JPH083018B2 - Thermoplastic resin composition - Google Patents

Description

TECHNICAL FIELD The present invention relates to a resin composition having excellent heat resistance, impact strength and chemical resistance. More specifically, it relates to a thermoplastic resin composition comprising an imidized copolymer, a polyamide and a copolymer of an α-olefin and an unsaturated carboxylic acid or a glycidyl ester of an α, β-unsaturated acid.

(Prior Art and Problems) Polyamide is widely used because of its excellent chemical resistance, heat resistance and abrasion resistance. However, polyamide has the drawbacks of large shrinkage at the time of molding, easy occurrence of sink marks and warpage in the molded product, and high hygroscopicity, large decrease in mechanical strength due to moisture absorption, and large dimensional change. In order to improve them, a method of mixing polystyrene or a styrene-acrylonitrile copolymer has been proposed (Japanese Patent Publication No. 40-7380). However, these resins have a poor compatibility with polyamide and have a drawback that the mechanical strength is significantly lowered. Further, a method of mixing an α, β-unsaturated carboxylic acid anhydride with styrene instead of polystyrene or a styrene-acrylonitrile copolymer (JP-A-56-5093)
No. 1) or a method of mixing an imide compound of an α, β-unsaturated dicarboxylic acid with a polyamide (Japanese Patent Laid-Open No. 58-71952), but the compatibility between the polyamide and these resins is still insufficient. Moreover, the heat resistance is insufficient.

On the other hand, α-olefin and unsaturated carboxylic acid or α, β-
A method for improving the weld strength by adding a copolymer of an unsaturated acid and a glycidyl ester to a mixture of an ABS resin and a saturated polyester or polycarbonate (JP-A-58-15).
Nos. 7848 and 60-63250) have been proposed, but their heat resistance was insufficient.

(Means for Solving the Problems) As a result of an investigation for the purpose of solving the above problems, the present inventor found that the imidized copolymer and the polyamide were further α-.
By blending the olefin copolymer, it was possible to improve the compatibility between the imidized copolymer and the polyamide and obtain a composition having excellent heat resistance and impact strength. Further, it was possible to obtain a resin composition having excellent impact strength, heat resistance, chemical resistance, and moldability. That is, the present invention relates to (A) component: rubbery polymer 0 to 39% by weight, aromatic vinyl monomer residue 30 to 69% by weight, unsaturated dicarboxylic acid imide derivative residue 30 to 60% by weight, unsaturated Imidized copolymer consisting of 1 to 10% by weight of dicarboxylic acid anhydride monomer residues and 0 to 39% by weight of vinyl monomer residues other than these 10 to 90% by weight
And (B) component: a resin composition comprising 99 to 80% by weight of polyamide 10 to 90% by weight, and (C) component: a mixture of an α-olefin and an unsaturated carboxylic acid or a glycidyl ester of an α, β-unsaturated acid. Polymer 1
The thermoplastic resin composition is characterized by containing ˜20% by weight.

First, the imidized copolymer as the component (A) and a method for producing the same will be described.

As the method for producing the component (A) copolymer, the aromatic vinyl monomer unsaturated dicarboxylic acid imide derivative, unsaturated dicarboxylic acid anhydride monomer, in the presence of a rubbery polymer, if necessary as the first production method, And a method of copolymerizing a vinyl monomer mixture copolymerizable therewith, an aromatic vinyl monomer, an unsaturated dicarboxylic acid anhydride and a copolymer thereof with the second production method, if necessary, in the presence of a rubbery polymer. A polymer obtained by copolymerizing a polymerizable vinyl monomer mixture is reacted with ammonia and / or a primary amine to the acid anhydride group in the polymer to form a part of the acid anhydride group into an imide group. Examples thereof include a method of converting, and an imidized copolymer can be obtained by any method.

Component (A) Copolymer As the aromatic vinyl monomer used in the first production method, styrene monomers such as styrene, α-methylstyrene, vinyltoluene, t-butylstyrene and chlorostyrene, and substituted single monomers thereof are used. It is a monomer, and of these, styrene is particularly preferable.

