JPH0488044A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To obtain a resin composition suitable for parts of electric devices, automobile parts, etc., having excellent balance of heat resistance, impact resistance, solvent resistance and oil resistance, comprising a glutarimide copolymer, a saturated polyester and a specific rubber-containing copolymer. CONSTITUTION:A resin composition comprising (A) 5-45wt.% glutarimide copolymer composed of A1: 5-99.5mol% glutarimide unit, A2: 0.5-10mol% acid and/or acid anhydride unit and A3: 94.5-0mol% ethylenic alpha-beta-unsaturated monomer unit, (B) 20-75wt.% saturated polyester (preferably PET or PBT) and (C) 20-75wt.% copolymer (e.g. ABS resin) prepared by polymerizing C2: 90-20wt.% at least one monomer of an aromatic ethylenic alpha,beta-unsaturated monomer, a cyano group-containing ethylenic alpha,beta-unsaturated monomer and an ethylenic alpha,beta-unsaturated carboxylic acid in the presence of C1: 10-80wt.% rubber-like polymer.

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a resin composition comprising three types of thermoplastic resins and having various excellent properties.

<Prior Art> Thermoplastic resins have different characteristics depending on their type, and are used in various fields.

Recently, it has been discovered and proposed to mix two or more different types of resin to create a material with higher performance.

Japanese Patent Publication No. 60-38404 proposes a method for producing a glucurimide polymer and blending the polymer with an ABS resin or an MBS resin as an impact modifier.

JP-A-59-41355 discloses a thermoplastic resin composition comprising a thermoplastic polyester, polyglutarimide, and an impact modifier.

<Problem to be solved by the invention> Glutarimide disclosed in Japanese Patent Publication No. 60-38404]
・Contains a blend of polymer and impact modifier, and for higher impact resistance requirements, the ratio of impact modifier increases, which increases the heat resistance characteristic of glutarimide polymers. That won't be enough.

The resin composition disclosed in JP-A-59-41355 is insufficient in heat resistance and impact resistance.

Therefore, it is an object of the present invention to provide a well-balanced resin composition that has high f14 heat resistance and rigidity, and is also excellent in impact resistance, solvent resistance, and oil resistance.

<Means for Solving the Problems> The present invention provides (8) glutarimide units in an amount of 5 to 99.5 mol%, acid and/or acid anhydride units in an amount of 0.5 to 10 mol%, and ethylenic α, β non-containing units. 94.5 to 94.5 saturated monomer units
Glutarimide copolymer consisting of 0 mol%; 5-45% by weight, (B) saturated polyester; 20-75% by weight, (
C) [1] In the presence of 10 to 80% by weight of rubbery polymer ■
Aromatic ethylenically α- and β-unsaturated monomers, ethylenic α- and β-unsaturated monomers with cyan group, ethylenic α2
The heat resistance of the composition of at least one type of unsaturated carboxylic acid ester derived from a β-unsaturated carboxylic acid ester monomer is insufficient.

The acid and acid anhydride units are 9 (meth)acrylic acid and glutaric anhydride units, and the proportion of these units is 0.5 to 10 mol%, preferably 1 to 5 mol%. This unit increases the impact resistance of the composition, but if it is present too much, water absorption increases, which is not preferable.

The ethylenic α, β unsaturated monomer unit of the glutarimide copolymer includes monomers such as (meth)acrylic acid ester, (meth)acrylic acid, styrene, α-methylstyrene, vinyltoluene, chlorostyrene, acrylonitrile, etc. Examples include body units.

Examples of (meth)acrylic esters include methyl (meth)acrylate, ethyl (meth)acrylate, (
Propyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, ter-butyl (meth)acrylate, dodecyl (meth)acrylate, (
Cyclohexyl meth)acrylate, (meth)acrylic 0
Rubber-containing copolymer obtained by polymerizing ~20% by weight; 20~
75% by weight of a thermoplastic resin composition.

The glutarimide unit of the (8) glutarimide copolymer used in the present invention is -Shipen (1)% formula% (In formula (1), R1 and R2 are hydrogen atoms or methyl groups, R1 is hydrogen atoms or aliphatic having 1 to 20 carbon atoms;
Represents aromatic or alicyclic hydrocarbons. ).

