JP3385103B2 - Resin composition - Google Patents

Description

Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition having excellent mechanical properties such as impact resistance, heat resistance and moldability. BACKGROUND OF THE INVENTION Polyamides have excellent mechanical properties, heat resistance and chemical resistance, but have the disadvantage of causing a decrease in rigidity and dimensional change upon absorption of water. [0003] In order to improve the physical properties of such polyamides, an ABS resin having impact resistance and water resistance is combined with a polyamide. Resin composition in which the change in mechanical properties is reduced (Japanese Patent Publication No. 38-23)
476, etc.). However, this resin composition has a problem in that the compatibility between the polyamide and the ABS resin is poor and the impact strength is low. Further, a blend of polyamide and an ABS resin modified with a functional group capable of performing a chemical reaction or chemical interaction has been proposed (Japanese Patent Laid-Open No. 1-294).
No. 76, 2-175755). However, with this resin composition, the moldability and impact resistance were improved to some extent, but the improvement effect was insufficient, and the mechanical strength, heat resistance, and dimensional stability were not satisfactory. Further, JP-A-2-29475 discloses a resin composition comprising a polyamide, an impact modifier and a layered silicate. This resin 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 pre-treatment for previously contacting with a swelling agent was performed. There is a problem that a process is required and the manufacturing cost increases. SUMMARY OF THE INVENTION The present invention is intended to solve the above-mentioned problems, and is excellent in mechanical properties such as impact resistance, heat resistance and moldability, and has a dimension due to water absorption. Another object of the present invention is to provide a resin composition mainly composed of a polyamide and an ABS resin in which the change in mechanical properties is further reduced. SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problems, and its gist is to provide a swellable fluorine obtained by polymerizing a monomer in the presence of a swellable fluoromica-based mineral. A resin composition obtained by melt-kneading 100 parts by weight of a polyamide containing 0.01 to 20% by weight of a mica-based mineral and 10 to 200 parts by weight of an ABS resin. [0008] In the present invention, the ABS resin is
A polymer mainly composed of an acrylonitrile compound, a butadiene compound and a styrene compound. Hereinafter, the present invention will be described in detail. Preferred polyamides in the present invention include nylon 6, nylon 46, nylon 66, nylon 610,
Nylon 612, Nylon 116, Nylon 11, Nylon 1
2, 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, polymetaxylylene adipa Mid, nylon
11T, polyundecamethylene hexahydroterephthalamide, bis (4-aminocyclohexyl) methanetere /
Isophthalate and bis (3-methyl-4-aminocyclohexyl) methane / hexamethylenediamine / I / T
Copolymers and the like may be mentioned, and two or more kinds may be used in combination. Here, 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, and nylon 66 / 6T. Although the relative viscosity of the polyamide is not particularly limited, a mixture of phenol and tetrachloroethane in a weight ratio of 60/40 is used as a solvent at a temperature of 25 ° C. and a concentration of 1 g / dl. A range of 5.0 is preferred. If the relative viscosity is too low, the mechanical performance of the resin composition decreases, and if the relative viscosity is too high, the moldability of the resin composition rapidly decreases, which is not preferable. The 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. If it is larger than this range, the melt viscosity of the obtained resin composition may undesirably increase. In the present invention, when the above polyamide is produced, a swellable fluoromica-based compound is added to a monomer, that is, a salt (nylon salt) or a mixture of an aminocarboxylic acid or a lactam, a diamine and a dicarboxylic acid. Polymerize by adding minerals. The swellable fluoromica-based mineral used in the present invention is represented by the following formula. αMF · β (aMgF ₂ · bMgO) · γSiO ₂ where M represents sodium or lithium, 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 fluorine mica-based mineral, oxides such as silicon oxide, magnesium oxide, and aluminum oxide are mixed with various fluorides, and the mixture is heated at 1400 to 1500 ° C. in an electric furnace or a gas furnace. There is a so-called melting method in which the molten mica is completely melted in the temperature range described above and the fluorine mica-based mineral grows in the reaction vessel during the cooling process. Another method is disclosed in JP-A-2-149415.
