JP3385104B2 - Resin composition - Google Patents

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel resin composition having excellent mechanical properties such as impact resistance and rigidity, and excellent chemical and thermal properties.

[0002]

Polyamide is excellent in mechanical properties, sliding properties, thermal properties, and chemical resistance, and has already been widely used as a molded product useful in the fields of electric equipment, automobiles, general machinery, miscellaneous goods, and the like. But, as is well known,
Polyamide has a high water absorbency, and has a drawback that it absorbs moisture contained in the atmosphere in actual use and causes deterioration of mechanical properties and dimensional change.

In order to complement the physical properties of such polyamides, there have been proposed a number of resin compositions containing a polycarbonate which is excellent in heat resistance and water resistance but has a problem in moldability and chemical resistance (for example, JP-A-50-116541,
59-68368, etc.). However, this resin composition has a problem that the toughness represented by impact strength is poor because the compatibility of both resins is insufficient.

JP-A-58-8760 discloses a mixture of polyamide and polycarbonate with a styrene-maleic anhydride copolymer or a rubber-modified styrene-maleic anhydride copolymer. Japanese Patent Laid-Open Publication Nos. 1993-242242 and 1994-1994 respectively disclose blends of an epoxy group-containing olefin-based copolymer and an olefin-based copolymer obtained by copolymerizing an anhydride of α, β-unsaturated dicarboxylic acid. Although these resin compositions have improved toughness represented by impact strength, they cause new performance inconveniences such as reduced heat resistance and reduced elastic modulus.

Further, JP-A-3-215558 discloses a resin composition comprising polyamide, polycarbonate and layered silicate. This composition was found to have excellent mechanical strength and heat resistance, but in order to uniformly disperse the layered silicate in the resin composition, a pretreatment step for contacting it with a swelling agent in advance. Is required
There is a problem that the manufacturing cost increases.

[0006]

SUMMARY OF THE INVENTION The present invention solves the above problems and provides a resin composition comprising polyamide and polycarbonate with excellent impact resistance and rigidity without impairing the excellent chemical properties, heat resistance and moldability. Is to greatly improve. Another object of the present invention is to provide a molding material which is excellent in mechanical properties such as impact resistance and rigidity, heat resistance, chemical resistance and moldability, and which gives a molded article having good gloss.

[0007]

The present invention is intended to solve the above-mentioned problems, and its gist is as follows. 0.01 to 20% by weight of swellable fluoromica mineral obtained by polymerizing monomers in the presence of swellable fluoromica mineral
Polyamide 30-90 wt% and Polycarbonate 70
A resin composition comprising 10 to 10% by weight. A resin composition in which 3 to 30% by weight of the following impact resistance-imparting material consisting of A and B is blended with the above resin composition. A: Epoxy group-containing olefin-based copolymer obtained by copolymerizing one or more kinds of unsaturated glycidyl monomer and one or more kinds of ethylenically unsaturated monomer, B: not compatible with polyolefin or olefin-based copolymer The acid anhydride-containing olefin-based copolymer obtained by copolymerizing a saturated dicarboxylic acid anhydride will be described in detail below.

Preferred polyamides in the present invention include nylon 6, nylon 46, nylon 66,
Nylon 610, Nylon 612, Nylon 116, Nylon
11, Nylon 12, Nylon 6I, Nylon 6/66, Nylon 6T / 6I, Nylon 6 / 6T, Nylon 66 /
6T, polytrimethylhexamethylene terephthalamide, polybis (4-aminocyclohexyl) methandodecamide, polybis (3-methyl-4-aminocyclohexyl) methandodecamide, polymethaxylylene adipamide, nylon 11T, polyundecamethylenehexa Hydroterephthalamide, bis (4-aminocyclohexyl)
Methanetere / isophthalate and bis (3-methyl-4)
-Aminocyclohexyl) methane / hexamethylenediamine / I / T copolymer and the like, and two or more kinds may be used in combination. In addition, I represents an isophthalic acid component and T represents a terephthalic acid component.