Among them, a methyl group in which R'' is hydrogen is particularly excellent in heat resistance, and a cyclohexyl group is excellent in that it has little hygroscopicity.

The glucurimide unit is 5 in the glucurimide copolymer.
~99.5 mol%.

Preferably it is 20 to 99 mol%.

The glucurimide 11' (norbornyl densate obtained when the position is small, 2-ethylhexynol (meth)acrylate, (
meth)acrylic acid Hensyl units, etc.

Note that these monomer units may be used alone or in combination of two or more types.

These monomer units are 94 in the glutarimide copolymer.
．． It accounts for 5 to 0 mol%.

The weight average molecular weight of glutarimide copolymer is usually 40,000~
500,000, preferably 40,000 to 200,000.

If the molecular weight is less than 40,000, the mechanical strength will be poor, and if it exceeds 500,000, the moldability will be poor.

The method for producing glutarimide copolymer is described in Japanese Patent Publication No. 60-3.
A known method such as that described in Japanese Patent No. 8404 may be used.

To give an example, among the monomers exemplified as the ethylenically α,β unsaturated monomer unit, (meth)acrylic acid or
It can be obtained by heating and melting a homopolymer or copolymer containing (meth)acrylic acid ester as an essential component, mixing with an imidizing agent, and reacting the mixture.

Examples of the imidizing agent include ammonia, methylamine,
Ethylamine butylamine hexylamine, octylamine, norylamine decylamine, hensylamine, cyclohexylamine, aniline, halogenated aniline 1-urea, dimethylurea, etc.

In the composition of the present invention, (A) the glucurimide copolymer contains 5
~45% by weight or 10-40% by weight.

If it is less than 5% by weight, only a composition with extremely low heat resistance will be obtained, and if it exceeds 45 weight %, the impact resistance of the composition will decrease, which is not preferable.

The saturated polyester (B) used in the present invention is a well-known polyester consisting of an ester of a dicarboxylic acid component and a diol component.

At least 40 mol% of the dicarboxylic acid component is terephthalic acid, and if necessary, other acids having 2 carbon atoms such as ampic acid, sebacic acid, and dodecanedicarboxylic acid are used.
If the aliphatic di-20 is less than 20% by weight, the solvent resistance of the composition will be insufficient, and if it exceeds 75% by weight, the heat resistance of the composition will be
This is not preferred because impact resistance decreases.

The rubber-containing copolymer (C) used in the present invention refers to rubber-like polymers such as polybutadiene rubber, acrylonitrile-butadiene copolymer rubber, styrene-butadiene copolymer rubber, ethylene-propylene-diene copolymer In the presence of rubber etc., aromatic ethylenically α,β unsaturated monomers such as styrene, α-methylstyrene, ethylenically α,β unsaturated monomers having a cyan group, such as acrylonitrile, methacrylate, etc. At least one monomer selected from ethylenically α, β-unsaturated carboxylic acid ester monomers such as lotril, for example, methyl (meth)acrylate, ethyl (meth)acrylate, etc. It is a polymer obtained by polymerization by methods such as emulsion polymerization, bulk polymerization, bulk-suspension polymerization, etc., or a mixture of this polymer and a polymer of these monomer units.

Carboxylic acid: Weigh out the aromatic dicarboxylic acids such as isophthalic acid and naphthalene dicarboxylic acid.

Diol components include aliphatic glycols such as ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, and decane diol; fatty acids such as cyclohexane diol; and aromatic diols such as bisphenol A. There are two or more types.

Among these saturated polyesters, polybutylene terephthalate or polyethylene terephthalate are particularly common.

In addition, these saturated polyesters have an intrinsic viscosity of 0.5 to 3.0 when measured at 25°C in an 0-chlorophenol solvent.
A range of 0 dl/g is preferable from the viewpoint of mechanical strength of the composition.

In the composition of the present invention, (11) the saturated polyester is 20
-75% by weight, preferably 25-70% by weight.

Typical examples include so-called ABS resin, MBS resin, A
Examples include ES resin.

The proportion of the rubbery polymer in this rubber-containing copolymer is preferably from 10 to 80% by weight, particularly from 30 to 70% by weight.

If the proportion of the rubbery polymer is less than 10% by weight, the resulting composition will have insufficient impact resistance, and if it exceeds 80% by weight, the resulting composition will have low rigidity and reduced heat resistance. Undesirable.

