JPH083439A - Resin composition - Google Patents

Abstract

PURPOSE:To provide a resin composition consisting of a polyamide and an ABS resin and excellent in mechanical properties, heat resistance, moldability, etc. CONSTITUTION:This composition is obtained by melt compounding 10-200 pts.wt. ABS resin and 100 pts.wt. polyamide produced by polymerizing a monomer in the presence of a swelling fluoromica mineral and containing 0.01-20wt.% swelling fluoromica mineral.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a resin composition excellent in mechanical properties such as impact resistance, heat resistance and moldability.

[0002]

BACKGROUND OF THE INVENTION Polyamide has excellent mechanical properties, heat resistance and chemical resistance, but on the other hand, it has a drawback that it causes a decrease in rigidity and a change in dimension when absorbing water.

In order to improve the physical properties of such a polyamide, an ABS resin having impact resistance and water resistance is combined with the polyamide to retain the excellent characteristics of the polyamide, but its drawbacks, particularly the dimension and the machine due to water absorption. Compositions having reduced changes in physical properties have been proposed (Japanese Patent Publication No. 38-23).
No. 476). However, this resin composition has a problem that the compatibility between the polyamide and the ABS resin is poor and the impact strength is low.

A blend of a polyamide and an ABS resin modified with a functional group capable of chemically reacting or chemically interacting has been proposed (JP-A-1-294).
No. 76, No. 2-175755). However, with this resin composition, although the moldability and impact resistance were improved to some extent, the improvement effect was insufficient, and the mechanical strength, heat resistance, and dimensional stability were not satisfactory.

Further, Japanese Patent Application Laid-Open No. 2-29475 discloses a resin composition comprising a polyamide, an impact resistance improving material and a layered silicate. Although this resin composition was found to have excellent mechanical strength and heat resistance, in order to uniformly disperse the layered silicate in the resin composition, a pretreatment for contacting it with a swelling agent in advance. There is a problem that the manufacturing cost is increased because the process is required.

[0006]

DISCLOSURE OF THE INVENTION The present invention is intended to solve the above problems and is excellent in mechanical properties such as impact resistance, heat resistance and moldability, and has dimensions and mechanical properties due to water absorption. An object of the present invention is to provide a resin composition containing a polyamide and an ABS resin as main components, in which changes in properties are further reduced.

[0007]

Means for Solving the Problems The present invention is to solve the above-mentioned problems, and its gist is to provide a swellable fluoromica-based mineral obtained by polymerizing a monomer in the presence of a swellable fluoromica-based mineral. Of 0.01 to 20% by weight of polyamide and 10 to 200 parts by weight of ABS resin are melt-kneaded.

In the present invention, the ABS resin means
A polymer mainly composed of an acrylonitrile compound, a butadiene compound and a styrene compound.

The present invention 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 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 adipate Mid, nylon
11T, polyundecamethylene hexahydroterephthalamide, bis (4-aminocyclohexyl) methane tere /
Isophthalate and bis (3-methyl-4-aminocyclohexyl) methane / hexamethylenediamine / I / T
Examples thereof include copolymers, 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 1.5-1.5. 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.

The preferred range of the concentration of amino groups and carboxyl groups in the polyamide is 20 to 200 equivalents /
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 fluorine cloud-based mineral used in the present invention is preferably one produced by this method.

The amount of alkali silicofluoride or alkali fluoride mixed with talc is preferably 10 to 35% by weight of the mixture, and if the amount is out of this range, the production rate of swelling fluoromica-based minerals is increased. 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 used in the present invention, a small amount of alumina is blended,
It is also possible to control the swelling property of the swelling fluoromica-based mineral produced.

The term "swelling property" as used in the present invention means that the fluoromica-based mineral 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. In addition, the fluoromica-based mineral represented by the above formula means the property of forming ultrafine particles, and exhibits such swelling property.

The swellable fluoromica-based mineral has a particle size of 15 μm.
It is particularly preferable that the layer 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 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 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.

