resin with a specific amount of a specified organic cyclic phosphite compound. CONSTITUTION:100 pts.wt. of a maleimide or alpha-methylstyrene-modified ABS resin is compounded with 0.001-5 pts.wt. of an organic phosphite compound of the formula (R1 is tertiary butyl or tertiary amyl; R2 is 1-9C alkyl; R3 is H or 1-4C alkyl; R4 is 1-30C alkyl), e.g. 2,2'-methylenebis(4,6-ditertiary butylphenyl)stearyl phosphite.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to an improved heat-resistant ABS resin composition, and more particularly, to an improved heat-resistant ABS resin composition.
The present invention relates to an improved heat-resistant ABS resin composition containing a resin and a specific organic cyclic phosphite compound.

[Conventional technology and its problems]

Maleimide or α-methylstyrene-modified ABS resin has an excellent balance of heat resistance, impact resistance, and fluidity, and can be molded and secondary processed in the same way as ABS resin. Because it has characteristics that resins and engineering plastics do not have, it is expected to be used in a wide range of applications, including automobile parts, electrical industry parts, and office machines.

However, in maleimide-modified ABS resins, as the ratio of the maleimide compound increases, the heat resistance improves, but the compatibility between the maleimide-containing copolymer and the graft copolymer deteriorates, and as a result, the impact resistance decreases, and the rubber There is a drawback that the excellent properties as a reinforced resin are impaired. Also, α−
Since methylstyrene-modified ABS resin is copolymerized with α-methylstyrene, it tends to undergo thermal decomposition due to depolymerization (it has drawbacks such as poor moldability and brittleness).

In addition, due to the introduction of maleimide or α-methylstyrene components, the fluidity within the mold during processing is reduced, so when manufacturing large molded parts, the processing temperature is higher than that of conventional ABS resin. , it is necessary to set the temperature to 260°C or higher. As a result, thermal oxidative deterioration of the resin becomes significant,
Silver streaks (or flash) are generated on the surface of the molded product, impairing the product appearance.

In order to improve this, for example, 1,3.5-tris (3
, 5-ditert-butyl-4-hydroxybenzyl) isocyanurate (JP-A-62-45643) or 3
- Phenol compounds such as tert-butyl-4-hydroxy-5-methylphenylpropionic acid ester (JP-A-62-181352 and JP-A-62-220544) or bis(2,6-di-tert-butyl -4-
Alkylphenyl) pentaerythritol diphosphite compounds (Japanese Unexamined Patent Publication No. 63-254157) have been proposed, and although some improvement has been recognized, it is still not sufficient (further improvements have been desired).

[Means for solving problems]

In view of the current situation, the inventors of the present invention have conducted extensive studies, and have found that
It has been discovered that by adding a specific organic cyclic phosphite compound to a maleimide-modified or α-methylstyrene-modified ABS resin, it not only has excellent heat resistance and weather resistance, but also significantly improves processability, and has developed the present invention. It is completed.

That is, the present invention provides the following general formula (I
) is an organic cyclic phosphite compound represented by 0.001
The object of the present invention is to provide a stabilized heat-resistant ABS resin composition containing 5 parts by weight.

R.

(In the formula, R represents a tert-butyl group or a tertiary amyl group, R2 represents an alkyl group having 1 to 9 carbon atoms, R3 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms,
R4 represents an alkyl group having 1 to 30 carbon atoms. ) above - at most 1 to 9 carbon atoms represented by R2;
Examples of alkyl groups include methyl, ethyl, propyl, isopropyl, butyl, nibutyl, tertiary butyl, isobutyl, amyl, tertiary amyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, tertiary octyl, nonyl, trinonyl, etc., and R3 and R2
Examples of the alkyl group having 1 to 4 carbon atoms represented by R4 include methyl, ethyl, propyl, isopropyl, butyl, nibutyl, tert-butyl, isobutyl, and the alkyl group having 1 to 30 carbon atoms represented by R4. Examples of alkyl groups include methyl, ethyl, propyl, isopropyl, butyl, nibutyl, tertiary butyl, isobutyl, amyl, tertiary amyl, hexyl, heptyl, octyl, isooctyl, 2-
Ethylhexyl, tertiary octyl, nonyl, tertiary nonyl,
Examples include decyl, isodecyl, dodecyl, tetradecyl, hexadecyl, octadecyl, eicosyl, tocosyl, tetradecyl, triacontyl, and the like.

