JP4995035B2 - Resin composition for extrusion machine processing and molding method thereof - Google Patents

Description

  The present invention relates to a resin composition having good processability when processed by an extrusion molding machine having a hopper, and a molding method thereof.

As a molded product raw material having a texture and weight similar to those of metals and ceramics, a composition in which the same amount or more of an inorganic filler is blended with a thermoplastic resin is known. However, when a large amount of inorganic filler is blended with the thermoplastic resin, there is a problem that it is difficult to stably feed a predetermined amount from the hopper of the extruder. In addition, there is a problem that drawdown occurs at the time of molding and the moldability is poor.
JP-A-2005-146124

  An object of the present invention is to provide a resin composition having good moldability when being molded by an extruder having a hopper and a molding method thereof.

The invention of claim 1, (A) 23 ° C. water under in water absorption after 24 hr or (ISO 62) 0.6% or more, the amount containing an average particle size of less 1mm is 10 mass% or more, relative viscosity 70 to 99% by mass of a thermoplastic resin having an A of 2.4 or less, and (B) an aromatic vinyl monomer, a vinyl cyanide monomer, acrylic acid, and an acrylic ester excluding the resin of the component (A) , With respect to 100 parts by mass of the base resin component containing 1 to 30% by mass of a rubber-containing polymer consisting of at least one selected from methacrylic acid, methacrylic acid ester and butadiene, (C) the average particle diameter is 0.05 to 100 μm. A resin composition for processing an extrusion machine having a hopper, comprising 100 to 400 parts by weight of an inorganic filler and (D) a lubricant of 0.01 to 5 parts by weight.

  The invention of claim 2 provides a resin composition for processing an extrusion machine having a hopper according to claim 1, wherein the rubber content of the rubber-containing polymer of component (B) is 30% by mass or more.

  Invention of Claim 3 is the processing method of the resin composition of Claim 1 or 2, Comprising: The process of throwing predetermined amount from a hopper, the process of melt-kneading in an extruder, the process of extrusion-molding to a desired shape, A processing method is provided.

  The invention according to claim 4 provides the processing method according to claim 3, wherein the step of extruding into a desired shape is a step of extruding into a strand shape.

  The resin composition of the present invention has good moldability such as supply stability and extrusion moldability when an extruder having a hopper is used.

<Resin composition>
[Component (A)]
(A) Thermoplastic resins having a water absorption rate (ISO 62) after 24 hours in water of 23 ° C. of 0.6% or more are polyamide resins, acrylate resins, cellulose resins, polyvinyl alcohol resins, poly Those selected from ether resins can be used, and among these, polyamide resins are preferred. By using a component that satisfies the water absorption rate as the component (A), the input from the hopper of the extruder is improved, so that a predetermined amount can be stably supplied.

  The thermoplastic resin of component (A) contains 10% by mass or more of a powder having an average particle size of 1 mm or less, preferably 0.5 mm or less, more preferably 0.3 mm or less, measured by the method described in the Examples. It is preferably contained at 30% by mass or more, more preferably 50% by mass or more.

The thermoplastic resin as component (A) preferably has a relative viscosity of 2.4 or less, more preferably 2.3 or less, still more preferably 2.2 or less, as measured by the method described in the Examples. .

  The polyamide-based resin is a polyamide resin formed from diamine and dicarboxylic acid and a copolymer thereof. For example, nylon 66, polyhexamethylene sebamide (nylon 6 · 10), polyhexamethylene dodecanamide (nylon 6 · 12), polydodecamethylene dodecanamide (nylon 1212), polymetaxylylene adipamide (nylon) MXD6), polytetramethylene adipamide (nylon 46) and mixtures and copolymers thereof; nylon 6/66, nylon 66 / 6T in which 6T component is 50 mol% or less (6T: polyhexamethylene terephthalamide) , Copolymers such as nylon 66 / 6I (6I: polyhexamethylene isophthalamide), nylon 6T / 6I / 66, nylon 6T / 6I / 610, etc., wherein the 6I component is 50 mol% or less; polyhexamethylene terephthalamide ( Nylon 6T), polyhexamethylene isophthalamide (nylon 6) ), Poly (2-methylpentamethylene) terephthalamide (nylon M5T), poly (2-methylpentamethylene) isophthalamide (nylon M5I), nylon 6T / 6I, nylon 6T / M5T, and the like. In addition, copolymer nylon such as amorphous nylon may be used, and examples of amorphous nylon include polycondensates of terephthalic acid and trimethylhexamethylenediamine.

