JPH0778164B2 - Polyamide resin composition - Google Patents

Description

TECHNICAL FIELD The present invention relates to a polyamide resin composition having excellent heat resistance and impact resistance, and more specifically, to a polyamide resin composition having a relatively low glass transition temperature. A polyamide phase (I) composed of a polyamide having a relatively high glass transition temperature, and a modifier phase (II) composed of a glycidyl group-containing ethylene-based copolymer and an acid anhydride-containing ethylene-based copolymer And a polyamide resin composition having excellent heat resistance and impact resistance.

The polyamide resin composition of the present invention is processed into various useful molded articles through injection molding, extrusion molding, etc., and can be applied to a wide range of industrial fields.

(Prior Art) Since polyamide has excellent physical and chemical properties,
It has been widely used as a molding material in recent years. This is because polyamide has high mechanical strength among general-purpose thermoplastics,
This is because it has excellent wear resistance, chemical resistance, heat resistance, and relatively high electrical properties, and has many performances required for engineering plastics. However, engineering plastics are not necessarily satisfactory in their heat resistance and impact resistance. For example, the heat deformation temperature under a load of ASTM D643, 18.56 kg / cm ² is approximately 100 ° C or less, which is insufficient compared with typical engineering plastics such as polycarbonate. Regarding impact strength, the Izod impact strength with ASTM D256 notch is about 10 kg · cm / cm or less, which is far below 70 kg · cm / cm of polycarbonate.

Attempts to improve the heat resistance and impact resistance of such polyamides have been made for a long time. For example, in an attempt to improve the impact resistance, Japanese Patent Publication No. 12546/42546 discloses a method in which 0.1 to 10 mol% of a copolymer of α, β-unsaturated carboxylic acid and olefin is blended with polyamide. −17665
In JP-A-55-44108, a method of blending a copolymer of ethylene, an α, β-unsaturated carboxylic acid derivative, and an olefinic unsaturated monomer into a polyamide is disclosed. Various methods for incorporating the modifiers that are included are disclosed.

As a method of increasing the heat resistance of polyamide, it is common to mix an inorganic material such as glass fiber or talc, but in this case, the impact strength is markedly reduced. A polymer having high heat resistance is blended for the purpose of increasing the heat resistance of polyamide. For example, JP-B-58-50260 discloses a method of blending polyamide with polyarylate, and JP-A-57-1777011 discloses a method of blending a phenol resin. In addition, JP-A-58-3875
Although the effect of improving heat resistance has not been clarified in Japanese Patent Publication No. 1, a method of incorporating a polyamide having high heat resistance is disclosed.

(Problems to be Solved by the Invention) However, for the purpose of enhancing both heat resistance and impact resistance, other polyamides having a high glass transition temperature and α, β-unsaturated dicarboxylic acids are used for the purpose of enhancing both heat resistance and impact resistance. When a modifier phase composed of an olefinic copolymer containing an anhydride as a copolymerization component is blended and melted using an extruder or the like to be extruded as a strand, which is cut to obtain chips, an extruder nozzle The balance effect of the molten polymer flow exiting the reactor is significantly increased, and the problem that strand formation is not possible often occurs.

The cause of this can often be attributed to the fact that the difference between the melt viscosity of various polyamides having a high glass transition temperature and that of one of the polyamides or the modifier phase is too large, but it is not clear.

The present invention blends another polyamide having a high glass transition temperature and an olefin-based copolymer containing α, β-unsaturated dicarboxylic acid anhydride as a copolymerization component into the polyamide,
In obtaining a polyamide resin composition having both excellent heat resistance and impact resistance, it is an object to find a composition having excellent production stability in which the above-mentioned balance effect is suppressed.

(Means for Solving Problems) As a result of earnest research by the present inventors, an olefin-based copolymer containing various polyamides having a high glass transition temperature and α, β-unsaturated dicarboxylic acid anhydride as a copolymerization component. And a polyamide resin composition in which a polyamide is further compounded with yet another olefinic copolymer containing an unsaturated glycidyl monomer as a copolymer component. The inventors have reached the present invention by finding out that the above objectives and all of them are satisfied.

