JP4001589B2 - Method for producing resin composition - Google Patents

Description

  The present invention relates to a method for producing a resin composition. More specifically, the present invention relates to a method for producing a resin composition having excellent impact resistance, high rigidity, and good appearance, obtained by blending a polymer alloy of an aromatic polycarbonate resin with talc having a bulk specific gravity of 0.4 to 0.9. .

  Conventionally, talc has been widely used as a reinforcing material for thermoplastic resins for the purpose of improving rigidity, improving dimensional stability, improving creep resistance and matting effect because of its scaly structure.

  Among thermoplastic resins, molded products of aromatic polycarbonate resins are widely used industrially because they have excellent mechanical properties and thermal properties. However, since it is inferior in workability and moldability, many polymer alloys with other thermoplastic resins have been developed for the purpose of improvement. Among them, polymer alloys with ABS resin, polyethylene terephthalate resin or polybutylene terephthalate resin are Widely used in the automotive field, OA equipment housing, and the like.

  On the other hand, in the automobile field, housings for office automation equipment, etc., the trend of lightness, thinness and miniaturization is becoming stronger, and accordingly, materials with higher rigidity are required, and in addition, there is a demand for good appearance and matting. Talc is usually used as a reinforcing material. However, conventional molded products are not sufficient in impact resistance, and improvements are required.

  An object of the present invention is to provide a method for producing a resin composition having excellent impact resistance, high rigidity, and good appearance.

  As a result of intensive research aimed at achieving this object, the present inventor was obtained by blending a specific amount of talc having a bulk specific gravity of 0.4 to 0.9 with a polymer alloy of an aromatic polycarbonate resin. The present inventors have found that a resin composition and a molded product therefrom have excellent impact resistance and good appearance while maintaining its rigidity as compared with conventional products, and have reached the present invention.

That is, according to the present invention, it is composed of (A) an aromatic polycarbonate resin (component A-1), an ABS resin (component A-2) and an elastic polymer (component A-3). %, A resin component (A component) in which the A-1 component is 30 to 70% by weight, the A-2 component is 30 to 70% by weight, and the A-3 component is 3 to 15% by weight, and (B) A method for producing a resin composition comprising kneading and pelletizing talc (component B) having a bulk specific gravity of 0.4 to 0.9 with respect to 100 parts by weight of the resin component is provided. The

  According to the present invention, a resin composition having excellent impact resistance, high rigidity, and good appearance can be obtained, and such a resin composition is suitably used as various molded products such as automobiles and housings for OA equipment. It is done.

In the present invention, as the component A, a resin component composed of an aromatic polycarbonate resin (component A-1), an ABS resin (component A-2) and an elastic polymer (component A-3) is used.

  In the present invention, the talc used as the component B has a bulk specific gravity of 0.4 to 0.9, and a range of 0.5 to 0.8 is preferable. When the bulk specific gravity is less than 0.4, the impact resistance is not sufficiently improved. When the bulk specific gravity is greater than 0.9, the talc does not collapse during kneading, resulting in poor dispersion.

  The talc used here has a bulk specific gravity of 0.4 to 0.9, and has a higher bulk specific gravity than that of the conventional bulk specific gravity of 0.1 to 0.3. Is done. As a method for producing the talc having a high bulk specific gravity, for example, a method of mechanically compressing a talc having a bulk specific gravity of 0.1 to 0.3 to obtain a talc having a bulk specific gravity of 0.4 to 0.9 is used. It is done.

  The talc having a bulk specific gravity of 0.4 to 0.9 used as the B component is in the range of 3 to 60 parts by weight with respect to 100 parts by weight of the resin used as the A component. When the amount is less than 3 parts by weight, the rigidity is not sufficiently improved. When the amount is more than 60 parts by weight, extrusion and molding are difficult, and it is difficult to obtain a good molded product.