There is a method disclosed in Japanese Patent Publication No. That is, this 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, fluorinated mica can be obtained by mixing talc with an alkali silicate or an alkali fluoride and heating the mixture in a magnetic crucible at 700 to 1200 ° C. for a short time. The swellable fluorine cloud-based mineral used in the present invention is preferably manufactured by this method. The amount of alkali silicate or alkali fluoride to be mixed with talc is preferably from 10 to 35% by weight of the mixture. If the amount is outside this range, the generation rate of the swellable fluoromica-based mineral will be reduced. descend. In order to obtain a swellable fluoromica-based mineral, it is necessary that the alkali metal of alkali silicate or alkali fluoride is sodium or lithium. These alkali metals may be used alone or in combination. Of the alkali metals, potassium is not preferable because a swellable fluoromica-based mineral cannot be obtained, but is used in combination with sodium or lithium, and is used for the purpose of adjusting the swellability in a limited amount. Is also possible. In the step of producing the swellable fluoromica-based mineral used in the present invention, a small amount of alumina is blended,
It is also possible to adjust the swellability of the resulting swellable fluoromica-based mineral. In the present invention, the swelling property means that a fluoromica-based mineral absorbs polar molecules or cations such as aminocarboxylic acid, nylon salt, water molecule or the like between the layers, thereby increasing the interlayer distance or further swelling cleavage. Thus, it means the property of becoming ultrafine particles, and the fluoromica-based mineral represented by the above formula exhibits such a swelling property. The swellable fluoromica mineral has a particle size of 15 μm.
It is 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 °. The swellable fluoromica-based mineral is added at the time of polymerization of the polyamide so as to be in the range of 0.01 to 20% by weight based on the polyamide to be produced. If the amount is too small, the effect of improving mechanical strength, heat resistance and dimensional stability is not sufficiently exhibited, and if it is too large, the toughness is greatly reduced. As a method for producing a polyamide containing a swellable fluoromica-based mineral, there is a method in which a polyamide and a swellable fluoromica-based mineral are melt-kneaded using a general extruder. Then, by polymerizing the monomer in a state where a predetermined amount of the swellable fluoromica-based mineral coexists, the swellable fluoromica-based mineral is sufficiently finely dispersed in the polyamide, and the effect of the present invention appears most remarkably. Examples of the ABS resin in the present invention include a terpolymer obtained by emulsion polymerization of acrylonitrile, butadiene and styrene, a mixture of acrylonitrile-styrene resin and nitrile rubber (acrylonitrile-butadiene rubber), and grafting of styrene onto nitrile rubber. A known material such as a copolymer can be used, but a terpolymer obtained by emulsion polymerization is preferably used. The copolymer composition is preferably such that the butadiene component is 15 to 80% by weight, the total of the acrylonitrile component and the styrene component is 85 to 20% by weight, and the weight ratio of the acrylonitrile component to the styrene component is 5/95 to 50/50. is there. In addition to these three components, a small amount of a copolymer component such as isoprene, phenylmaleimide, methyl acrylate and methyl methacrylate may be contained. The amount of the ABS resin is 10 to 10 parts by weight based on 100 parts by weight of the polyamide containing the swellable fluoromica-based mineral.
200 parts by weight. If the ABS resin content is less than 10 parts by weight, the effects of dimensional change and impact resistance improvement due to water absorption are small.
If the amount is more than 100 parts by weight, the heat resistance decreases and
It is not preferable because chemical resistance is remarkably reduced. The resin composition of the present invention is produced by melt-kneading a polyamide containing a swellable fluoromica-based mineral and an ABS resin at a predetermined ratio. At the time of melt kneading, an unsaturated compound for improving impact resistance and an organic peroxide for accelerating the reaction are added as a modifier for the ABS resin, if necessary.