As a method for producing the swellable fluoromica-based mineral-containing polyamide, there is a method of melt-kneading the polyamide and the swellable fluoromica-based mineral using a general extruder. Then, by polymerizing the monomer in a state where a predetermined amount of the swellable fluoromica-based mineral is allowed to coexist, the swellable fluoromica-based mineral is sufficiently finely dispersed in the polyamide, and the effect of the present invention is most remarkable.

As the ABS resin in the present invention, 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. Known copolymers and the like can be used, but a terpolymer obtained by emulsion polymerization is preferably used. The copolymer composition is such that the butadiene component is 15 to 80% by weight, the total acrylonitrile component and styrene component is 85 to 20% by weight, and the weight ratio of the acrylonitrile component and the styrene component is 5/95 to 50/50. is there.

In addition to these three components, a small amount of a copolymerization component such as isoprene, phenylmaleimide, methyl acrylate and methyl methacrylate may be contained.

The blending amount of the ABS resin is 10 to 100 parts by weight of the polyamide containing the swelling fluorinated mica based mineral.
It is 200 parts by weight. If the ABS resin content is less than 10 parts by weight, the dimensional change due to water absorption and the effect of improving impact resistance are small.
When it exceeds the weight part, the heat resistance decreases,
It is not preferable because the chemical resistance is significantly 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 in 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 of the ABS resin, if necessary.
As the unsaturated compound, acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, endo-bicyclo- (2,2,1) -5-heptene-2,3-dicarboxylic acid and its acid anhydride, etc. 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 an unsaturated compound is added, its amount is
It is suitable to be 0.05 to 5% by weight of the resin composition. If this amount is too small, the effect of improving impact resistance is poor,
If it is too large, not only the impact resistance improving effect is saturated, but also gelation occurs and the color tone deteriorates, which is not preferable. Further, the content of the organic peroxide is preferably 3% by weight or less, and if it is too large, gelation may occur or the color tone may deteriorate, which is not preferable.

The melt-kneading temperature mainly depends on the kind of polyamide and the composition ratio of polyamide and ABS resin. 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 it in a temperature range higher by 50 to 150 ° C. than the glass transition temperature of the polymer having the highest glass transition temperature among the components constituting the resin composition.

The melt-kneading time depends on the temperature and the melt-kneading apparatus used, but 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. For example, first, a method of supplying an ABS resin, an unsaturated compound, and optionally an organic peroxide from a supply port on the side far from the tip of the extruder, and supplying a polyamide from a supply port on the side close to the tip. There is. By using this method, a resin composition having more excellent performance can be obtained.

According to the resin composition of the present invention, the toughness is reduced and the fibrous material is deteriorated, which is observed in the conventional resin composition reinforced with the glass fiber or carbon fiber or the inorganic filler such as calcium carbonate. Problems such as warpage of a molded product of a reinforced resin composition and a problem that the mechanical strength and the heat resistance cannot be improved unless the resin composition reinforced with an inorganic filler is blended in a large amount can be solved. The polymer composition of the present invention may further contain other polymer, if necessary, as long as its characteristics are not significantly impaired. In this case, the blending amount is preferably 30% by weight or less based on the resin composition. Examples of such polymers include polycarbonate, polyethylene terephthalate, polybutylene terephthalate, polyarylate, polysulfone, polyether sulfone, polyether ketone, polyether ether ketone, polyetherimide, polyphenylene sulfide, polyphenylene ether, PMMA, polyvinyl chloride. , Phenoxy resin, liquid crystal polymer and the like.

The resin composition of the present invention may contain pigments, heat stabilizers, antioxidants, weathering agents, flame retardants, plasticizers, mold release agents, other reinforcing materials, etc., as long as the characteristics are not significantly impaired. It can also be added. As such heat stabilizers and antioxidants, 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-based flame retardant or a halogen-based 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 sulphate, potassium tan, sodium ban, iron ban, glass balloon, carbon black, zinc oxide,
Antimony trioxide, boric acid, borax, zinc borate, zeolite, hydrotalcide, metal fibers, metal whiskers, ceramic whiskers, potassium titanate whiskers, boron nitride, mica, graphite, glass fibers,
Carbon fiber etc. are mentioned.

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

[0036]

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 ABS resin is finely dispersed, and excellent physical properties are obtained.