Next, as representative examples of the organic cyclic phosphite compound represented by the above-mentioned maximum (I) used in the present invention, the compounds shown in the following Table 1 can be mentioned.

Table-1 t-C,)l.

t-CaHq t-Cn)lv -C4Hw -CaHq -CJq t-Cs)I ■ t-CaHq The organic cyclic phosphite compound represented by maximum (1) above used in the present invention is, for example, phosphorus trichloride. and 2.2”
- It can be easily produced by reacting an alkylidene bisphenol to produce a compound in which R4-0- is a chlorine atom in the maximum CI) above, and reacting this with an alcohol represented by R4-OH. can.

Next, a specific synthesis example of the organic cyclic phosphite compound used in the present invention will be shown.

Synthesis Example 2 (methylenebis 46-ditributylphenyl),
Completed.

42.5 g of 2.2' in a 500 quart flask
-methylenebis(4,6-di-tert-butylphenol),
100 g toluene and 0.86 g triethylamine
16.5 g of phosphorus trichloride was added to 60 to 60 g of phosphorus trichloride without stirring.
It was added dropwise at 5°C. After the dropwise addition was completed, the temperature was gradually raised under a nitrogen stream, and the mixture was stirred under reflux for 2 hours.

Excess phosphorus trichloride was distilled off under reduced pressure, and after cooling to 60''C, 12.1 g of triethylamine and 27 g of stearyl alcohol were added, and the mixture was stirred at 80°C for 4 hours.

After cooling, the generated triethylamine hydrochloride was filtered off, and the solvent was distilled off.

The residue was crystallized from methanol to give a white powder product with a melting point of 65°C.

IR(am-') 2925, 2850: methylene, 1230.1200
: tert-butyl, 1too: -o-phenyl, 102
0: P-0-alkyl, 840: P-0-phenyl H'-NMR (in CDC13, 60 MHz, TMS
Standard) δ value; 0.8: 3H, t, methyl group (stearyl group end) 1.2-1.3: 73H, sss, tert-butyl group and stearyl group 3.2-4.4: 4H, dd , methylene group and -
o-cut-7,2:4H,s, aromatic hydrogen The amount of these organic cyclic phosphite compounds added is from o, ooi to 5 parts by weight per 100 parts by weight of the synthetic resin.

The method of adding the organic cyclic phosphite compound represented by (I) of the present invention to the heat-resistant ABS resin is not particularly limited, and commonly used methods can be applied as is.

For example, a method of tri-blending resin powder or pellets with additive powder, a method of spraying a solution or melt of the additive onto the resin powder or pellets, a method of mixing a dispersion of the additive with resin latex, and then salting out. method etc. can be used.

The heat-resistant ABS resin in the present invention includes, for example, an aromatic vinyl monomer, a copolymer in which a maleimide compound is blended with a vinyl cyan monomer, and an aromatic vinyl monomer and A resin composition consisting of a graft copolymer obtained by copolymerizing a vinyl cyan monomer, a resin composition in which a maleimide compound is also blended into the grafts of the graft copolymer, and a resin composition in the presence of a conjugated diolefin rubber. , a graft copolymer obtained by copolymerizing an aromatic vinyl monomer, a vinyl cyan monomer, and a maleimide compound, an ABS resin obtained by graft polymerizing styrene and acrylonitrile to a diene polymer, and α-methylstyrene. Method for blending acrylonitrile copolymer, α-methylstyrene/acrylonitrile/styrene copolymer, α-methylstyrene/acrylonitrile/2,5-dichlorostyrene copolymer, or α-methylstyrene/acrylonitrile/methyl methacrylate copolymer , a method in which styrene and acrylonitrile are grafted onto a diene rubber latex, and then α-methylstyrene and acrylonitrile are grafted thereon, a method in which a part of the styrene is replaced with α-methylstyrene using an NBR/As blend, or a method in which a part of the styrene is replaced with α-methylstyrene, or butadiene, acrylonitrile, and styrene. It is obtained by blending a copolymer with an α-methylstyrene/acrylonitrile copolymer, and has a high heat distortion temperature.