  Further, a ring-opening polymer of cyclic lactam, a polycondensate of aminocarboxylic acid, and a copolymer comprising these components, specifically, nylon 6, poly-ω-undecanamide (nylon 11), poly-ω-dodecanamide. (Nylon 12) and other aliphatic polyamide resins and copolymers thereof, and copolymers with polyamides comprising diamines and dicarboxylic acids, specifically nylon 6T / 6, nylon 6T / 11, nylon 6T / 12, Mention may be made of nylon 6T / 6I / 12, nylon 6T / 6I / 610/12, and mixtures thereof.

  Among the polyamide-based resins, PA (nylon) 6, PA (nylon) 66, and PA (nylon) 6/66 are preferable among the above.

[(B) component]
By combining the component (B) with the component (A), the extrusion moldability is improved, and in particular, even when extruded in a strand shape, the occurrence of drawdown is prevented.

  Component (B) is at least one selected from aromatic vinyl monomer, vinyl cyanide monomer, acrylic acid, acrylic ester, methacrylic acid, methacrylic ester, and butadiene, excluding the resin of (A). A rubber-containing polymer comprising: As the rubber-containing polymer of component (B), ASA (acrylic ester-styrene-acrylonitrile) resin, MAS (methacrylic ester-acrylonitrile-styrene) resin, MBS (methacrylic ester-butadiene-styrene) resin, ABS ( An acrylonitrile-butadiene-styrene resin is preferable.

  The rubber-containing polymer (B) preferably has a rubber content of 30% by mass or more, more preferably 40 to 90% by mass, and still more preferably 60 to 90% by mass.

[Component (C)]
As the inorganic filler of component (C), a fibrous material can be used in addition to a non-fibrous material such as powder, plate, scale, granule, indeterminate shape, and crushed product. The inorganic filler of component (C) can be subjected to a known surface treatment for improving dispersibility.

  Non-fibrous fillers include mica, talc, kaolin, silica, calcium carbonate, barium sulfate, glass beads, glass flakes, glass microballoons, clay, molybdenum disulfide, wollastonite, calcium polyphosphate, metal powder, metal flakes Metal ribbons, metal oxides (alumina, zinc oxide, titanium oxide, etc.), carbon powder, graphite, carbon flakes, scaly carbon, carbon nanotubes, and the like can be used.

  Examples of fibrous fillers include glass fibers, PAN-based and pitch-based carbon fibers, stainless steel fibers, metal fibers such as aluminum fibers and brass fibers, gypsum fibers, ceramic fibers, zirconia fibers, alumina fibers, silica fibers, and titanium oxide. A fiber, silicon carbide fiber, rock wool, potassium titanate whisker, barium titanate whisker, barium strontium titanate whisker, aluminum borate whisker, silicon nitride whisker, zinc oxide whisker, or the like can be used.

  (C) As an inorganic filler of a component, a powdery thing is preferable, that whose average particle diameter measured by the method as described in an Example is 0.05-100 micrometers is preferable, More preferably, 0.1-50 micrometers, More preferably, it is 0.1-20 micrometers.

[Component (D)]
The (D) component lubricant is a known one, and examples thereof include fatty acid metal salts, ester compounds, amide group-containing compounds, epoxy compounds, phosphate esters described in paragraphs 72 to 80 of Patent Document 1. Can be used.