That is, the present invention provides a blending ratio of the polyamide phase (I) composed of the component (A) and the component (B), and the modifier phase (II) composed of the component (C) and the component (D). Is the range represented by formula (1), The component (A) composed of the polyamide phase (I) is selected from polyamides having a glass transition temperature of 30 ° C to 100 ° C, and the component (B) is also selected from polyamides having a glass transition temperature of 120 ° C to 220 ° C. And the weight blending ratio of the component (A) and the component (B) is in the range that satisfies the following formula (2), The component (C) that constitutes the modifier phase (II) is a copolymer of ethylene, an unsaturated glycidyl monomer, and optionally an ethylenically unsaturated monomer, and the component (D) is ethylene. And a copolymer of unsaturated dicarboxylic acid anhydride and optionally an ethylenically unsaturated monomer,
The present invention relates to a polyamide resin composition characterized in that a weight mixing ratio of the component (C) and the component (D) is within a range satisfying the following formula (3).

In the present invention, not only the object of the present invention is achieved by blending an oleyl-based copolymer containing an unsaturated glycidyl monomer as a copolymerization component, but also surprisingly, the impact resistance is further improved. Became clear.

In the present invention, the polyamide phase (I) constitutes (A).
Glass transition temperature used as a component is 30 ℃ or more 100 ℃
Examples of the following polyamides are polytetramethylene adipamide (nylon 46), polyhexamethylene adipamide (nylon 66), polyhexamethylene azamide (nylon 69), polyhexamethylene sebacamide (nylon).
610), polyhexamethylene dodecanoamide (nylon 6
12), polymeta-xylylene adipamide (nylon MXD
6), polycaprolactam (nylon 6), polylauryllactam (nylon 12), etc.
It is not limited to this, and a copolyamide may be used. A mixture of two or more polyamides having a glass transition temperature of 30 ° C or higher and 100 ° C or lower may be used.

In the present invention, the polyamide phase (I) constitutes (B).
Glass transition temperature used as a component is 120 ℃ or more and 220 ℃
Specific examples of the following polyamides include, but are not limited to, copolyamides having the monomer composition shown in Table 1, and two or more polyamides having a glass transition temperature of 120 ° C to 220 ° C. You may use the mixture of.

The polyamide used in the present invention can be produced by a general polymerization method including melt polymerization, but the molecular weight is preferably at least 10.000 or more. Also,
Diamines may be used to provide excess amine end groups over carboxyl groups in the polyamide if desired. It is also possible to use dicarboxylic acid to give an excess of acid end groups. It is also possible to produce these polyamides from acid-forming and amine-forming derivatives of the acids and amines, such as esters, acid chlorides, amine acids and the like.

In order to satisfy both heat resistance and moldability, the compounding ratio of the component (A) and the component (B) of the polyamide phase (I) is expressed by the formula (2)
It is desirable to be within the range.

The component (C) constituting the modifier phase (II) of the present invention is a copolymer of ethylene, an unsaturated glycidyl monomer, and optionally an ethylenically unsaturated monomer.

The unsaturated glycidyl monomer as used herein means one unsaturated bond which can be copolymerized with ethylene monomers in one molecule of the monomer.
It has one or more epoxy groups. For example, general formula (4) (Wherein R ₁ represents a hydrocarbon group having an ethylenically unsaturated bond) and an unsaturated glycidyl ester represented by the general formula (5) (Where X is --CH ₂ --O-- or And R ₁ is the same as in equation (4). ) Unsaturated glycidyl ethers and general formula (6) (Where R ₂ is hydrogen or methyl group and R ₁ is the formula (4)
Is the same as. ) Epoxy alkenes, etc., specifically, glycidyl acrylate, glycidyl methacrylate, itaconic acid monoglycidyl ester,
Itaconic acid diglycidyl ester, butene tricarboxylic acid monoglycidyl ester, butene tricarboxylic acid diglycidyl ester, butene tricarboxylic acid triglycidyl ester, p-styrenecarboxylic acid glycidyl ester, allyl glycidyl ether, 2-methyl allyl glycidyl ether, styrene p-glycidyl ester Ether or p-glycidyl styrene, 3,4-epoxy-1-butene,
3,4-epoxy-3-methyl-1-butene, 3,4-epoxy-1-pentene, 3,4-epoxy-3-methyl-1-pentene, 5,6-epoxy-1-hexene and vinylcyclohexene Examples thereof include monoxide.