Examples of unsaturated compounds include acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, endo-bicyclo- (2,2,1) -5-heptene-2,3-dicarboxylic acid and anhydrides thereof. And unsaturated epoxy compounds such as glycidyl acrylate and glycidyl methacrylate. Examples of the organic peroxide include benzoyl peroxide, p-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, t-butyl peroxide, di-t-butyl peroxide, dicumyl peroxide, and the like. When the unsaturated compound is blended, its amount is
It is appropriate that the content is 0.05 to 5% by weight of the resin composition. If the amount is too small, the effect of improving the impact resistance is poor,
If the amount is too large, not only the effect of improving the impact resistance is saturated, but also gelation occurs and the color tone deteriorates, which is not preferable. Further, the compounding amount of the organic peroxide is preferably 3% by weight or less. If it is too large, gelation occurs or the color tone deteriorates, which is not preferable. The melt-kneading temperature mainly depends on the kind of polyamide and the composition ratio of polyamide and ABS resin. In general, when a crystalline polyamide is used, the melting and kneading temperature is preferably in the range of the melting point to the melting point plus 80 ° C. When an amorphous polyamide is used, it is preferable to melt-knead in a temperature range 50 to 150 ° C. higher than the glass transition temperature of the polymer having the highest glass transition temperature in the components constituting the resin composition. The melt-kneading time is usually in the range of 1 to 30 minutes, depending on the temperature and the melt-kneading equipment used. As the melt kneading apparatus, 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 apparatus at one time, or each component may be supplied to the melt-kneading apparatus in a multi-stage system in which the components are supplied from different supply ports. For example, a method in which an ABS resin, an unsaturated compound and, if necessary, an organic peroxide are supplied from a supply port far from the tip of the extruder and a polyamide is supplied from a supply port near the tip. There is. By using this method, a resin composition having better performance can be obtained. According to the resin composition of the present invention, a decrease in toughness, which is observed in a conventional fiber composition such as glass fiber or carbon fiber or a resin composition reinforced with an inorganic filler such as calcium carbonate, is observed. The problem of warpage of a molded article of the reinforced resin composition and the problem that the mechanical strength and heat resistance of the resin composition reinforced with an inorganic filler do not improve unless a large amount of the resin composition is incorporated are all solved. Other polymers may be added to the resin composition of the present invention, if necessary, as long as the properties are not significantly impaired. In this case, the compounding amount is desirably 30% by weight or less based on the resin composition. Examples of such a polymer include polycarbonate, polyethylene terephthalate, polybutylene terephthalate, polyarylate, polysulfone, polyethersulfone, polyetherketone, polyetheretherketone, polyetherimide, polyphenylene sulfide, polyphenylene ether, PMMA, and polyvinyl chloride. Phenoxy resin, liquid crystal polymer and the like. The resin composition of the present invention contains a pigment, a heat stabilizer, an antioxidant, a weathering agent, a flame retardant, a plasticizer, a release agent, and other reinforcing materials as long as the properties 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.
