JPH0273841A - Reinforced thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To obtain a reinforced resin composition having excellent compatibility, heat distortion resistance, rigidity, chemical resistance and impact resistance containing a polyamide resin, unsaturated carboxylic acid-containing copolymer, rubber-containing graft copolymer and glass fibers. CONSTITUTION:100pts.wt. total amouints of (A) 5-90pts.wt. polyamide resin, (B) 5-90pts.wt., preferably 50-80pts.wt. unsaturated carboxylic acid-containing copolymer, preferably copolymer prepared by copolymerizing 40-80wt.% aromatic vinyl compound with 15-50wt.% vinyl cyanide compound, 0.5-40pts.wt. unsaturated carboxylic acid compouind and 0-30pts.wt. vinyl compound (e.g. methyl methacrylate) copolymerizable with these monomers and (C) 5-60pts.wt., preferably 20-50pts.wt. graft copolymer prepared by grafting 95-5wt.% vinyl compound in the presence of 5-95wt.% diene-based rubber are blended with (D) 2-50pts.wt. glass fibers.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a novel reinforced thermoplastic resin composition that provides a molded article with excellent heat deformation resistance and rigidity, as well as excellent chemical resistance and impact resistance. .

[Prior Art/Problems to be Solved by the Invention] Polyamide resins provide molded products with excellent heat deformation resistance, rigidity, and chemical resistance, so they are used in the manufacture of electrical parts, automobile parts, etc. Further improvements in impact resistance, water absorption, etc. are desired.

On the other hand, ABS resin, which is a typical rubber-reinforced resin, provides molded products with excellent impact resistance and workability, so it is used in the manufacture of automobile parts, electrical parts, miscellaneous goods, etc.
Further improvements in chemical resistance, heat deformation resistance, rigidity, etc. are desired.

Attempts have been made to blend polyamide resin and ABS resin to take advantage of the characteristics of both, but polyamide resin and ABS resin are originally a combination with very poor compatibility and dispersibility, so it is difficult to use a mixture of them. When molded products are manufactured using this method, they exhibit extreme non-uniformity, resulting in poor surface appearance, delamination, and reduced impact resistance, resulting in molded products that cannot be used in practical applications.

Therefore, by adding compatibilizers and modifying ABS resin,
Attempts have been made to improve the compatibility between polyamide resins and ABS resins. For example, a method in which a monomer containing an unsaturated carboxylic acid is graft-polymerized onto a rubber component is reacted with the amine end of a polyamide resin (Japanese Unexamined Patent Publication No. 4
7-6284) or emulsion graft polymerization of unsaturated carboxylic acids, the polymerization stability is poor and a large amount of aggregates are generated, but to avoid this, unsaturated carboxylic acid ester monomers are used. This method involves graft polymerizing a rubbery polymer and then saponifying it to improve its compatibility with a polyamide resin (Japanese Unexamined Patent Publication No. 11159/1983).

These methods improve the compatibility between polyamide resin and ABS resin, and it is certainly possible to improve impact resistance.

However, although the heat resistance under low loads improves by blending polyamide resin, which is a crystalline polymer compound, the heat resistance under high loads actually decreases, which may limit the application. arise.

[Means and effects for solving the problem] As a result of extensive research into improving the compatibility of ABS resin with polyamide resin and improving the physical properties of molded products from the mixture, the present inventors found that aromatic vinyl compound, an unsaturated carboxylic acid compound, a vinyl cyanide compound, and another vinyl compound copolymerizable with these, and the resulting copolymer is combined with a rubber-containing graft copolymer, a polyamide resin, and a glass fiber. When blended, a reinforced thermoplastic resin composition with excellent compatibility can be obtained, which can be easily molded and has excellent heat deformation resistance and rigidity, as well as oil resistance, impact resistance, surface hardness, paintability, and water resistance. The present invention has been completed based on the discovery that a molded article with well-balanced physical properties can be obtained.

That is, the present invention includes (A) 5 to 90 parts (parts by weight, the same applies hereinafter) of polyamide resin;
, by graft polymerizing 95 to 5% of a vinyl compound in the presence of (B) 5 to 90 parts of an unsaturated carboxylic acid-containing copolymer and (C) 5 to 95% (by weight, the same applies hereinafter) of a diene rubber. Total amount of 5 to 60 parts of graft copolymer obtained: 100
This invention relates to a reinforced thermoplastic resin composition containing 2 to 50 parts of glass fiber per part of the present invention.

[Example] Polyamide resin (A) component used in the present invention (
The polyamide resin (hereinafter also referred to as (A)) is a component for improving the heat deformation resistance, rigidity, chemical resistance, fluidity during processing, etc. of the molded product obtained from the reinforced thermoplastic resin composition.