  The aromatic polycarbonate resin used as the component A-1 in the present invention is a resin usually used as an engineering resin, and is an aromatic polycarbonate resin obtained by reacting a dihydric phenol and a carbonate precursor. Typical examples of the dihydric phenol used here include 2,2-bis (4-hydroxyphenyl) propane (commonly called bisphenol A), bis (4-hydroxyphenyl) methane, 1,1-bis (4 -Hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 2,2-bis (4-hydroxy-3, 5-dibromophenyl) propane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, bis (4-hydroxyphenyl) ether, 4,4′-dihydroxydiphenyl, bis (4-hydroxyphenyl) sulfide and Bis (4-hydroxyphenyl) sulfone etc. are mentioned. A preferred dihydric phenol is bis (4-hydroxyphenyl) alkane, and bisphenol A is particularly preferred. Examples of the carbonate precursor include carbonyl halide, diaryl carbonate, haloformate, and the like, and specific examples include phosgene, diphenyl carbonate, dihaloformate of dihydric phenol, and the like.

  In producing the aromatic polycarbonate resin by reacting the dihydric phenol and the carbonate precursor, the dihydric phenol can be used alone or in combination of two or more kinds. A branched polycarbonate resin copolymerized with a functional aromatic compound or a mixture of two or more aromatic polycarbonate resins may be used. Moreover, you may use a catalyst, a molecular weight modifier, and antioxidant as needed. Any molecular weight of the aromatic polycarbonate resin can be used. For example, when the aromatic polycarbonate resin is obtained using bisphenol A as the dihydric phenol and phosgene as the carbonate precursor, the concentration is 0.7 g / dl methylene chloride. A specific viscosity of 0.15 to 1.5 measured with a solution at a temperature of 20 ° C. is preferably used.

That is, according to the present invention, the (A) resin component comprises an aromatic polycarbonate resin (A-1 component), an ABS resin (A-2 component), and an elastic polymer (A-3 component). When the total is 100% by weight, the resin component in which the A-1 component is 30 to 70% by weight, the A-2 component is 30 to 70% by weight, and the A-3 component is 3 to 15% by weight and (B) bulk A resin composition having a specific gravity of substantially 0.4 to 0.9 talc (component B) and having 3 to 60 parts by weight of the B component with respect to 100 parts by weight of the resin component is provided.

The polymer alloy composed of the A-1 component, the A-2 component, and optionally the A-3 component is widely used in the automotive field, the housing of OA equipment, etc. as described above. The resin composition comprising the polymer alloy of the present invention and talc having a bulk specific gravity of 0.4 to 0.9 and a molded product therefrom are excellent in impact resistance, high in rigidity and good in appearance. Particularly preferably used.
Compared to aromatic polycarbonate resin alone, when this polymer alloy is mixed with talc and extruded and molded, there is no decrease in mechanical properties due to a decrease in molecular weight, and this is preferable.

In this invention, the weight ratio of A-1 component in all the resin components is 30 to 70 weight%. When the amount is less than 30% by weight, the heat resistance is inferior, and when it exceeds 70% by weight, the molding and workability deteriorate, which is not preferable.
The resin used as the A-2 component of the present invention is an ABS resin . The weight ratio of the A-2 component in all the resin components is 30 to 70% by weight. If the amount is less than 30% by weight, the molding and workability deteriorate, and if it exceeds 70% by weight, the heat resistance is inferior.

The ABS resin used as one of the A-2 components is a resin that is usually used as a general-purpose resin. This ABS resin is a copolymer obtained by graft polymerization of an aromatic vinyl compound component and a vinyl cyanide compound component to a diene rubber component.
As the diene rubber component, 80% by mole or more, preferably 90% by mole or more of the total diene rubber component is polybutadiene, and as other components, polyisoprene, styrene-butadiene copolymer, and the like can be used. The proportion of the diene rubber component is preferably in the range of 10 to 95% by weight in all components. As the aromatic vinyl compound component grafted on the diene rubber component, 80 mol% or more, preferably 90 mol% or more of the total aromatic vinyl compound component is styrene, and α-methylstyrene and nucleus-substituted styrene are other components. Etc. The ratio of the aromatic vinyl compound component is preferably in the range of 50 to 95% by weight in the graft component. Further, as the vinyl cyanide compound component grafted on the diene rubber component, 80 mol% or more, preferably 90 mol% or more of the total vinyl cyanide compound component is acrylonitrile, and other components include methacrylonitrile. Further, maleic anhydride, N-substituted maleimide and the like can be mixed and used. The proportion of the vinyl cyanide compound component is preferably in the range of 50 to 5% by weight in the graft component.