Of these, particularly preferred are nylon 6, nylon 46, nylon 66, nylon 6T /
6I, nylon 6 / 6T, nylon 66 / 6T.

The relative viscosity of the polyamide is not particularly limited, but a relative viscosity determined from a mixture of phenol and tetrachloroethane in a weight ratio of 60/40 as a solvent at a temperature of 25 ° C. and a concentration of 1 g / dl of 1.5 to. The range of 5.0 is preferable. If the relative viscosity is too small, the mechanical performance of the resin composition will deteriorate, and if it is too large, the moldability of the resin composition will rapidly decrease, which is not preferable.

A preferred range of the concentration of amino groups and carboxyl groups in the polyamide is 20 to 200 equivalents / both.
Tons. If it is smaller than this range, the effect of the present invention tends to be small, and if it is larger than this range, the melt viscosity of the obtained resin composition may excessively increase, which is not preferable.

In the present invention, when the above polyamide is produced, a swellable fluoromica-based system is added to a monomer, that is, a salt of aminocarboxylic acid or lactam, a salt of diamine and dicarboxylic acid (nylon salt) or a mixture. Add minerals and polymerize.

The swelling fluoromica mineral used in the present invention is represented by the following formula. αMF · β (aMgF ₂ · bMgO) · γSiO ₂ Here, M represents sodium or lithium, and α, β,
γ, a, and b each represent a coefficient, and 0.1 ≦ α ≦ 2, 2 ≦ β
≦ 3.5, 3 ≦ γ ≦ 4, 0 ≦ a ≦ 1, 0 ≦ b ≦ 1, a + b
= 1.

As a method for producing such a fluoric mica-based mineral, oxides such as silicon oxide, magnesium oxide, and aluminum oxide are mixed with various fluorides, and the mixture is heated to 1400 to 1500 ° C. in an electric furnace or a gas furnace. There is a so-called melting method in which the fluorinated mica-based mineral is crystallized in the reaction vessel during the cooling process by completely melting it.

Another method is disclosed in Japanese Patent Laid-Open No. 2-149415.
There is a method disclosed in the publication. That is, it is a method in which talc is used as a starting material and alkali ions are intercalated into the starting material to obtain a fluoromica-based mineral. In this method, talc is mixed with alkali silicofluoride or alkali fluoride and heat-treated in a magnetic crucible at 700 to 1200 ° C for a short time to obtain fluoromica. The swellable fluoromica-based mineral used in the present invention is particularly preferably one produced by this method.

The amount of alkali silicofluoride or alkali fluoride to be mixed with talc is preferably 10 to 35% by weight of the mixture, and if it is out of this range, the production rate of swelling fluoromica-based minerals descend.

In order to obtain a swelling fluoromica-based mineral, it is necessary that the alkali metal silicofluoride or alkali metal fluoride is sodium or lithium. These alkali metals may be used alone or in combination. Among the alkali metals, potassium is not preferable because it does not give a swelling fluoromica-based mineral, but it is used in combination with sodium or lithium, and if it is a limited amount, it is used for the purpose of adjusting the swelling property. Is also possible.

Further, in the step of producing the swellable fluoromica-based mineral, it is possible to mix a small amount of alumina to control the swelling property of the swellable fluoromica-based mineral produced.

The term "swelling property" as used in the present invention means that the fluoromica absorbs polar molecules such as aminocarboxylic acid, nylon salt and water molecules or cations between the layers to increase the interlayer distance or further swelling and cleavage. , Means the property of forming ultrafine particles, and the fluoromica represented by the above formula exhibits such swelling property.

The swellable fluoromica-based mineral has a particle size of 15 μm.
It is particularly preferable that the thickness is 10 μm or less and the layer thickness in the C-axis direction measured by the X-ray powder method is 9 to 20 Å.

The swelling fluoromica-based mineral is compounded during the polymerization of the polyamide so as to be in the range of 0.01 to 20% by weight with respect to the polyamide produced. If the content is too small, the effect of improving mechanical strength, heat resistance, and dimensional stability will not be sufficiently exhibited, and if it is too large, the toughness will be significantly reduced.