As the unsaturated dicarboxylic acid imide derivative, maleimide, N-methylmaleimide, N-butylmaleimide, N
-Phenylmaleimide, N-methylphenylmaleimide, N-hydroxyphenylmaleimide, N-methoxyphenylmaleimide, N-chlorophenylmaleimide,
Maleimide derivatives such as N-carboxyphenylmaleimide, N-nitrophenylmaleimide, N-cyclohexylmaleimide and N-isopropylmaleimide, and itaconic acidimide derivatives such as N-methylitaconic acid imide and N-phenylitaconic acid imide. Of these, N-phenylmaleimide is particularly preferable.

Examples of unsaturated dicarboxylic acid anhydrides include anhydrides such as maleic acid, itaconic acid, citraconic acid, and aconitic acid, with maleic anhydride being particularly preferred.

Examples of vinyl monomers copolymerizable with these include acrylonitrile, methacrylonitrile, vinyl cyanide monomers such as α-chloroacrylonitrile, and acrylate monomers such as methyl acrylate and ethyl acrylate. There are methacrylic acid ester monomers such as methyl methacrylic acid ester and ethyl methacrylic acid ester, acrylic acid, vinyl carboxylic acid monomers such as methacrylic acid, acrylamide, methacrylamide and the like, among which acrylonitrile, Monomers such as methacrylic acid esters, acrylic acid and methacrylic acid are preferred.

As the aromatic vinyl monomer, the unsaturated dicarboxylic anhydride and the vinyl monomer copolymerizable therewith, the one used in the first production method can be used.

Further, the ammonia or primary amine used in the imidization reaction may be in an anhydrous or aqueous state, and examples of the primary amine include alkylamines such as methylamine, ethylamine, butylamine and cyclohexylamine, and Examples thereof include aromatic amines such as chloro- or bromo-substituted alkylamines, aniline, tolylamine and naphthylamine, and halogen-substituted aromatic amines such as chloro- or bromo-substituted aniline.

Further, when the imidization reaction is performed in a solution state or a suspension state, it is preferable to use a normal reaction vessel, for example, an autoclave, and when the imidization reaction is performed in a bulk molten state, an extruder equipped with a devolatilizer may be used. Good. Further, a catalyst may be present at the time of imidization, and for example, a tertiary amine or the like is preferably used.

The temperature of the imidization reaction is about 80 to 350 ° C, preferably 100 to 300 ° C. If the temperature is lower than 80 ° C, the reaction rate is slow and the reaction takes a long time, which is not practical. On the other hand, when the temperature exceeds 350 ° C, the physical properties are deteriorated due to thermal decomposition of the polymer.

The amount of acid anhydride residue is adjusted by the molar equivalent of ammonia and / or primary amine added to the acid anhydride group.

As the solvent for imidization in a solution state, there are acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, tetrahydrofuran, dimethylformamide and the like. Among these, methyl ethyl ketone and methyl isobutyl ketone are preferable. The non-aqueous medium used for imidization in suspension in a non-aqueous medium includes aliphatic hydrocarbons such as heptane, hexane, pentane, octane, 2-methylpentane, cyclopentane and cyclohexane.

Component (A) copolymer is a rubbery polymer 0 to 39% by weight,
Preferably 0 to 30% by weight, aromatic vinyl monomer residue 30 to
69% by weight, preferably 40 to 64% by weight, unsaturated dicarboxylic acid imide derivative residue 30 to 60% by weight, preferably 35 to 55% by weight, unsaturated dicarboxylic acid anhydride monomer residue 1 to 10% by weight , And preferably 1 to 5% by weight, and 0 to 39% by weight, preferably 0 to 30% by weight, of vinyl monomer residues other than these, and the amount of the rubber-like polymer is 39.
If it exceeds the weight%, the heat resistance, moldability and dimensional stability of the composition are impaired.

When the amount of the aromatic vinyl monomer residue is less than 30% by weight, moldability and dimensional stability are impaired, and when it exceeds 69% by weight, impact strength and heat resistance are impaired. When the amount of the unsaturated dicarboxylic acid imide derivative residue is less than 30% by weight, the effect of improving the heat resistance is insufficient, while when it exceeds 60% by weight, the resin composition becomes brittle and the moldability also deteriorates.