The following are specific examples of the ethylenically unsaturated monomer. Olefins such as propylene, butene-1, decene-1, octacene-1, styrene; vinyl esters containing 2 to 6 carbon atoms in the saturated carboxylic acid component, such as vinyl acetate, vinyl propionate, vinyl benzoate, etc. 1 for saturated alcohol component
Esters of acrylic acid and methacrylic acid containing 8 to 8 carbon atoms such as methyl-, ethyl-, propyl-, butyl-, 2-ethylhexyl-, cyclohexyl-, dodecyl-, octadecyl-; α, β-unsaturated dicarboxylic acids Acid esters such as maleic acid diesters; vinyl chlorides, vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, N-vinyl lactams such as N-vinyl pyrrolidone or N-vinyl caprolactam; and acrylic acid amide compounds, secondary N- Examples include vinylcarboxylic acid amides and N-vinyl-N-alkylcarboxylic acid amides.

Of the above ethylenically unsaturated monomers, vinyl acetate and acrylic acid esters are particularly conveniently used among them.

The copolymerization ratio of the unsaturated glycidyl monomer of the component (C) used in the present invention is 0.05 to 95 mol%, preferably 0.1 to 5
It is 0 mol%.

The component (D) constituting the modifier phase (II) of the present invention is a copolymer of ethylene, an α, β-unsaturated dicarboxylic acid anhydride and, if necessary, an ethylenically unsaturated monomer. .

The α, β-unsaturated dicarboxylic acid anhydride referred to here is represented by the following formula (7). (Wherein R ₃ and R ₄ represent hydrogen, an alkyl group or halogen), and examples thereof include maleic anhydride, methylmaleic anhydride, chloromaleic anhydride, citraconic anhydride, Examples include butenyl succinic anhydride and tetrahydrophthalic anhydride.

Specific examples of the ethylenically unsaturated monomer optionally used as the copolymerization component of the component (D) are the same as those of the component (C).

The copolymerization ratio of the α, β-unsaturated dicarboxylic acid anhydride as the component (D) used in the present invention is 0.05 to 95 mol%, preferably 0.1 to 50 mol%.

Further, α. Constituting the component (C) used in the present invention. Part or all of the β-unsaturated carboxylic acid anhydride or carboxylic acid ester may be a metal salt.

The compounding ratio of the component (C) and the component (D) constituting the modifier phase (II) is determined by formula (3) in order to obtain satisfactory impact resistance and molding processability. It is desirable to be within the range.

As a method for producing the ethylene-based copolymer that constitutes the component (C) or the component (D), a so-called known radical copolymerization method is used, or a radical generator is present in the ethylene-based copolymer, A method in which one or more unsaturated monomers having a group is subjected to a radical graft reaction in the presence or absence of a solvent or a dispersion medium can also be mentioned. In particular, in the case of grafting in a molten state, by using a melt-kneading machine such as an extruding group, a kneader or a Banbury mixer, the intended product can be obtained in a very short time by a simplified treatment method.

In the resin composition of the present invention, in order to satisfy both heat resistance and impact resistance, the compounding ratio of the polyamide phase (I) and the modifier phase (II) is within the range of the formula (1). preferable.

The glass transition temperature of the polyamide used in the present invention is measured by a differential scanning calorimeter (DSC). The rate of temperature rise is 20 ° C / min, and the glass transition temperature is determined by a conventional method.

In the polyamide resin composition of the present invention, additives such as a heat stabilizer, an oxidation stabilizer, a light stabilizer, a lubricant, a pigment, a flame retardant and a plasticizer may be further mixed.

Also, glass fibers, metal fibers, potassium titanate whiskers,
Fibrous reinforcing agents such as carbon fibers, talc, calcium carbonate, mica, glass flakes, milled fibers, metal flakes, filler type reinforcing agents such as metal powders may be mixed. In particular, by mixing glass fibers in an amount of 10 to 50% by weight with respect to 50 to 90% by weight of the polyamide resin composition of the method of the present invention, not only the mechanical strength and heat resistant temperature are greatly improved, but also the water resistance is improved. , Further improvement can be seen, which is preferable in achieving the object of the present invention.

Hereinafter, the present invention will be described in more detail with reference to Examples.
The present invention is not limited to this.