With respect to the monomers forming the polyamide,
By polymerizing the monomer in the presence of a predetermined amount of the swellable fluoromica mineral, the swellable fluoromica mineral is sufficiently finely dispersed in the polyamide, and the effect of the present invention is remarkably exhibited.

In the present invention, the matrix resin is composed of the polyamide containing the swelling fluoromica-based mineral and the polycarbonate.

As the polycarbonate, those obtained by reacting bisphenols, particularly bisphenol A [2,2-bis (4'-hydroxyphenyl) propane], with a carbonic acid ester or phosgene are preferably used. Then, in order to obtain a resin composition having preferable physical properties, it is preferable to use a polycarbonate having an average molecular weight of 5,000 to 100,000.

In the resin composition of the present invention, the ratio of the polyamide containing a swelling fluoromica mineral and the polycarbonate is 30 to 90% by weight, the former is 40 to 70% by weight, and the latter is 70 to 10% by weight. In particular, it is suitable to set it to 60 to 30% by weight.

Further, in the resin composition of the present invention, an impact resistance-imparting material comprising an epoxy group-containing olefin copolymer A and an acid anhydride-containing olefin copolymer B is added to the above resin composition. It is a thing.

Epoxy group-containing olefin copolymer A
Is obtained by polymerizing one or more kinds of unsaturated glycidyl monomers and one or more kinds of olefinic monomers, and the mode of the copolymerization may be random, block, graft or alternating.

Specific examples of the epoxy group-containing olefinic copolymer A include ethylene-glycidyl methacrylate copolymer, ethylene-glycidyl acrylate copolymer, ethylene-glycidyl methacrylate-vinyl acetate copolymer and ethylene-glycidyl acrylate-polymer. Examples thereof include vinyl acetate copolymer.

The copolymerization amount of the unsaturated glycidyl monomer in the epoxy group-containing olefinic copolymer A is 0.
05-95 mol%, especially 0.1-50 mol% is suitable.

The acid anhydride-containing olefin copolymer B is
It is obtained by copolymerizing an unsaturated dicarboxylic acid anhydride with a polyolefin or an olefin-based copolymer.

Specific examples of the acid anhydride-containing olefin copolymer B include ethylene-propylene copolymer or ethylene-propylene-diene copolymer and endo-bicyclo- (2,2,1) -5-heptene. -Copolymer of 2,3-dicarboxylic acid anhydride or maleic anhydride, copolymer of ethylene-acrylic acid ester copolymer or ethylene-methacrylic acid ester copolymer with maleic anhydride And so on.

The amount of the unsaturated dicarboxylic acid anhydride copolymerized in the acid anhydride-containing olefin copolymer B is 0.
05-95 mol%, preferably 0.1-50 mol% is suitable.

The mixing ratio of the epoxy group-containing olefin copolymer A and the acid anhydride-containing olefin copolymer B is such that the epoxy group / acid anhydride equivalent ratio is 1/9 to 9/1, particularly 3
It is preferable to set it in the range of / 7 to 7/3.

The proportion of the impact resistance imparting material in the resin composition must be 3 to 30% by weight. This amount is 3
If it is less than 30% by weight, the impact strength improving effect cannot be obtained.
If it exceeds, the heat resistance is greatly reduced. The resin composition of the present invention is produced by melt-kneading the above-mentioned components. The melt-kneading temperature at that time mainly depends on the kind of polyamide and the composition ratio of polyamide and polycarbonate. Generally, when a crystalline polyamide is used, it is preferable that the melt-kneading temperature is within the temperature range from the melting point to the melting point plus 80 ° C. When the amorphous polyamide is used, it is preferable to melt-knead in a temperature range which is usually 50 to 150 ° C. higher than the highest glass transition temperature of the polymer in the components constituting the resin composition. Although the melt-kneading time depends on the temperature and the melt-kneading apparatus used, it is usually in the range of 1 to 30 minutes. As the melt-kneading device, a Banbury mixer, a roll mixer, a kneader, a single-screw extruder, a multi-screw extruder or the like can be used. Further, all the components constituting the resin composition may be supplied to the melt-kneading device at once, or each component may be supplied to the melt-kneading device in a multi-stage system in which each component is supplied from different supply ports.