Specific examples of the polyamide resin (A) include aliphatic polyamides such as nylon 6, nylon 6/6, nylon 6/10, nylon 11, nylon 12, and nylon 6/12, and polyhexamethylene diamine terephthalate. Examples include aromatic polyamides such as amide, polyhexamethylene diamine isophthalamide, and the like. These may be used alone or in combination of two or more. Alternatively, it may be a copolymer obtained by copolymerizing the raw materials for the polyamide resin.

The unsaturated carboxylic acid-containing copolymer (hereinafter also referred to as copolymer (B)), which is the component (B) used in the present invention, has excellent heat deformation resistance of molded articles from the resulting reinforced thermoplastic resin composition. It is a component for improving the dimensional stability and rigidity of molded products.

The copolymer (B) is not particularly limited as long as it contains an unsaturated carboxylic acid unit in the copolymer; A copolymer obtained by the above reaction is preferable, and when the above-mentioned compounds are reacted, a vinyl compound copolymerizable with these may be further copolymerized. Furthermore, the proportions of these compounds when copolymerizing are 40-80% aromatic vinyl compound, 15-50% vinyl cyanide compound, and 0.0% unsaturated carboxylic acid compound.
It is more preferable to react at a ratio of 5 to 40%, preferably 1 to 15% (total of 100%);
In the entire compound including the vinyl compound copolymerizable with the above compound, 3 vinyl compounds copolymerizable with the above compound are added.
Copolymerization may be carried out within a range of up to 0%.

If the proportion of aromatic vinyl compound units in the copolymer (B) exceeds 80%, the oil resistance and impact resistance of the resulting molded product will tend to decrease, while if it is less than 40%, the molding processability will deteriorate. A tendency to decline occurs. In addition, if the proportion of vinyl cyanide compound units exceeds 50%, thermal stability during molding will decrease, and coloring due to heating will tend to increase, while if it is less than 15%, chemical resistance, impact resistance, etc. tends to decrease. Furthermore, if the proportion of unsaturated carboxylic acid compound units exceeds 40%, thermal stability during molding processing will decrease, and not only will coloring by heating become severe, but also stability during polymerization will tend to decrease. If the amount is less than 0.5%, the compatibility with the polyamide resin decreases, delamination occurs on the surface of the molded product, and the impact resistance tends to decrease significantly.

Specific examples of the aromatic vinyl compound used in the production of copolymer (B) include styrene, α-methylstyrene, chlorostyrene, methylstyrene, and the like. Among these, α-methylstyrene is recommended from the viewpoint of improving heat resistance.

Specific examples of vinyl cyanide compounds include acrylonitrile, methacrylate, and the like.

Further, specific examples of unsaturated carboxylic acid compounds include acrylic acid, methacrylic acid, and the like.

Specific examples of vinyl compounds that can be copolymerized with the above compounds include alkyl esters of methacrylic acid and acrylic acid such as methyl methacrylate, ethyl methacrylate, methyl acrylate, and ethyl acrylate, and maleimide compounds such as maleimide and phenylmaleimide. can be given.

The graft copolymer (hereinafter also referred to as graft copolymer (C)), which is component (C) used in the present invention, is obtained by graft copolymerizing 95 to 5% of a vinyl compound to 5 to 95% of a diene rubber. It is a graft polymer consisting of a polyester resin, and is a component for improving the impact resistance of molded products of the resulting reinforced thermoplastic resin composition.

The diene rubber used in the graft copolymer (C) is not particularly limited, but for example, a diene rubber or a diene copolymer rubber with a diene component of 50% or more, and an average particle diameter of the rubber particles of 0.05 to 2. A specific example of a preferable example is one that is ubiquitous.

Specific examples of the vinyl compounds to be graft copolymerized include aromatic vinyl compounds, vinyl cyanide compounds, unsaturated carboxylic acid compounds, and vinyl compounds copolymerizable with these as raw materials for the copolymer (B). etc., and one or more of these can be used.

The composition of the vinyl compound to be graft copolymerized is 20 to 80% aromatic vinyl compound, 15% vinyl cyanide compound.
-50%, unsaturated carboxylic acid compound 0-40%, and vinyl compound copolymerizable with these 0-30% (total of 100%).

If the proportion of diene rubber in the graft copolymer (C) exceeds 95%, impact resistance, chemical resistance, etc. will decrease, and if it is less than 5%, impact resistance will decrease, which is not preferable.

If the proportion of the aromatic vinyl compound in the vinyl compound to be graft copolymerized exceeds 80%, the resulting molded product will tend to have poor impact resistance, chemical resistance, etc., and if it is less than 20%, the molding processability will deteriorate. There will be a tendency for this to occur. Additionally, if the proportion of vinyl cyanide compounds exceeds 50%, there will be a tendency for heat coloring to occur during molding.
If it is less than 15%, impact resistance, chemical resistance, etc. tend to deteriorate.