The amount of unsaturated dicarboxylic acid anhydride monomer residue is 10% by weight
If it exceeds the range, the thermal stability and hot water resistance of the composition decrease, which is not preferable. If it is less than 1% by weight, the moldability is poor.

Examples of the polyamide used as the component (B) in the present invention include a polyamide obtained from an aliphatic, aromatic or alicyclic dicarboxylic acid and a diamine, and a polyamide obtained from an aminocarboxylic acid or a cyclic lactam. , Specific examples are nylon 6, nylon 6,6,
Nylon 6,10, Nylon 11, Nylon 12, Nylon 6,12
Aliphatic polyamides such as, polyhexamethylenediamine terephthalamide, aromatic polyamides such as polyhexamethylenediamine isophthalamide, and the like,
It can also be used as a mixture or copolymer of two or more of these.

The copolymer of the α-olefin used as the component (C) in the present invention and an unsaturated carboxylic acid or a glycidyl ester of an α, β-unsaturated acid will be described. As the α-olefin, ethylene, propylene, butene-1,
4-methylpentene-1 and the like, particularly ethylene,
Propylene is preferred.

As the unsaturated carboxylic acid, acrylic acid, monocarboxylic acid such as methacrylic acid, dicarboxylic acid such as maleic acid, fumaric acid and itaconic acid, maleic anhydride, dicarboxylic acid anhydride such as itaconic anhydride, methyl acrylate and methacrylic acid. Examples thereof include carboxylic acid alkyl esters such as methyl acidate, ethyl acrylate, and ethyl methacrylate.

Glycidyl esters of α, β-unsaturated acids are represented by the general formula (Wherein R is a hydrogen atom or a lower alkyl group), and specific examples thereof include glycidyl acrylate and glycidyl methacrylate.

Further, as the unsaturated monomer copolymerizable with the above copolymer, specifically, vinyl ethers, vinyl acetate,
Vinyl esters such as vinyl propionate, methyl,
One or more kinds of esters of acrylic acid and methacrylic acid such as ethyl and propyl may be copolymerized.

In the present invention, the proportion of the component (A), the component (B) and the component (C) is 10 to 90% by weight, preferably 20 to 80% by weight of the component (A).
1 to 20% by weight of component (C), preferably 3 to 15% by weight, relative to 99 to 80% by weight of a resin composition consisting of 10% to 90% by weight of component (B), preferably 20 to 80% by weight. The range of is taken.

If the proportion of the component (A) is less than 10% by weight, the effect of improving heat resistance is insufficient.

On the other hand, when the content of the component (A) exceeds 90% by weight in the total amount of the components (A) and (B), the impact strength of the composition is lowered and the moldability is deteriorated, and the ratio of the component (B) is 10% by weight. If it is less than the above range, the effect of reinforcing the composition of the present invention against impact is insufficient, and satisfactory impact strength cannot be obtained. Also, the chemical resistance is poor. On the other hand, if this ratio of the component (B) exceeds 80% by weight, the water absorption rate and molding shrinkage rate of the composition of the present invention increase, which is not preferable. When the proportion of the component (C) in the composition of the present invention is less than 1% by weight, the impact improving effect is poor and the compatibility improving effect between the component (A) and the component (B) is not sufficient. If it exceeds 5% by weight, the heat resistance is significantly deteriorated, which is not preferable.

The method for mixing the resin composition of the present invention is not particularly limited, and known means can be used. Examples of the means include a Banbury mixer, a tumbler mixer, a mixing roll, a single-screw or twin-screw extruder, and the like.

As a mixing form, there are methods such as ordinary melt mixing, multistage melt kneading using master pellets, and blending in a solution to obtain a composition.

Further, in the composition of the present invention, glass fiber, carbon fiber, aramid fiber, stabilizer, flame retardant, plasticizer, lubricant, ultraviolet absorber, colorant and talc, silica, clay, mica, filler such as calcium carbonate, etc. It is also possible to add.

(Examples) Hereinafter, the present invention will be described with reference to examples.

All parts and% in the examples are expressed on a weight basis.