In addition, these heat-resistant ABS resins include, for example, polycarbonate resin, saturated polyester resin, polyamide resin,
By using it in combination with engineering resins such as polyphenylene ether resin and polyacetal resin, one of the drawbacks of these engineering resins, which is low notched impact strength, can be improved.

The oxidative stability of the composition of the present invention can be further improved by further adding a phenolic antioxidant. Examples of this phenolic antioxidant include 2
, 6-di-tert-butyl-p-cresol, 2,6-diphenyl-4-octadecyloxyphenol, distearyl (3,5-di-tert-butyl-4-hydroxybenzyl) phosphonate, 4.4°-thiobis(6 -tert-butyl-m-cresol), 2-octylthio-4,6-di(
3'5'-dihydroxyphenoxy) -S-triazine, 2,2°-methylenebis(4-methyl-6-tert-butylphenol), 2,2'methylenebis(4-ethyl-6-tert-butylphenol), bis[ 3,3-bis(4°-hydroxy-3"-tert-butylphenyl]butyric acid] glycol ester, 4,4"-butylidenebis(6-tert-butyl-m-cresol L2°2'-ethylidenebis( 4,6-di-tert-butylphenol), 2,2'-ethylidenebis(4-sec-butyl-
6-tert-butylphenol), 2-tert-butyl-4-methyl-6-(2'-acryloyloxy-3'-tert-butyl-5'-methylbenzyl)phenol, bis[2
-tert-butyl-4-methyl-6-(2°-hydroxy-
3°-tert-butyl-5′-methylbenzyl)phenyl]
Terephthalate, 1.1.3-)Lis(2′-methyl-4°-hydroxy-5”-tert-butylphenyl)butane, 1.3.5-)Lis(2°,6′-dimethyl-3
゛-Hydroxy-4゛-tert-methylbenzyl) isocyanurate, 1,3,5-tris(3°,5゛-ditert-butyl-4"-hydroxybenzyl) isocyanurate,
1,3,5-tris(3',5'-di-tert-butyl-4
(°hydroxybenzyl)-2,4,6-)listylbenzene and the like.

It is also possible to further add a sulfur-based antioxidant to the composition of the present invention to improve its oxidative stability.

Examples of the sulfur-based antioxidant include dialkyl thiodipropionates such as dilauryl, simiristyl, and distearyl esters of thiodipropionic acid, and β-alkyl esters of polyols such as pentaerythritol tetra (β-dodecylmercaptopropionate). Examples include mercaptopropionate esters.

By adding a light stabilizer such as an ultraviolet absorber or a hindered amine compound to the composition of the present invention, its light resistance can be further improved.