(Examples) Examples 1 to 11 (Synthesis of nylon salt) (1) HMD / TPA salt (hexamethylenediamine / terephthalate) 23.7 g of a 64.4% HMD aqueous solution was heated to 70 ° C, and 25 g of T
PA was added in small portions with stirring. The TPA dissolved as the salt was formed. Then, the remaining insoluble portion was removed by filtration, the filtrate was cooled, salt was deposited, and this was collected by filtration. This was dried under reduced pressure at 100 ° C. for 24 hours and used for polyamide synthesis.

(2) HMD / IPA salt (hexamethylenediamine / isophthalate) At room temperature, 25 g of IPA was added to 200 ml of methanol to obtain a suspension. There, a 64.4% aqueous solution of hexamethylenediamine 2
3.7 g was added dropwise with stirring. IPA in suspension with fever
Melted. When stirring was continued and the solution was cooled, salt was precipitated. This was collected by filtration and dried under reduced pressure at 100 ° C. for 24 hours to be used for polyamide synthesis.

(3) PACM • IPA salt (bis (p-aminocyclohexyl) methane • isophthalate) At room temperature, 50 g of IPA was added to 1.5 of methanol to obtain a suspension solution. A solution of 71.6 g of PACM dissolved in 30 ml of methanol was added dropwise thereto with stirring. In a suspended state with fever
IPA dissolved. When stirring was continued and the solution was cooled, salt was precipitated. This was collected by filtration and dried under reduced pressure at 100 ° C. for 24 hours to be used for polyamide synthesis.

(4) Dimethyl PACM ・ IPA salt (bis (3-methyl-4-aminocyclohexyl) methane ・ isophthalate) (5) Tetraethyl PACM ・ IPA salt (bis (3,5-dimethyl-4-aminocyclohexyl))
Methane / isophthalate) (4) and (5) were obtained in the same manner as (3).

(6) MXD / IPA salt (meta-xylylenediamine / isophthalate) 83 g of IPA was added to 1.5 of methanol to obtain a suspension solution. 68 g of MXD was added to this while heating and stirring at 60 ° C. When stirring was continued for 30 minutes and the solution was cooled, salt was precipitated. Collect it by filtration
It was heated and dried under reduced pressure at 100 ° C. for 24 hours, and was used for synthesis of polyamide.

(7) 1,3-BAMC • IPA salt (1,3-diaminomethylcyclohexane • isophthalate) 83 g of IPA was added to methanol 1 to obtain a suspension solution. this
71 g of 1,3-BAMC was added while heating and stirring at 60 ° C. Then I
PA was completely dissolved and a clear solution was obtained. The solution was cooled and the precipitated salt was collected by filtration and dried under reduced pressure with heating at 100 ° C for 24 hours to synthesize polyamide.

(8) 1,4-DAC • IPA salt (1,4-diaminocyclohexane • isophthalate) 83 g of IPA was added to methanol 1 to obtain a suspension solution. this
While heating and stirring at 60 ° C., 575 g of 1,4-DAC was added little by little. Then, IPA was completely dissolved and a transparent solution was obtained.
The solution was cooled, the precipitated salt was collected by filtration, and heated and dried under reduced pressure at 100 ° C for 24 hours to synthesize polyamide.

(9) 1.3-BAMC.AA salt (1,3-diaminomethylcyclohexane.isophthalate) 73 g of AA was added to 500 ml of methanol to obtain a suspension solution. this
While heating and stirring at 60 ° C., 71.5 g of 1,3-BAMC was added little by little. Then, AA was completely dissolved and a transparent solution was obtained. The solution was cooled, and the precipitated salt was collected by filtration and dried under reduced pressure with heating at 100 ° C. for 24 hours to synthesize polyamide.

(10) PACM • AA salt (bis (p-aminocyclohexyl) methane adipate) 73 g of AA was added to 500 ml of methanol to obtain a suspension solution. While heating and stirring this at 60 ° C, 105.5 g of PACM was added to 70 m of methanol.
The solution dissolved in 1 was added dropwise. Then, AA was completely dissolved and a transparent solution was obtained. The solution was cooled, and the precipitated salt was collected by filtration and dried under reduced pressure at 100 ° C for 24 hours for synthesis of polyamide.