Experimental Example (1) Manufacture of a polymer obtained by imidizing a copolymer obtained by polymerizing an aromatic vinyl monomer and maleic anhydride in the presence of a rubber-like polymer 100 parts of styrene in an autoclave equipped with a stirrer ,
And 50 parts of methyl ethyl ketone, 24 parts of polybutadiene cut into small pieces were charged, and after the system was replaced with nitrogen gas,
The rubber was dissolved by stirring overnight at room temperature. After raising the temperature to 83 ° C, 67 parts of maleic anhydride and benzoyl peroxide were added.
A solution prepared by dissolving 2 parts and 0.2 part of azobisisobutyronitrile in 400 parts of methyl ethyl ketone was added over 8 hours. After the addition, the polymerization was kept at 83 ° C. for another 3 hours to complete the polymerization. 0.85 molar equivalents of aniline (54.0 parts) and triethylamine (2 parts) were added to maleic anhydride contained in the copolymer solution obtained here, and the mixture was reacted at 140 ° C. for 7 hours. The maleic anhydride monomer residue in the imidized copolymer obtained by the degassing treatment was 4.3% by weight. This was designated as a polymer (A).

Experimental Example (2) Production of an imidized polymer obtained by polymerizing aromatic vinyl, unsaturated dicarboxylic acid anhydride and a copolymerizable vinyl monomer with these in the presence of a rubbery polymer. Instead of 100 parts of styrene of Example (1), 100 parts of styrene and 10 parts of acrylonitrile were used, and 67 parts of maleic anhydride was added.
The same operation as in Experimental Example (1) was carried out except that the amount was changed to 57 parts and 46 parts was used instead of 54 parts of aniline to obtain an imidized polymer. This was designated as a polymer (B).

Experimental Example (3) Manufacture of a polymer obtained by imidizing a copolymer obtained by polymerizing an aromatic vinyl monomer and maleic anhydride: 60 parts of styrene and 50 parts of methyl ethyl ketone were charged into an autoclave equipped with a stirrer, and a system was prepared. After replacing the inside with nitrogen gas, the temperature was raised to 85 ° C, and 40 parts of maleic anhydride and 0.15 part of benzoyl peroxide were added to 250 ml of methyl ethyl ketone.
The solution dissolved in 1 part was continuously added over 8 hours. The temperature was maintained at 85 ° C for a further 3 hours after the addition. A portion of the viscous reaction solution was sampled and the polymerization rate was quantified by gas chromatography. As a result, styrene 99%, maleic anhydride
It was 99%. 34 parts of aniline and 0.3 part of triethylamine, 0.90 molar equivalents to maleic anhydride, were added to the copolymer solution obtained here, and the mixture was reacted at 140 ° C. for 7 hours. 200 parts of methyl ethyl ketone was added to the reaction solution, cooled to room temperature, poured into 1500 parts of vigorously stirred methanol, precipitated, separated by filtration and dried to obtain an imidized copolymer. From C-13 NMR analysis, the maleic anhydride monomer residue was 3.1% by weight. This was designated as a polymer (C).

Experimental Example (4) Production of Copolymer by Polymerization of Aromatic Vinyl Monomer and Unsaturated Dicarboxylic Acid Imide Derivative 100 parts of styrene in an autoclave equipped with a stirrer,
After charging 10 parts of methyl ethyl ketone and substituting the inside of the system with nitrogen gas, the temperature was raised to 100 ° C., and 100 parts of N-phenylmaleimide dissolved in 200 parts of methyl ethyl ketone and the initiator perbutyl Z (NOF Corporation) Made) 0.35 parts
Polymerization was carried out by dropping in 10 hours. After completion of the polymerization, the reaction solution was devolatilized to obtain a polymer. From the elemental analysis, the N-phenylmaleimide content in this polymer was 49.5% by weight. This was designated as a polymer (D).

Experimental Example (5) Manufacture of a polymer obtained by imidizing a copolymer obtained by polymerizing an aromatic vinyl monomer and maleic anhydride, except that 22 parts of aniline was used instead of 34 parts of aniline in Experimental Example (3). In the same manner as in Experimental Example (3), an imidized polymer was obtained. Maleic anhydride monomer residue 14.1% by weight
Met. This was designated as a polymer (E).