General benzophenones and benzotriazoles are used as weathering agents. As the flame retardant, general phosphorus-based flame retardants and halogen-based flame retardants are 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 bright van, sodium bright van, iron bright van, glass balloon, carbon black, zinc oxide,
Antimony trioxide, boric acid, borax, zinc borate, zeolite, hydrotalside, metal fibers, metal whiskers, ceramic whiskers, potassium titanate whiskers, boron nitride, mica, graphite, glass fibers,
And carbon fiber. According to the present invention, a resin composition excellent in mechanical properties such as impact resistance, water resistance, heat resistance, moldability and the like can be obtained. Utilizing its excellent performance, it is used as a molded article useful in electric machines, automobiles, machinery, miscellaneous goods, and other fields. In the present invention, a swellable fluoromica-based mineral-containing polyamide obtained by adding a swellable fluoromica-based mineral to a polyamide monomer and polymerizing the swellable fluoromica-based mineral is used. It is sufficiently finely dispersed in the polyamide, and as a result, the melt-kneaded product with the ABS resin is finely dispersed in each other, and excellent physical properties are obtained. Next, the present invention will be described in detail with reference to examples. In addition, the raw materials and measuring methods used in Examples and Comparative Examples are as follows. 1. Raw Material (1) Talc crushed by a fluorine mica ball mill to have an average particle size of 2 μm, a silicofluoride shown in Table 1 having an average particle size of 2 μm, and alumina were mixed in the proportions (parts by weight) shown in Table 1, Put this in a magnetic crucible, hold at 800 ℃ for 1 hour in an electric furnace,
Fluorine mica of M-1 to M-3 was synthesized. The average particle size 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 a peak corresponding to a thickness of 9.2 mm in the C-axis direction of the raw material talc. It disappeared and a peak corresponding to 12 to 16 ° indicating the formation of swellable fluoromica was observed. [Table 1] (2) ABS resin (manufactured by Sumitomo Nogatack Co.) K3125: polymer of 16% by weight of acrylonitrile, 45% by weight of butadiene rubber, 39% by weight of styrene K2540: 19% by weight of acrylonitrile, 35% by weight of butadiene rubber % Of styrene, 46% by weight of styrene: K3272: 25% by weight of acrylonitrile, 18% by weight of butadiene rubber, 57% by weight of styrene Polymer modified ABS: 100 parts by weight of K2540, 1.0 part by weight of maleic anhydride and 0.1 part of benzoyl peroxide After mixing parts by weight with a Henschel mixer, a twin-screw extruder (PCM manufactured by Ikegai Iron Works Co., Ltd.)
−30), melt-kneaded at a cylinder temperature of 220 ° C,
Pelletized. (3) Unsaturated compound Maleic anhydride (special grade reagent) Glycidyl methacrylate (special grade reagent) Measuring method (a) Flexural strength and flexural modulus Measured according to ASTM D790 using a 1/8 inch thick flexural test piece. The value after the moisture absorption treatment is 60 ° C. and 95% RH.
This is a value measured in the same manner after the moisture absorption treatment for 168 hours. (b) Izod impact test The above test piece was measured based on ASTM D256. (c) Heat distortion temperature (HDT) Using the above test piece, load 4.5kg based on ASTM D648.
/ Cm ² . (e) Moisture absorption rate A square test piece with a thickness of 2 mm and a width of 50 mm was used at 60 ° C and 95%
A moisture absorption treatment was performed for 168 hours under the condition of RH, and a moisture absorption rate was determined from a change in weight. (d) Dimensional change The same test piece as described above was subjected to the same moisture-absorbing treatment, and the thickness and vertical and horizontal dimensional changes were measured, and the average value was taken as the dimensional change. Examples 1 to 5 For 10 kg of ε-caprolactam, 2 kg of water and M-1 were used.
300 g of each of M-2 or M-3 was added, and the mixture was placed in a reaction vessel having a content of 30 liters and heated to 250 ° C. with stirring to gradually release water vapor while gradually releasing steam from 4 kg / cm ² to 15 kg.
/ 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. When the polymerization was completed, the reaction product was discharged into a strand, cooled, solidified, and cut into pellets. The resulting pellets were treated with hot water at 95 ° C. to scour and dry. The obtained pellets of fluoromica-containing nylon 6 are referred to as A-1, A-2, and A-3, respectively. The relative viscosities and terminal group concentrations (equivalents / ton) of the 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 composition (parts by weight) shown in Table 2,
Using a twin-screw extruder (PCM-45 manufactured by Ikegai Iron Works), temperature 2
The mixture was melt-kneaded under conditions of 60 ° C. and an average residence time of 2 minutes and 23 seconds, and pelletized. After drying the obtained pellet, a test piece was molded at 260 ° C. cylinder temperature and 80 ° C. mold temperature using an injection molding machine. Table 2 shows the results of various performance evaluations using the obtained test pieces. [Table 2] Examples 6 to 10 Using the raw materials having the composition shown in Table 3 (parts by weight), supply the ABS resin, maleic anhydride, glycidyl methacrylate and benzoyl peroxide from the distal end of the twin-screw extruder. Examples 1 to 5 except that the polyamide was supplied and melt-kneaded while the polyamide was supplied from the supply port closer to the tip.