Examples of the light stabilizer include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-bitroxy-4-octoxybenzophenone, and 5,5'-methylenebis(2-hydroxy-4-methoxybenzophenone). 2-hydroxybenzophenone [; 2-(2°-hydroxy-5'-methylphenyl)benzotriazole, 2-(2''-hydroxy-
5'-tertiary octylphenyl)benzotriazole, 2
-(2°-hydroxy-3',5"-di-tert-butylphenyl)benzotriazole, 2-(2"hydroxy-
3"5"-di-tert-butylphenyl)-5-chlorobenzotriazole,2-(2"-hydroxy-3°-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2 ° -Hydroxy-3゛,5”
-dicumylphenyl)benzotriazole, 2,2°
-2-(2”-hydroxyphenyl)benzotriazoles such as methylenebis(4-tert-octyl-6-benzotriazolyl)phenol; phenyl salicylate, resorcinol monobenzoate, 2° 4-di-tert-butylphenyl-3° , 5'-di-tert-butyl-4''-hydroxybenzoate, hexadecyl-3,5-di-tert-butyl-4-hydroxybenzoate, and other benzoates; 2
-Substituted oxanilides such as ethyl-2''-ethoxyoxanilide, 2-ethoxy-4'-dodecyloxanilide; ethyl-α-cyano-β, β-diphenylacrylate, methyl-2-cyano-3-methyl- Cyanoacrylates such as 3-(p-methoxyphenyl)acrylate; 2.2,6.6-tetramethyl-4-piperidyl stearate, 1,2,2°6.6-bentamethyl-4-piperidyl stearate, 2 .2,6.6-tetramethyl-4-piperidylbenzoate, bis(2,2,6,6
-tetramethyl-4-piperidyl) sebacate, bis(
1,2,2,6,6-bentamethyl-4-piperidyl)
sebacate, tetrakis(2,2,6゜6-tetramethyl-4-piperidyl)butane tetracarboxylate,
Tetrakis (1,2,2゜6.6-bentamethyl-4-
piperidyl)-1゜2.3.4-butanetetracarboxylate, bis(1,2,2,6,6-bentamethyl-4-piperidyl) di(tridecyl)-1,2,3,4
Butane tetracarboxylate, bis(1,2°2.6
．． 6-bentamethyl-4-piperidyl)-2-butyl-
2-(3,5-ditert-butyl-4hydroxybenzyl)
malonate, 1-(2-hydroxyethyl)-2,2,
6,6-tetramethyl-4-piperiditul/diethyl succinate polycondensate, 1,6-bis(2,2,6,6-tetramethyl-4-piperidylamino)hexane/dibromoethane polycondensate, 6-bis (2,2', 6゜6-
Tetramethyl-4-piperidylamino)hexane/2,
4-dichloro-6=tertiary octylamino-5-) riazine polycondensate, 1,6-bis(2°2.6.6-tetramethyl-4-piperidylamino)hexane/2.4-dichloro-6 Examples include hindered amine compounds such as -morpholino-5-) riazine polycondensates.

In addition, if necessary, the composition of the present invention may contain a heavy metal deactivator, a nucleating agent, a metal soap, a pigment, a filler, an organic tin compound, a plasticizer, an epoxy compound, a blowing agent, an antistatic agent, and a flame retardant. , lubricants, processing aids, and the like.

〔Example〕

Next, the present invention will be specifically explained using examples.

However, the present invention is not limited to these examples.

Example 1 (Blend) Organic phosphite (Table 1) 0.3 The above blend was triblended and then dried at 80°C for 6 hours. Next, the cylinder temperature was 250°C and the rotation speed was 20Orp.
m two-wheel extruder (L/D=30, vent up 4 Q
m+*Hg) was used to create pellets. The pellet was dried again at 80°C for 6 hours. Using this pellet, injection molding area (1 oz, cylinder temperature 280°C and 300°C, nozzle temperature 300°C, 1 mold 60 x 36
A test piece with a thickness of 2 mm was prepared at
Silver streaks on the surface of the test piece were observed before residence and after residence at 300° C. for 5 minutes. The generation status of silver streaks is displayed on a scale of 10 to 1 (no) to 10.
C large) is shown. At the same time, the yellowness of the test piece was measured using a Hunter colorimeter.
The color difference ΔE from the yellowness after staying at 0° C. for 5 minutes was measured, and the results are shown in Table 2.

Example (Blend) Organic phosphite (Table 1) 0.3 The same test as in Example 1 was conducted using the above blend, and the results are shown in Table 3.

Example 3 (Blend) Polycarbonate resin 50 parts by weight Organic phosphite (Table 1) 0.2 Test specimens were prepared in the same manner as in Example 1 with the above formulation, and the Izot impact strength (notched) and The color difference between the test pieces was measured when the test piece was not stored at 280°C and when it was stored at 300°C for 5 minutes. The results are shown in Table-4.

Claims (1)

[Claims] Maleimide or α-methylstyrene modified ABS resin 1
A stabilized heat-resistant ABS resin composition obtained by adding 0.001 to 5 parts by weight of an organic phosphite compound represented by the following general formula (I) to 00 parts by weight. ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, R_1 represents a tertiary butyl group or tertiary amyl group, R_2 represents an alkyl group having 1 to 9 carbon atoms, and R
_3 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R_4 represents an alkyl group having 1 to 30 carbon atoms. )