[Other ingredients]
The composition of the present invention is an antioxidant, a heat stabilizer, a weathering agent, a release agent, a pigment, a dye, a crystal nucleating agent, a plasticizer, an antistatic agent, a flame retardant, etc. These known components can be contained.

[Content ratio]
The ratio of the component (A) and the component (B) in the base resin is
(A) 70-99 mass% is preferable, More preferably, it is 80-98 mass%, More preferably, it is 85-97 mass%,
As for (B) component, 1-30 mass% is preferable, More preferably, it is 2-20 mass%, More preferably, it is 3-15 mass%.

  When (A) component and (B) component are the said ratio, the supply stability of the composition at the time of using a hopper can be improved, and extrusion processability, especially the moldability at the time of extruding in a strand form are improved. be able to.

  (C) The ratio of a component is 100-400 mass parts with respect to 100 mass parts of base resin components, Preferably it is 100-350 mass parts, More preferably, it is 100-300 mass parts. When the proportion of the component (C) is in the above range, it is possible to impart a texture and weight feeling such as metal or ceramics to a molded product obtained from the composition.

  (D) The ratio of a component is 0.01-5 mass parts with respect to 100 mass parts of base resin components, Preferably it is 0.05-3 mass parts, More preferably, it is 0.1-1 mass part. When the ratio of the component (D) is in the above range, the supply stability of the composition when a hopper is used can be enhanced by a synergistic action with the component (A).

  The specific gravity of the composition of the present invention is preferably 1.6 or more, and preferably 1.7 to 4.5, from the viewpoint of enhancing the texture and weight of the molded product.

<Molding method>
Next, a method for extruding the above resin composition into a desired shape using an extrusion molding machine having a hopper will be described. In addition, each process is performed continuously and is not a separate process.

  In the first step, a predetermined amount is charged from the hopper. When the content of the inorganic filler (C) was high, it was difficult to feed a predetermined amount from the hopper. However, in the processing method of the present invention, a predetermined amount of the composition can be easily charged from the hopper by the action of the components (A) and (D) contained in the composition.

  In the second step, after melt-kneading in an extruder, in a third step, it is extruded into a desired shape such as a strand. When the content of the inorganic filler of component (C) is high, there is a problem that the molded product easily draws down during extrusion, and as described in the Examples of Patent Document 1, not by extrusion but by tableting. A molding method is applied. However, in the processing method of the present invention, the above-described problems are solved by the action of the component (B) contained in the composition.

  By extruding into a strand shape, pellets that are easy to handle at the time of molding can be obtained, and therefore, it is more suitable for molding by injection molding or the like than when it is made into tablets as in Patent Document 1.

  The molded product obtained from the resin composition of the present invention has a texture and weight and can be used as a substitute for metal or ceramics. For example, a pen housing, a hand shaver, a model gun housing, a cup It can be applied to dishes such as dishes, food containers (heat-resistant containers), kitchen knife stockers, soap holders, and the like.

1. Measurement method (1) Judged from the average particle size photograph of component (A). Measuring instrument: Keyence Microscope VHX-500F
(2) Relative viscosity of component (A) [viscosity in 98% sulfuric acid (25 ° C.) solution]
In an environment at a temperature of 25 ° C., relative viscosity (relative viscosity with respect to 100 ml of 98% concentration sulfuric acid not dissolving the polymer) in which 1 g of polymer was dissolved in 100 ml of 98% concentration sulfuric acid was expressed as an intrinsic viscosity (98 % Sulfuric acid) In the graph showing the relationship of relative viscosity, converted into intrinsic viscosity (3) Average particle diameter of component (C) Judged from the photograph. Measuring instrument: Microscope VHX-500F manufactured by Keyence Corporation.