Examples 1 to 3 Polymer (A) obtained in Experimental Example (1), nylon-6
(Ube Industries, Ltd., 1013B) and ethylene-glycidyl methacrylate copolymer (Sumitomo Chemical Co., Ltd., Bondfast E) were mixed at the ratio shown in Table-1 and extruded at 270 ° C with a vented extruder to form pellets, then at 270 ° C. Injection molding was performed to mold a test piece. The results are shown in Table-1.

Example 4 Nylon-12 in place of Nylon-6 in Example 1
(Ube Industries, Ltd., 3024U) was used in the same manner as in Example 1 except for using. The results are shown in Table-1.

Examples 5-6 Polymers (B) obtained in Experimental Examples (2) and (3),
(C) was mixed in the proportion shown in Table-1 and the physical properties were measured in the same manner as in Example 1. The results are shown in Table-1.

Examples 7 to 8 Instead of the ethylene-glycidyl methacrylate copolymer in Example 1, ethylene-vinyl acetate-glycidyl methacrylate copolymer (Sumitomo Chemical Co., Ltd., Bondfast 7B), ethylene-ethyl acrylate-maleic anhydride copolymer. (Sumitomo Chemical Co., Ltd., Bondyne AX-806
Example 1 was repeated except that (0) was used. The results are shown in Table-1.

Example 9 Polymer (C) obtained in Experimental Example (3), nylon-6
(Ube Industries, 1013B) and maleated ethylene-propylene copolymer (Mitsui Petrochemical, Tuffmer MP-062)
0) was mixed in the proportions shown in Table-1, pelletized by extrusion with a vented extruder at 270 ° C, and injection-molded at 270 ° C to form test pieces. The results are shown in Table-1.

Comparative Examples 1 to 4 The imidized copolymer used in Example 1, nylon-6,
Table 1 shows ethylene-glycidyl methacrylate copolymer.
The mixture was mixed in the proportion of and the physical properties were measured in the same manner as in Example 1. The results are shown in Table-1.

Comparative Examples 5-6 Polymers (D) obtained in Experimental Examples (4) and (5),
(E), Nylon-6 and ethylene-glycidyl methacrylate copolymer were mixed at the ratio shown in Table-1 and the physical properties were measured in the same manner as in Example 1. The results are shown in Table-1.

In Comparative Example 5, resin sagging occurred from the nozzle of the molding machine during injection molding, and in Comparative Example 6, the test piece turned yellow and silver streaks occurred on the surface.

Comparative Examples 7 to 8 Polymers (D) obtained in Experimental Examples (4) and (5),
(E), nylon-6 and maleated ethylene-propylene copolymer were mixed at the ratio shown in Table-1, and the physical properties were measured in the same manner as in Example 1. The results are shown in Table-1.

In Comparative Example 7, resin sagging occurred from the nozzle of the molding machine during injection molding, and in Comparative Example 8, the test piece turned yellow and silver streaks occurred on the surface.

Test method for measuring physical properties 1) Heat distortion temperature Load 18.6 kg / cm ² , conforming to ASTM D-648.

2) Izod impact strength 1/4 inch width without notch, conforming to ASTM D-256.

3) Gasoline resistance It is expressed by the critical strain% at which cracking occurs when gasoline is in contact with it.

4) Peeling of molded product The measurement was performed by visually observing the periphery of the gate of the injection-molded test piece (ASTM No. 1 dumbbell).

Claims (1)

[Claims] 1. Component (A): 0 to 39% by weight of a rubber-like polymer,
Aromatic vinyl monomer residues 30 to 69% by weight, unsaturated dicarboxylic acid imide derivative residues 30 to 60% by weight, unsaturated dicarboxylic acid anhydride monomer residues 1 to 10% by weight, and vinyl monomers other than these Imidized Copolymer Consisting of 0 to 39% by Weight of Monomer Residue
Resin composition consisting of 10 to 90% by weight and (B) component: 10 to 90% by weight of polyamide 99 to 80% by weight and (C) component: α-olefin and unsaturated carboxylic acid or α, β-unsaturated acid Copolymer 1 with glycidyl ester
The thermoplastic resin composition is characterized by containing -20% by weight.