The reinforced thermoplastic resin composition of the present invention is prepared from the polyamide resin (A), copolymer (B), graft copolymer (C), and glass fiber.

The blending ratio of polyamide resin (A), copolymer (B) and graft copolymer (C) is 5
~90 parts, 5 to 90 parts of copolymer (B), preferably 50 parts
~80 parts and graft copolymer (C) 5 to 60 parts, preferably 20 to 50 parts, and the total amount is 100 parts.

If the amount of polyamide resin (^) contained in the total amount of 100 parts is less than 5 parts, the resulting molded product will have poor oil resistance, and if it exceeds 90 parts, physical properties will change due to water absorption. I don't like it because it gets bigger.

If the amount of copolymer (B) contained in the total amount of 100 parts is less than 5 parts, heat deformation resistance and moldability will decrease, and if it exceeds 90 parts, oil resistance will decrease. This is not preferable because it may cause a decrease in

In addition, the graft copolymer (
If the amount of C) is less than 5 parts, the impact resistance will be lowered, and if it exceeds 60 parts, the processability will be lowered, which is not preferable.

The glass fiber used in the present invention is not particularly limited, and any glass fiber that is normally used for reinforcing plastics can be used, but the glass fiber has a diameter of 5 to 15 μm and a length of 1.5 to 1.5 μm.
A diameter of 50 mm is preferably used.

The amount of glass fiber used is (A), (B) and (C)
The amount is 2 to 50 parts, preferably 5 to 50 parts, based on 100 parts of the total amount of components. If the amount is less than 2 parts, the effect of the blending will not be sufficiently achieved, and if it exceeds 50 parts, the processability and surface properties of the molded product will deteriorate.

Mixing when preparing the reinforced thermoplastic resin composition of the present invention,
Granulation, molding, etc. can be carried out by various known methods.

For example, polyamide resin (A), copolymer (B), graft copolymer (C), and glass fiber are blended using a blender such as a Henschel mixer, then melt-mixed in an extruder, formed into a pellet, and then injected. Alternatively, only the components (A) to (C) may be made into pellets in advance, and glass fibers may be added thereto, and the pellets may be re-made into pellets or directly subjected to injection molding.

Alternatively, a copolymer (B) or a graft copolymer (C) polymerized in the presence of glass fibers may be used. At this time, stabilizers, pigments, lubricants, fillers, etc. may be added as necessary.

Next, a method for producing the copolymer (B) and the graft copolymer (C) will be explained.

The copolymer (B) and the graft copolymer (C) are preferably obtained by emulsion polymerization, but are not necessarily limited to emulsion polymerization. For example, bulk polymerization, suspension polymerization, solution polymerization, emulsion-suspension polymerization, emulsion-bulk polymerization, etc., which are combinations thereof, may be used.

In the case of emulsion polymerization, the above compounds may be reacted in an aqueous medium in the presence of a radical initiator according to a conventional method. In this case, the above-mentioned compounds may be used as a mixture or, if necessary, may be used separately. Furthermore, there is no particular limitation on the method of adding the compound, and the entire amount may be added at once, or may be added sequentially.

Specific examples of the radical initiator include water-soluble or oil-soluble peroxides such as potassium persulfate, ammonium persulfate, cumene hydroperoxide, and paramenthane hydroperoxide. In addition, polymerization accelerators, polymerization degree regulators, and emulsifiers may be appropriately selected from those used in known emulsion polymerization methods.

A method for obtaining dry resin from the obtained latex is, for example, adding an acid such as hydrochloric acid, sulfuric acid, or acetic acid, or a metal salt such as calcium chloride, magnesium chloride, or aluminum sulfate to the latex to coagulate the latex, followed by dehydration and drying. Any known method may be used. At that time, copolymer (B
) and the latex of the graft copolymer (C) may be mixed, and then the dry resin may be obtained, or the dry resins may be obtained separately and mixed in powder form.

Hereinafter, the present invention will be described in detail based on Examples, but these are merely illustrative and the present invention is not limited thereto.

Production Examples 1 to 8 A reaction vessel equipped with a stirrer, a reflux condenser, a nitrogen inlet, a monomer inlet, and a thermometer was charged with 200 parts of water and 3 parts of sodium alkylbenzenesulfonate.

While stirring, raise the temperature to 60°C under a nitrogen stream to 60°C.
After reaching the temperature, a mixture of the monomers shown in Table 1, t-dodecylmercaptan (tDM) and cumene hydroperoxide (CHP) was continuously added dropwise over 6 hours. After the dropwise addition was completed, stirring was continued for 1 hour at 60°C to complete polymerization and obtain latex.