In the composition of the present invention, the rubber-containing copolymer (C) contains 20
~75% by weight, preferably 25-70% by weight.

If the weight is less than 20%, the impact resistance of the composition will be insufficient;
If it exceeds 75% by weight, the heat resistance, rigidity, and solvent resistance of the composition will decrease, which is not preferable.

A well-known method can be used to blend the above polymers (A), (B), and (c) to form a composition.

For example, there is a method in which liquids of each polymer are mixed and then the solvent is evaporated or poured into a non-solvent to precipitate; a method in which each polymer is kneaded in a molten state;
- There are methods that use kneading devices such as single-screw or twin-screw extruders, various kneaders, etc. used for boat fishing, and methods that knead directly during melt processing operations such as injection molding and extrusion molding.

The thermoplastic resin composition of the present invention may contain antioxidants such as well-known hindered phenol antioxidants, phosphorus antioxidants, and sulfur antioxidants, as well as ultraviolet absorbers and hindered amine light stabilizers. Weathering agents, lubricants, antistatic agents,
It is also possible to add flame retardants, colorants, pigments, etc.
Further, depending on the purpose, reinforcing fibers such as glass fibers, inorganic fillers, etc. may also be blended.

<Effects of the Invention> The thermoplastic resin composition of the present invention has an excellent balance of heat resistance represented by heat distortion temperature, impact resistance, rigidity represented by flexural modulus, and solvent resistance. Examples: 15 mol%, acid value 5 mol%) and polybutylene terephthalate as a saturated polyester,
N100O, manufactured by Mitsubishi Rayon 021, open viscosity 1.
13), and ABS resin as a rubber copolymer (Clarastic MV Sumitomo Naugatac Co., Ltd., 220°C1
, the melt flow index 9) at Okg is the first
After blending the amounts listed in the table, the resin compositions were extruded using a twin-screw extruder at a resin temperature of 250°C to obtain pellets of the resin composition.

This pellet was molded using an injection molding machine at a cylinder temperature of 26°C.
Test pieces were prepared by injection molding at a mold temperature of 0°C and 60°C, and their physical properties were evaluated.

The results obtained are shown in Table 1.

Comparative Example 1 Glutarimide copolymer was mixed with KAMAX 0T-240 (
The same operation as in Example 1 was performed except that the glutarimide content was 75 mol % and the acid value was 0 mol %), and the physical properties were evaluated.

The results obtained are shown in Table 1.

Comparative Examples 2 to 4 It can be used, for example, for electrical equipment parts, automobile parts such as automobile interiors and exterior panels, miscellaneous goods, and the like.

<Example> The present invention will be further explained below with reference to Examples.

The measurement method used in the examples is as follows.

Heat distortion temperature: 18, according to ASTM D 648
Measured under a load of 6 kg/cm2.

Solvent resistance: Drop toluene onto the test piece-1-, leave it at room temperature for 4 hours, and then visually observe the changes. ○ No corrosion: ○ Slight erosion: △ Significantly eroded surface. Those with unevenness were marked as ×.

Examples 1 to 5 Glutarimide copolymer (eT-150 to KAM8X,
Manufactured by Rom &Haas; Glutarimide unit 7 Example 1
Glutarimide copolymer saturated polyester used in A
The BS resin was evaluated in the same manner as in Example 1 using the quantitative ratios shown in Table 1.

The results are shown in Table 1.

14 complete

Claims (1)

[Claims] (1) (A) 5 to 99.5 mol% of glutarimide units
, 0.5 to 10 mol% of acid and/or acid anhydride units,
and 94.5 to 0 ethylenically α,β unsaturated monomer units
Glutarimide copolymer consisting of mol%; 5-45% by weight, (B) saturated polyester; 20-75% by weight, (C) [
1] In the presence of 10 to 80% by weight of a rubbery polymer, [2] Aromatic ethylenic α, β unsaturated monomer, ethylenic α, β unsaturated monomer having a cyan group, ethylenic α A thermoplastic resin composition comprising: a rubber-containing copolymer obtained by polymerizing 90 to 20% by weight of at least one monomer selected from β-unsaturated carboxylic acid ester monomers; 20 to 75% by weight; .