[0037]

EXAMPLES Next, the present invention will be described in detail with reference to examples. The raw materials and measuring methods used in Examples and Comparative Examples are as follows. 1. Raw materials (1) Talc pulverized with a fluorine mica ball mill to an average particle size of 2 μm, fluorinated mica having an average particle size of 2 μm and silica fluoride shown in Table 1 and alumina were 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.

[0038]

[Table 1]

(2) ABS resin [Sumitomo Nogatac Co., Ltd.] K3125: 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 %, Polymer of 46% by weight of styrene K3272: 25% by weight of acrylonitrile, 18% by weight of butadiene rubber, 57% by weight of styrene 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 from Ikegai Tekko KK
-30), melt and knead at a cylinder temperature of 220 ° C,
Pelletized.

(3) Unsaturated compound Maleic anhydride (special grade reagent) Glycidyl methacrylate (special grade reagent) 2. Measuring Method (a) Bending Strength and Bending Elastic Modulus A bending test piece having a thickness of 1/8 inch was used and measured according to ASTM D790.

The value after 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 . (e) Moisture absorption rate Using a square test piece with a thickness of 2 mm and a width of 50 mm, 60 ℃, 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. (d) 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 to 5 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.

When the polymerization was completed, the reaction product was discharged in a strand form, cooled and solidified, and then cut into pellets. The obtained pellets were treated with hot water at 95 ° C., scoured, and dried. The obtained pellets of 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 Table 2,
Using a twin-screw extruder (PCM-45 manufactured by Ikegai Tekko Co., Ltd.), temperature 2
The mixture was melt-kneaded under the conditions of 60 ° C. and an average residence time of 2 minutes and 23 seconds, and 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. Table 2 shows the results of various performance evaluations using the obtained test pieces.

[0044]

[Table 2]

Examples 6 to 10 Using the raw materials having the blending composition (parts by weight) shown in Table 3, ABS resin, maleic anhydride, glycidyl methacrylate and benzoyl peroxide were supplied to the feed port far from the tip of the twin-screw extruder. Examples 1 to 5 except that the polyamide was supplied from the above and the polyamide was supplied from a supply port closer to the tip end and melt-kneaded.
A test piece was obtained in the same manner as in. Table 3 shows the results of various performance evaluations using the obtained test pieces.

[0046]

[Table 3]

Examples 11 to 13 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 fluoromica-containing nylon 6
Let 6 pellets be A-4, A-5, and A-6, respectively. 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 Using the raw materials of the compounding composition (parts by weight) shown in Table 4, Example 11
Then, 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 nearer to the tip, and the temperature is 280 ° C and the average residence time is 2
It was melt-kneaded and pelletized under the condition of 23 minutes per minute. 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. Table 4 shows the results of various performance evaluations using the obtained test pieces.

[0048]

[Table 4]

Comparative Examples 1 to 3 Comparative Example 1 using raw materials having the composition (parts by weight) shown in Table 5
Then, polyamide and ABS resin are mixed and supplied to a twin-screw extruder, and in Comparative Examples 2 to 3, 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 was supplied from the supply port closer to the tip, and in Comparative Examples 1 and 2, the temperature was 260
℃, average residence time 2 minutes 25 seconds, in Comparative Example 3 temperature 280 ℃,
The mixture was melt-kneaded and pelletized under the condition of an average residence time of 2 minutes and 37 seconds. After drying the obtained pellets, using an injection molding machine, in Comparative Examples 1 and 2, the cylinder temperature was 260 ° C. and the mold temperature was 260 ° C.
80 ℃, in Comparative Example 3 cylinder temperature 280 ℃, mold temperature 90
Test pieces were molded at ° C. Table 5 shows the results of various performance evaluations using the obtained test pieces.

[0050]

[Table 5]

[0051]

According to the present invention, the conventional polyamide and A
Provided is a reinforced resin composition having excellent performance in which mechanical properties and heat resistance are improved as compared with a resin composition containing a BS resin, and changes in dimensions and mechanical properties due to water absorption are reduced.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Kenichi Kikuchi, 23 Uji Kozakura, Uji-shi, Kyoto Prefecture Central Research Institute of Unitika Co., Ltd. In-house

Claims (1)

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