  The ABS resin may be produced by any of bulk polymerization, suspension polymerization, or emulsion polymerization, and the copolymerization method may be copolymerized in one stage or in multiple stages. Furthermore, not only one ABS resin but also two or more ABS resins can be mixed and used.

Po triethylene terephthalate letter DOO resin is a resin which is usually used as engineering resins, and terephthalic acid as a main acid component, a polymer containing ethylene glycol as a main glycol component.

  As the dicarboxylic acid component, 80 mol% or more, preferably 90 mol% or more of the total dicarboxylic acid component is terephthalic acid. Dicarboxylic acid components other than terephthalic acid include aromatic dicarboxylic acids such as naphthalene dicarboxylic acid, isophthalic acid, diphenylethane dicarboxylic acid, diphenyl dicarboxylic acid, diphenyl ether dicarboxylic acid, diphenyl sulfone dicarboxylic acid, diphenyl ketone dicarboxylic acid and anthracene dicarboxylic acid And aliphatic dicarboxylic acids such as adipic acid and sebacic acid, and alicyclic dicarboxylic acids such as cyclohexane-1,4-dicarboxylic acid.

  As a glycol component, 80 mol% or more, preferably 90 mol% or more of all glycol components is ethylene glycol. As glycol components other than ethylene glycol, aliphatic glycols such as trimethylene glycol, tetramethylene glycol, pentamethylene glycol, hexamethylene glycol and decamethylene glycol, alicyclic diols such as cyclohexanedimethanol, hydroquinone, resorcin and 2, Aromatic diols such as 2-bis (4-hydroxyphenyl) propane, aliphatic diols having aromaticity such as 1,4-dihydroxymethylbenzene, polyalkylene glycols such as polyethylene glycol, polypropylene glycol and polytetramethylene glycol (poly Oxyalkylene glycol) and the like.

The port triethylene terephthalate resins, such as aromatic oxyacid such as hydroxybenzoic acid, .omega.-hydroxy components derived from oxycarboxylic acid such as an aliphatic oxy acid such as caproic acid, dicarboxylic acid component and the oxycarboxylic acid component Those copolymerized at less than 20 mol% with respect to the total of the above are also included.

The amount ranges in port triethylene terephthalate resin is substantially linear, for example in an amount of less than 2 mole% relative to the total acid component, trifunctional or higher polycarboxylic acid or polyhydroxy compound such as trimellitic acid, pentaerythritol And the like are also included.

  Any molecular weight of the polyethylene terephthalate resin can be used. For example, in the case of a polymer of terephthalic acid and eletin glycol, the intrinsic viscosity measured at 25 ° C. with an o-chlorophenol solution is 0.4 to 1. Those having a range of .3 dl / g are preferably used.

Po polybutylene terephthalate resin is a resin which is usually used as engineering resins, and terephthalic acid as a main acid component is a polymer whose main glycol component tetramethylene glycol.

  The dicarboxylic acid component and the glycol component are the same as those in the description of the polyethylene terephthalate resin in which ethylene glycol is replaced with tetramethylene glycol and conversely tetramethylene glycol is replaced with ethylene glycol.

  Any molecular weight of the polybutylene terephthalate resin can be used. For example, in the case of a polymer of terephthalic acid and tetramethylene glycol, the intrinsic viscosity measured at 25 ° C. with an o-chlorophenol solution is 0.4 to 0.4. Those having a range of 1.3 dl / g are preferably used.