According to the resin composition of the present invention, the toughness is lowered and the fibrous material is deteriorated, which is observed in the conventional resin composition reinforced with glass fiber or carbon fiber or inorganic filler such as calcium carbonate. Problems such as warping of a molded product of a reinforced resin composition and a problem that a resin composition reinforced with an inorganic filler cannot be improved in mechanical strength and heat resistance unless a large amount thereof is blended are solved.

The resin composition of the present invention contains a pigment, a heat stabilizer, an antioxidant, a weatherproofing agent, a flame retardant, a plasticizer, a release agent, and other reinforcing materials as long as the characteristics are not significantly impaired. It can also be added. Such heat stabilizers and antioxidants include hindered phenols, phosphorus compounds,
There are hindered amines, sulfur compounds, and copper compounds.
As the weather resistance agent, general benzophenones and benzotriazoles are used. As the flame retardant, a general phosphorus flame retardant or a halogen flame retardant is used.

Examples of the reinforcing material include clay, talc,
Calcium carbonate, zinc carbonate, wollastonite, silica,
Alumina, magnesium oxide, calcium silicate, sodium aluminate, calcium aluminate, sodium aluminosilicate, magnesium silicate, aluminum hydroxide, calcium hydroxide, barium sulfate, potassium alum, sodium alum, iron amylon, glass balloon, Carbon black, zinc oxide, antimony trioxide, boric acid, borax, zinc borate, zeolite, hydrotalcide, metal fiber, metal whiskers, ceramic whiskers, potassium titanate whiskers, boron nitride, mica, graphite, glass fibers, carbon fibers And so on.

According to the present invention, a resin composition having excellent mechanical properties such as impact resistance, water resistance, heat resistance and moldability can be obtained. Utilizing its excellent performance, it is used as a molded body useful in electric fields, automobiles, machines, sundries, and other fields.

[0039]

In the present invention, since the swellable fluoromica-based mineral-containing polyamide obtained by adding the swellable fluoromica-based mineral to the monomer of the polyamide and polymerizing the swellable fluoromica-based mineral is used, The particles are sufficiently finely dispersed, and as a result, the melt-kneaded product with the polycarbonate is finely dispersed with respect to each other, and excellent physical properties are obtained.

When the epoxy group-containing olefin-based copolymer A and the acid anhydride-containing olefin-based copolymer B are used together as the impact resistance-imparting material, gelation, coloring, and It is surprising that defects such as decomposition or phase separation and defective gloss on the surface of the molded product are eliminated, and the impact strength is improved.

[0041]

EXAMPLES Next, the present invention will be described in detail with reference to examples. In addition, the raw materials and measuring methods in Examples and Comparative Examples are as follows. 1. Raw material (1) Talc pulverized by a fluorine mica ball mill to have an average particle size of 2 μm, fluorinated silica and alumina having an average particle size of 2 μm shown in Table 1 are mixed at a ratio (parts by weight) shown in Table 1, Put this in a magnetic crucible and hold it in an electric furnace at 800 ° C for 1 hour.
Fluorine mica of M-1 to M-3 was synthesized. The average particle diameter of the generated fluoromica was 1.8 μm, and as a result of measurement by the X-ray powder method, M-1 to M-3 showed that the peak corresponding to the thickness 9.2Å of the raw talc in the C-axis direction. Peaks corresponding to 12 to 16Å indicating disappearance and formation of swelling fluoromica were observed.

[0042]

[Table 1]

(2) Polycarbonate Mitsubishi Gas Chemical Co., Ltd., Iupilon S-2000 (bisphenol A type polycarbonate) (3) Epoxy group-containing olefin copolymer ethylene-glycidyl methacrylate-vinyl acetate copolymer (Sumitomo Chemical Co., Ltd. Bondfast E) (4) Olefin copolymer containing acid anhydride (modified EPR) Melt index 2.0 g / 10 min (190 ° C), ethylene-propylene copolymer with ethylene content of 72.0% by weight (EP
R) 1000 parts by weight, endo-bicyclo- (2,2,1) -5-heptene-2,3-dicarboxylic acid anhydride 3 parts by weight and di-t
A mixture of 1.0 part by weight of butyl peroxide and room temperature by a Henschel mixer was supplied to a twin-screw extruder and extruded at 200 ° C. to obtain cylindrical pellets having a diameter of 2 mm and a length of 3 mm.