(11) Piperazine / IPA salt (piperazine / isophthalate) IPA (83 g) was added to methanol 1 to obtain a suspension solution. While heating and stirring this at 60 ° C, 43 g of piperazine was added little by little. Then, IPA was completely dissolved and a transparent solution was obtained. The solution is cooled and the precipitated salt is collected by filtration and kept at 100 ° C for 2
It was dried under reduced pressure for 4 hours and used for the synthesis of polyamide.

Examples 12 to 25 (Synthesis of Polyamide with High Glass Transition Temperature) The 11 nylon salts, lauryl lactam salts and caprolactam salts obtained in Examples 1 to 11 were used and weighed so as to have the monomer composition shown in Table 2. I took it. Then, this was put into a glass polymerization tube, and after nitrogen substitution was performed 5 times, the mixture was stirred and mixed at normal pressure (under nitrogen stream) at the temperature of Table 1 for 3 hours to obtain a polyamide.

The glass transition temperature of the obtained polyamide was measured using a Perkin-Elmer DSC-2C type device at a temperature rising rate of 20 ° C./min. The results obtained are listed in Table 1.

Examples 26, 27 (Production of Polyamide with High Glass Temperature) 1990 g of dimethyl PACM • IPA salt, 985 g of lauryl lactam and water 3 were placed in an autoclave. Next, the aqueous solution was heated to raise the pressure to 20 kg / cm ² , and excess water was gradually discharged while maintaining the pressure. When the temperature reached about 290 ° C, the pressure was gradually reduced to atmospheric pressure over about 90 minutes and kept at atmospheric pressure for about 50 minutes. The polymer was then extruded from the autoclave by nitrogen pressure and cut into pellets. The sample name of this polyamide was PA15.

Similarly, 1,3-BAMC • IPA 1540 g and PACM • AA salt 445 g were used to obtain a polyamide. The sample name of this polyamide is PA
16

The glass transition temperatures of PA15 and PA16 were 152 ℃ and 190 ℃, respectively.

Examples 28 to 33 Nylon 6 (Unitika Nylon A1030B) as the component (A)
RL, glass transition temperature 51 ° C), nylon 66 (ICI's Maranille A125, glass transition temperature 63 ° C) and nylon 46 (DSM's Stannyl TS-300, glass transition temperature 81 ° C), PA15 and PA16 as (B) component, As the component (C), Bond First-2C (Sumitomo Chemical Co., Ltd., hereinafter referred to as BF-2C) and Bond First-E (Sumitomo Chemical Co., Ltd., hereinafter referred to as BF-E),
As component (D), bondyne A × 8040 (produced by Sumika CDF, hereinafter referred to as BDA × 8040), bondine L × 4110 (sumika CDF
Manufactured by BDL × 4110) and Keltaflex N35 (DSM)
(Manufactured by K.K., hereinafter referred to as K-N35) was mixed and blended at a ratio of Table 2. This was vacuum dried at 80 ° C for 24 hours and then extruded at a cylinder temperature of 270-300 ° C with a PCM45 type twin-screw extruder manufactured by Ikegu Tekko.

The production stability of the resin composition in Table 2 was judged by the presence or absence of the balance effect during extrusion. ○ indicates good extrudability, and × indicates extremely unstable extrudability due to occurrence of the balance effect.

(Effect of Invention) As shown in the results of Table 2, the polyamide resin composition of the present invention has improved production stability and significantly improved impact strength. In addition, the heat resistance indicated by the heat distortion temperature was also extremely high.

Claims (1)

[Claims] 1. A compounding ratio of a polyamide phase (I) composed of a component (A) and a component (B) and a modifier phase (II) composed of a component (C) and a component (D). Is a range represented by the formula [I], The component (A) constituting the polyamide phase (I) is selected from polyamides having a glass transition temperature of 30 ° C. or higher and 100 ° C. or lower,
Similarly, the component (B) has a glass transition temperature of 120 ° C to 220 ° C.
Selected from the following polyamides, and also with (A) component and (B)
The weight blending ratio of the components is in the range that satisfies the following formula [2], The component (C) that constitutes the modifier phase (II) is a copolymer of ethylene, an unsaturated glycidyl monomer, and optionally an ethylenically unsaturated monomer, and the component (D) is ethylene. A copolymer of unsaturated dicarboxylic acid anhydride and optionally an ethylenically unsaturated monomer,
A polyamide resin composition characterized in that a polymerization compounding ratio of the component (C) and the component (D) is within a range satisfying the following formula [3].