2. Components of Composition (A) Component Polyamide 1: Novamid manufactured by Mitsubishi Engineering Plastics, Polyamide 6 1007PJ, Average particle size of 300 μm or less, Relative viscosity 2.2
Polyamide 2: Novamid manufactured by Mitsubishi Engineering Plastics, Polyamide 6 1007J, average particle diameter of about 2.0 mm, relative viscosity of 2.2
Polyamide 3: Novamid manufactured by Mitsubishi Engineering Plastics, Polyamide 6 1013PJ, average particle size of 300 μm or less, relative viscosity 2.8
(B) component
ASA: UGS AXS resin A400N: Acrylic rubber 45%
MAS: Rohm and Haas acrylic polymer, paraloid EXL2315, 80% acrylic rubber
MBS: Rohm and Haas MBS, Paraloid EXL2602, 80% butadiene rubber
ABS: Technopolymer ABS, DP611, butadiene rubber 40%
AS: “Cebian 020” manufactured by Daicel Polymer Co., Ltd.
Component (C) Filler 1: Barium sulfate B55 manufactured by Sakai Chemical Industry Co., Ltd., average particle size 0.6 μm
Filler 2: Barium sulfate B54 manufactured by Sakai Chemical Industry Co., Ltd., average particle size 1.2μm
Filler 3: Barium sulfate B34 manufactured by Sakai Chemical Industry Co., Ltd., average particle size 0.03μm
Component (D) Lubricant: Ethylene bisstearylamide, Van Lube N-18 manufactured by Harima Chemicals
3. Test method As a testing machine, Nippon Steel Works, twin screw extruder TEX30
(Hopper: lower base 200 mm × 200 mm, upper base 300 mm × 300 mm, height 800 mm, die: strand diameter 3.0 mm, 3 holes) was used.

(1) Material supply stability When 5 kg of the composition was supplied to the hopper of the tester, the material supply stability was measured based on the difference from the amount that could be charged into the extruder. Tested 5 times and evaluated by average value.
○: The difference between the supply amount and the actual input amount is less than ± 20% ×: The difference between the supply amount and the actual input amount is ± 20% or more (2) Mass production stability 240 ° C.), whether or not the drawn-down strands were continuously drawn out from the die was evaluated based on whether or not the extruded strands could be drawn with a roller.
○: There was no drawdown at all, and it could be taken up with a roller. X: A drawdown occurred, and it could not be taken up with a roller. (3) Appearance of molded product Injected under the following conditions using each composition Molded product obtained by molding (color plate:
Dimension 50 × 90 mm) was observed with the naked eye.
○: No almost floating Kiga inorganic filler to the entire molded article ×: obtained in tests there are floating filler in a portion of the molded article (4) texture of the molded article "(3) Appearance of molded article" molding The product was evaluated for texture (feel) in comparison with a ceramic (ceramic plate) molded product of the same shape.
○: The molded product has a texture similar to a ceramic plate.
X: The molded article has a texture different from that of a ceramic plate.

Claims (4)

(A) In 23 ° C. water, the water absorption after 24 hours (ISO 62) is 0.6% or more, the average particle size is 1 mm or less, the content is 10% by mass or more, and the relative viscosity is 2.4 or less. 70-99% by mass of thermoplastic resin and (B) aromatic vinyl monomer, vinyl cyanide monomer, acrylic acid, acrylic ester, methacrylic acid, methacrylic ester, excluding the resin of component (A) An inorganic filler having an average particle diameter of 0.05 to 100 μm with respect to 100 parts by mass of a base resin component containing 1 to 30% by mass of a rubber-containing polymer consisting of at least one selected from butadiene A resin composition for processing an extrusion molding machine having a hopper, containing 100 to 400 parts by mass and (D) 0.01 to 5 parts by mass of a lubricant.   The resin composition for processing an extrusion machine having a hopper according to claim 1, wherein the rubber content of the rubber-containing polymer (B) is 30% by mass or more. It is a processing method of the resin composition of Claim 1 or 2,
A molding method comprising a step of feeding a predetermined amount from a hopper, a step of melt-kneading in an extruder, and a step of extrusion molding into a desired shape.   The molding method according to claim 3, wherein the step of extruding into a desired shape is a step of extruding into a strand shape.