2. Measurement method (a) Bending strength and flexural modulus A bending test piece having a thickness of 1/8 inch was used and measured according to ASTM D790.

The value after the moisture absorption treatment is 60 ° C. and 95% RH.
It is a value measured in the same manner after moisture absorption treatment for 168 hours. (b) Izod impact test It measured based on ASTMD256 using the said test piece. (c) Heat distortion temperature (HDT) Using the above test piece, a load of 4.5 kg based on ASTM D648.
It was measured at / cm ² . (d) Moisture absorption rate Using a square test piece with a thickness of 2 mm and a width of 50 mm, 60 ° C, 95%
Moisture absorption treatment was performed under the condition of RH for 168 hours, and the moisture absorption rate was calculated from the weight change. (e) Dimensional change Using the same test piece as above, moisture absorption treatment was carried out in the same manner, and then dimensional change in thickness, length and width was measured, and the average value was taken as dimensional change.

Examples 1-10 10 kg of ε-caprolactam, 2 kg of water and M-1,
Mix 300 g of M-2 or M-3 into a reactor with an internal volume of 30 liters, heat to 250 ° C with stirring, and gradually release water vapor, 4 kg / cm ² to 15 kg
The pressure was raised to a pressure of / cm ² . Thereafter, the pressure was released to a pressure of ² kg / cm ² and polymerization was carried out at 260 ° C. for 3 hours.

At the end of the polymerization, the reaction product was discharged in the form of strands, cooled, solidified, and then cut into pellets. The obtained pellets were treated with hot water at 95 ° C., scoured, and dried. The obtained pellets of swellable fluoromica-containing nylon 6 are designated as A-1, A-2, and A-3, respectively. The relative viscosity and end group concentration (equivalent / ton) of pellets A-1, A-2, and A-3 were as follows. Relative Viscosity Amino group Carboxyl group A-1 2.64 57 59 A-2 2.66 56 57 A-3 2.65 57 58 After mixing the raw materials with the compounding composition (parts by weight) shown in Tables 2 and 3, a twin-screw extruder (Ikegai) Tektronix PCM-45) and melt kneading at a temperature of 270 ° C. and an average residence time of 2 minutes and 23 seconds,
Pelletized. After drying the obtained pellets, a test piece was molded using an injection molding machine at a cylinder temperature of 260 ° C and a mold temperature of 80 ° C. The results of various performance evaluations using the obtained test pieces are shown in Tables 2 and 3.

[0048]

[Table 2]

[0049]

[Table 3]

Examples 11 to 20 To 10 kg of nylon 66 salt, 3 kg of water and M-1, M-
150 g of 2 or M-3 is blended, and the content is 30
It was placed in a liter reactor and heated at 230 ° C. with stirring until the internal pressure became 18 kg / cm ² . After reaching that pressure,
The pressure was maintained by heating while gradually releasing water vapor. When the temperature reached 280 ° C., the pressure was released to normal pressure, and the polymerization was further performed for 2 hours. When the polymerization was completed, the reaction product was discharged in a strand shape, cooled, solidified, cut into pellets, and dried. The obtained pellets of the swellable fluoromica-containing nylon 66 were A-4, A-5, and A-6, respectively.
And The relative viscosities and end group concentrations (equivalents / ton) of pellets A-4, A-5, and A-6 were as follows. Relative Viscosity Amino group Carboxyl group A-4 2.70 51 62 A-5 2.71 50 64 A-6 2.70 51 63 After mixing the raw materials with the compounding composition (parts by weight) shown in Tables 4 to 5, a twin-screw extruder (Ikegai) Tektronix PCM-45), melt kneading at a temperature of 280 ° C and an average residence time of 2 minutes 37 seconds,
Pelletized. After drying the obtained pellets, a test piece was molded using an injection molding machine at a cylinder temperature of 280 ° C and a mold temperature of 90 ° C. The results of various performance evaluations using the obtained test pieces are shown in Tables 4-5.