However, in the case of Production Example 1, α-methylstyrene (
75 parts of αMSt) and 0.4 parts of tDM were charged in advance into a reaction vessel.

In the case of Production Example 8, a large amount of agglomerates were produced during polymerization, so subsequent evaluation could not be carried out.

Further, in Table 1, AN represents acrylonitrile, St represents styrene, HMA represents methyl methacrylate, and M^^ represents methacrylic acid.

[Left below] Production Examples 9 to 11 In a reaction vessel similar to that used in Production Examples 1 to 8, add 250 ml of water.
part, sodium formaldehyde sulfoxylate 0
．． 3 parts, 0.0025 parts of ferrous sulfate, 0.01 parts of sodium ethylenediaminetetraacetate, and 60 parts of polybutadiene.
I prepared a section.

While stirring, raise the temperature to 60°C under a nitrogen stream to 60°C.
After reaching °C, the monomers, tDM and CHP shown in Table 2
A mixture of these was continuously added dropwise over 5 hours. After the dropwise addition was completed, stirring was continued for 1 hour at 60°C to complete polymerization and obtain latex.

The polybutadiene used had an average particle size of 0.25μ.
It was latex-like with a gel content of 90%.

[Margins below] Table 1. Mix the solid content in the latex state to the predetermined ratio shown in Table 3, and add 0.5 part of a phenolic antioxidant (AO50 manufactured by Adeka Argus) to this mixed latex. The mixture was coagulated with magnesium chloride, dehydrated, washed with water, and dried to obtain a powdered blend of an unsaturated carboxylic acid copolymer and a graft copolymer.

E Space below Production Examples 12 to 18 Copolymers produced in Production Examples 1 to 7 (hereinafter referred to as Copolymers (B-1) to Copolymer (B-7), respectively) and Production Examples 9 to 11. The produced graft copolymers (hereinafter referred to as graft copolymers (C-1) to graft copolymers (C-3))
) are respectively Examples 1 to 9 and Comparative Examples 1 to 3 Polyamide resin (A), a blend of the unsaturated carboxylic acid-containing copolymer and graft copolymer obtained in Production Examples 12 to 18 (hereinafter referred to as formulations (D-1) to (D-7), respectively) and glass fibers (average diameter 15μ, average length approximately 3mm) were mixed in a predetermined ratio shown in Table 4, and a vent type Pelletize using an extruder and injection mold (molding temperature 24
0° C.) to prepare test pieces and evaluate their physical properties. The evaluation results are shown in Table 4.

In addition, evaluation was performed by the following method.

Heat distortion temperature: ASTM D-848, 18,8kg/
cd (“C) Izod impact value: ASTM D-
256, with notch (kg- mark/C1l+) tensile crab ASTM D-836, 23℃ (kg/
cJ) Bending strength: ASTM D-790, 23℃ (
kg/cj) Flexural modulus: ASTM D-79
0,23℃ (kg/ci) Oil resistance: 1 with notch
Fix one side of the 4-inch bar and attach 200 mm to the other side.
DOP was dropped into the notch while a load was applied, and the time until breakage was measured.

(Time) [Left below] From the results of Examples 1 to 9 and Comparative Examples 1 to 3 shown in Table 4, the reinforced thermoplastic resin composition of the present invention has excellent heat deformation resistance and good rigidity. I understand.

[Effects of the Invention] The composition of the present invention has excellent compatibility of each resin component constituting the composition, can be easily molded, has excellent heat deformation resistance and rigidity, and has good oil resistance, impact resistance, and surface hardness. , provides molded products with well-balanced physical properties such as paintability and water resistance.

Special permission

Claims (1)

[Scope of Claims] 1 In the presence of (A) 5 to 90 parts by weight of polyamide resin, (B) 5 to 90 parts by weight of unsaturated carboxylic acid-containing copolymer, and (C) 5 to 95 parts by weight of diene rubber. A reinforced thermoplastic resin composition containing 2 to 50 parts by weight of glass fiber to 100 parts by weight of a total of 5 to 60 parts by weight of a graft copolymer obtained by graft polymerizing 95 to 5% by weight of a vinyl compound. thing. 2 The unsaturated carboxylic acid-containing copolymer contains 40 to 80% by weight of an aromatic vinyl compound and 15% by weight of a vinyl cyanide compound.
~50% by weight, 0.5 to 40% by weight of unsaturated carboxylic acid compounds, and 0 to 30% of vinyl compounds copolymerizable with these.
The reinforced thermoplastic resin composition according to claim 1, which is a copolymer obtained by copolymerizing % by weight.