  As the A-2 component, an ABS resin is particularly preferably used. ABS resin is a well-balanced resin composition that can improve the molding and processability of aromatic polycarbonate resin by polymer alloying with aromatic polycarbonate resin, and also has a matte effect, especially Preferably used.

Elastic polymer as the A-3 component of the present invention is used. The weight ratio of the A-3 component in all resin components is 3 to 15% by weight. If it exceeds 15 % by weight, the mechanical strength is undesirably lowered.

  The elastic polymer is preferably used because the impact strength is further improved by blending it. Examples of the elastic polymer include acrylic elastic polymers such as butadiene-alkyl methacrylate-styrene copolymer, butadiene-alkyl methacrylate-styrene-divinylbenzene copolymer, and butadiene-alkyl acrylate-alkyl methacrylate copolymer, Examples thereof include composite elastic polymers having a structure in which an organosiloxane rubber and a polyalkyl (meth) acrylate rubber component are intertwined with each other, and these can be used alone or in combination of two or more.

The talc used as the component B in the present invention has a bulk specific gravity of 0.4 to 0.9, and preferably 0.5 to 0.8. When the bulk specific gravity is less than 0.4, the impact resistance is not sufficiently improved. When the bulk specific gravity is greater than 0.9, the talc does not collapse during kneading, resulting in poor dispersion.
The talc having a bulk specific gravity of 0.4 to 0.9 used as the B component with respect to 100 parts by weight of the resin component is preferably in the range of 3 to 60 parts by weight. If the amount is less than 3 parts by weight, the rigidity is not sufficiently improved. If the amount is more than 60 parts by weight, extrusion and molding are difficult, and it is difficult to obtain a good molded product.

In the present invention, there are several other advantages of using talc having a bulk specific gravity of 0.4 to 0.9 instead of talc having a bulk specific gravity of 0.1 to 0.3.
For example, talc with a low bulk density has a problem in safety due to dust scattering during supply, but the generation of dust is reduced by using a talc with a high bulk density. In addition, in the work of mixing talc and thermoplastic resin using a blender or the like before extrusion, a blend with the same weight is prepared by using talc having a high bulk specific gravity as compared with that having a low bulk specific gravity. In this case, time and labor are simplified and work efficiency is improved. In addition, talc with low bulk specific gravity entails a lot of air, making it difficult to supply it smoothly from the hopper to the extruder, etc., or causing variations in extrusion amount, poor quality of pellets or molded products, etc. . For this reason, the thermoplastic resin composition highly filled with talc having a low bulk specific gravity has had problems such as poor supply and cannot be produced, but talc having a high bulk specific gravity does not cause the above problem.

  The improvement in impact resistance due to the use of talc having a high bulk specific gravity in the present invention is considered to be due to an improvement in the amount of extrusion of a resin composition containing talc having a low bulk specific gravity. That is, when a resin composition containing talc with a low bulk specific gravity accompanied by a large amount of air is supplied to the extruder, if the resin dissolves in the resin dissolution zone in the extruder, the air accompanying the talc may travel further. In the extruder feed zone, the resin supplied due to the backflow air cannot proceed further, and the amount of extrusion decreases, so the residence time of the resin composition in the extruder In addition, it is considered that a dispersion failure due to insufficient kneading was caused and the impact resistance of the extruded resin composition was lowered. Moreover, it is thought that the dispersion | distribution failure by the length of the said residence time or kneading | mixing lack had a bad influence also about the external appearance. On the other hand, the resin composition containing the talc having a high bulk specific gravity of the present invention is considered to have no impact resistance deterioration or appearance deterioration because kneading in the extruder proceeds efficiently and talc is uniformly dispersed. It is done.