[0051]

[Table 4]

[0052]

[Table 5]

Comparative Examples 1 to 10 Nylon 6 containing no swelling fluoromica mineral
(A1030 manufactured by Unitika Ltd.) and nylon 66 (A125 manufactured by DuPont) were used to mix the raw materials in advance with the compounding compositions (parts by weight) shown in Tables 6 to 7, and the twin-screw extruder (P manufactured by Ikegai Tekko KK) was used.
CM-45) and melt-kneaded to obtain pellets.
The kneading conditions were a temperature of 270 ° C. for nylon 6 and an average residence time of 2 minutes and 25 seconds, and a temperature of 280 ° C. for nylon 66 and an average residence time of 2 minutes and 37 seconds. Using the obtained pellets,
The test pieces were molded in the same manner as in the above-mentioned examples, and various performance evaluations were performed. The results are shown in Tables 6 to 7.

[0054]

[Table 6]

[0055]

[Table 7]

[0056]

EFFECTS OF THE INVENTION According to the present invention, mechanical properties such as impact strength and rigidity and heat resistance are improved as compared with the conventional resin composition comprising polyamide and polycarbonate, and the size and mechanical properties due to water absorption are improved. Provided is a reinforced resin composition having excellent performance with reduced change.

Front page continuation (72) Inventor Mioko Watanabe 23 Uji Kozakura, Uji City, Kyoto Prefecture Unitika Ltd. Central Research Laboratory (56) References JP-A-6-80820 (JP, A) JP-A-2-29457 (JP, A) (58) Fields surveyed (Int.Cl. ⁷ , DB name) C08L 69/00 C08L 77/00-77/12

Claims (6)

(57) [Claims] 1. A swellable fluoromica mineral obtained by polymerizing a monomer in the presence of a swellable fluoromica mineral is 0.01
A resin composition comprising 30 to 90% by weight of polyamide and 20 to 10% by weight of polycarbonate and 70 to 10% by weight of polycarbonate. 2. A resin composition comprising the resin composition according to claim 1 and 3 to 30% by weight of the following impact resistance-imparting material consisting of A and B. A: Epoxy group-containing olefin-based copolymer obtained by copolymerizing one or more kinds of unsaturated glycidyl monomer and one or more kinds of ethylenically unsaturated monomer, B: not compatible with polyolefin or olefin-based copolymer Acid anhydride-containing olefin-based copolymer obtained by copolymerizing saturated dicarboxylic acid anhydride 3. An epoxy group-containing olefin-based copolymer A
Is an ethylene-glycidyl methacrylate copolymer, an ethylene-glycidyl acrylate copolymer, ethylene-
The resin composition according to claim 2, which is a copolymer selected from a glycidyl methacrylate-vinyl acetate copolymer and an ethylene-glycidyl acrylate-vinyl acetate copolymer. 4. An acid anhydride-containing olefin-based copolymer B
Is an ethylene-propylene copolymer or ethylene-propylene-diene copolymer endo-bicyclo- (2,2,1)
Copolymerization of 5-heptene-2,3-dicarboxylic acid anhydride or maleic anhydride, ethylene-acrylic acid ester copolymer or ethylene-methacrylic acid ester copolymer with maleic anhydride The resin composition according to claim 2, which is a copolymer selected from the above copolymers. 5. The impact resistance-imparting material comprises an epoxy group-containing olefin-based copolymer A and an acid anhydride-containing olefin-based copolymer B having an equivalent ratio of epoxy groups and acid anhydrides of 1/9 to 9.
The resin composition according to claim 2, wherein the resin composition is mixed so as to be in a range of / 1. 6. The polycarbonate is bisphenol A.
The resin composition according to claim 1, which is a type carbonate.