A test piece was obtained in the same manner as described above. Table 3 shows the results of various performance evaluations performed using the obtained test pieces. [Table 3] Examples 11 to 13 For 10 kg of nylon 66 salt, 3 kg of water and M-1, M-
150g of 2 or M-3 respectively, and the content is 30
The mixture was placed in a liter reaction vessel and heated at 230 ° C. while stirring until the internal pressure reached 18 kg / cm ² . After reaching that pressure,
While gradually releasing water vapor, the pressure was maintained by heating. When the temperature reached 280 ° C., the pressure was released to normal pressure, and polymerization was further performed for 2 hours. When the polymerization was completed, the reaction product was discharged into a strand, cooled, solidified, cut into pellets, and dried. Nylon 6 containing fluorine mica obtained
The pellets No. 6 are designated as A-4, A-5, and A-6, respectively. The relative viscosities and terminal group concentrations (equivalents / ton) of the 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 Using raw materials having the composition shown in Table 4 (parts by weight),
In the above, polyamide and ABS resin are mixed and supplied to a twin-screw extruder. In Examples 12 to 13, the ABS resin, maleic anhydride and benzoyl peroxide are supplied from a supply port far from the tip of the twin-screw extruder. Then, the polyamide is supplied from the supply port near the tip, at a temperature of 280 ° C and an average residence time of 2
The mixture was melt-kneaded under the conditions of minutes and 23 seconds and pelletized. After drying the obtained pellet, a test piece was molded at a cylinder temperature of 280 ° C. and a mold temperature of 90 ° C. using an injection molding machine. Table 4 shows the results of various performance evaluations using the obtained test pieces. [Table 4] Comparative Examples 1 to 3 Comparative Examples 1 to 3 were prepared using raw materials having the composition shown in Table 5 (parts by weight).
In the above, polyamide and ABS resin are mixed and supplied to a twin-screw extruder. In Comparative Examples 2-3, the ABS resin, maleic anhydride and benzoyl peroxide are supplied from a supply port farther from the tip of the twin-screw extruder. Then, the polyamide was supplied from the supply port closer to the tip, and in Comparative Examples 1 and 2, the temperature was 260 ° C.
℃, average residence time 2 minutes 25 seconds, in Comparative Example 3 temperature 280 ℃,
The mixture was melt-kneaded under the conditions of an average residence time of 2 minutes and 37 seconds to form pellets. After drying the obtained pellets, using an injection molding machine, in Comparative Examples 1 and 2, the cylinder temperature was 260 ° C.
80 ° C, Cylinder temperature 280 ° C, Mold temperature 90 in Comparative Example 3
Specimens were molded at ° C. Table 5 shows the results of various performance evaluations using the obtained test pieces. [Table 5] According to the present invention, the conventional polyamide and A
There is provided a reinforced resin composition having improved mechanical properties and heat resistance as compared with a resin composition comprising a BS resin, and having excellent performance in which changes in dimensions and mechanical properties due to water absorption are reduced.

────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Mioko Watanabe 23 Uji Kozakura, Uji City, Kyoto Unitika, Central Research Laboratory, Inc. (56) References JP-A-6-80820 (JP, A) JP-A-3-203959 (JP, A) (58) Field surveyed (Int. Cl. ⁷ , DB name) C08L 55/02 C08L 77/00-77/12

Claims (1)

(57) [Claims 1] The swellable fluoromica-based mineral obtained by polymerizing a monomer in the coexistence of the swellable fluoromica-based mineral is 0.01%.
100% by weight of polyamide containing up to 20% by weight and ABS resin
A resin composition obtained by melt-kneading 10 to 200 parts by weight.