The resin composition of the present invention may be blended with a flame retardant, a flame retardant aid, a nucleating agent, a stabilizer, an antioxidant, a release agent, an ultraviolet absorber, and the like as long as the purpose and effect are not impaired.
Arbitrary methods are employ | adopted in order to manufacture the resin composition of this invention. For example, a method of mixing thermoplastic resin, talc and other additives as appropriate using a mixing means such as a V-type blender and then pelletizing with a vented uniaxial or biaxial ruder, thermoplastic resin and other additives Prepare a pre-mixed agent using a powerful means such as a super mixer and supply it from the first chute of the vented biaxial ruder, and supply other thermoplastic resin from the second chute in the middle of the ruder. Generally, industrially used methods such as a method of kneading and pelletizing are appropriately used. The resin composition thus obtained can be easily molded by any method such as injection molding, extrusion molding, compression molding or rotational molding.

The following examples further illustrate the present invention. The evaluation was based on the following method.
(1) Impact strength: measured according to ASTM D-256.
(2) Rigidity (flexural modulus): Measured according to ASTM D-790.
(3) Appearance, workability, safety, productivity: For these, ◯ is used when talc having a bulk specific gravity of 0.2 (P-3 manufactured by Nippon Talc Co., Ltd.) is used, and ◎, When it was inferior, x was described.
Workability showed the work efficiency of pre-blending, etc., safety showed dust generation, and productivity showed stability during extrusion.
Moreover, the symbol which shows each component of Table 1 and Table 2 is as follows.
PC: Aromatic polycarbonate resin [Panlite L-1225 manufactured by Teijin Chemicals Ltd.]
ABS: ABS resin [Mitsui Toatsu Chemical Co., Ltd. Santac UT-61]
PBT: Polybutylene terephthalate resin [TRB-J manufactured by Teijin Limited]
Elastic polymer: butadiene-alkyl acrylate-alkyl methacrylate copolymer [Karaha Chemical Industry Co., Ltd., Paraloid EXL-2602]
P-3: Talc (bulk specific gravity 0.2) [Nippon Talc Co., Ltd. P-3]
HS-T0.5: Talc (bulk specific gravity 0.5) [HS-T0.5 manufactured by Hayashi Kasei Co., Ltd.]
HS-T0.8: Talc (bulk specific gravity 0.8) [HS-T0.8 manufactured by Hayashi Kasei Co., Ltd.]

Examples 1 and 2 and Comparative Example 1
Each component shown in Table 1 was mixed at a ratio shown in Table 1 by a blender, and then pelletized at a cylinder temperature of 240 ° C. with a vent type twin screw extruder (Nippon Steel Works TEX-30) having a diameter of 30 mmφ. Next, this was dried at 110 ° C. for 5 hours, and then a test piece was prepared and evaluated at an injection molding machine [FANUC T-150D] at a cylinder temperature of 250 ° C. and a mold temperature of 60 ° C.

Reference Examples 1-3
Each component shown in Table 2 was mixed in a blender at the ratio shown in Table 2, and then pelletized at a cylinder temperature of 260 ° C. using a vented twin-screw extruder having a diameter of 30 mmφ [Nippon Steel Works TEX-30]. Next, after drying this at 120 degreeC for 5 hours, the test piece was created and evaluated with the injection molding machine [FANUC T-150D] at the cylinder temperature of 260 degreeC, and the metal mold | die 70 degreeC.

Claims (2)

(A) It consists of an aromatic polycarbonate resin (A-1 component), an ABS resin (A-2 component), and an elastic polymer (A-3 component). When the total of all resins is 100% by weight, A-1 The resin component (component A) in which the component is 30 to 70% by weight, the A-2 component is 30 to 70% by weight, and the A-3 component is 3 to 15% by weight, and (B) 100 parts by weight of the resin component A method for producing a resin composition, comprising kneading and pelletizing 3 to 60 parts by weight of talc (component B) having a bulk specific gravity of 0.4 to 0.9. The production method according to claim 1, wherein the bulk specific gravity of the component B is 0.5 to 0.8.