JP2017057276A - Flame resistant resin extrusion molded article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To add flame retardancy which is characteristic of polyvinyl chloride to a molded article while improving low usual heat resistant temperature which is disadvantage of the polyvinyl chloride.SOLUTION: There is provided a three-component mixing thermoplastic resin composition containing polyvinyl chloride of 35 wt.% or more and at least two selected from polyolefin, polystyrene and ABS resin of the same volume as the polyvinyl chloride, where the polyvinyl chloride is dispersed in a flaky shape.SELECTED DRAWING: None

Description

  The present invention relates to a flame-retardant resin extruded product such as a film, a sheet, an injection-molded product, a blow-molded product, a wire coating material, and a fiber.

Polyvinyl chlorides, which are flame retardant resins (hereinafter abbreviated as “polyvinyl chloride”), include homopolymers such as hard polyvinyl chloride and soft polyvinyl chloride. Soft polyvinyl chloride uses a plasticizer for hard polyvinyl chloride. By adding, the mechanical properties can be changed softly to the rubber state. Soft polyvinyl chloride has good moldability, but hard polyvinyl chloride needs to use a special dedicated molding apparatus and cannot be processed by a general molding apparatus.
Moreover, hard polyvinyl chloride has a low normal heat resistance temperature of 60 to 80 ° C., and in order to increase the normal heat resistance temperature, it is necessary to make it a composite with glass fiber or the like, which has a drawback of hindering recycling. Hard polyvinyl chloride has a Vicat softening point of 92 ° C, lower than 127 ° C for polyethylene and 152 ° C for polypropylene.

In Patent Document 1, as a method for recycling and processing a carpet waste material or plasticized polyvinyl chloride sheet waste material backed with plasticized polyvinyl chloride pulverized into powder of 1 mm or less, it is heated and kneaded and heated and pressed. A method and apparatus for molding are described. The carpet waste material includes fibers made of a thermoplastic resin such as polypropylene and PET constituting the pile. However, in this document, since these fibers are used as a reinforcing material for the product sheet, the fibers are processed below the melting point of these fibers.

Polyvinyl chloride and polyolefin and polyester are not compatible, so even if they are simply kneaded, they are simply dispersed and phase-separated in a sea-island state and drip during combustion.

JP 2004-11463 A

The problem to be solved is to impart flame retardancy, which is a characteristic of polyvinyl chloride, to a resin molded product while improving the low ordinary heat resistance temperature, which is a drawback of polyvinyl chloride.

The present invention is a three-component mixed thermoplastic resin composition in which polyvinyl chloride is composed of at least two types of polyolefin, polystyrene, and ABS resin having an equal volume of 35% by weight or more, and polyvinyl chloride is dispersed in the form of flakes. This is the main feature.
Further, in the resin composition, the polyvinyl chloride is a mixture of a polyvinyl chloride homopolymer and a plasticizer, or a copolymer composed of vinyl chloride and a comonomer. The resin composition is preferably 45% by weight or more of the polyvinyl chloride.

The flame-retardant three-component mixed thermoplastic resin composition of the present invention is excellent in processability, heat resistance, and flame retardancy like general-purpose resins, is free from drip during combustion, and is inexpensive.

In the embodiment of the present invention, the polyvinyl chloride is composed of two kinds of polyolefin, polystyrene, and ABS resin having an equal volume of 35% by weight or more, and the flame retardant three-component mixed thermoplastic in which the polyvinyl chloride is dispersed in the form of flakes. It is a resin composition (hereinafter abbreviated as “resin composition”).
Further, in the resin composition, the polyvinyl chloride is a mixture of a polyvinyl chloride homopolymer and a plasticizer, or a copolymer composed of vinyl chloride and a comonomer.
Preferably, the resin composition has a polyvinyl chloride content of 45% by weight or more. When the amount of the polyvinyl chloride is less than 35% by weight, the flame retardancy is insufficient. Flame retardancy improves as the amount of polyvinyl chloride increases. The evaluation of flame retardancy was measured according to the oxygen index (LOI) and UL94 method.
When the amount of polyvinyl chloride exceeds 50% by volume, there is no improvement in heat resistance such as ordinary heat resistance temperature and Vicat softening point, which are disadvantages of polyvinyl chloride.

Another embodiment of the present invention is an injection-molded article, a fiber, a sheet, a film, and a wire covering material made of the resin composition made of the resin composition. Artificial hair is also a type of fiber, and in the case of human hair, the thickness is about 50 microns.

The plasticizers used in the polyvinyl chloride used in the present invention are phthalic acid esters such as di (2-ethylhexyl) phthalate and diisononylphthalate, adipic acid, trimellitic acid, citric acid, benzoic acid, terephthalic acid, and phosphoric acid. And at least one of epoxidized products such as fat esters, fat amides or epoxidized soybean oil. The plasticizer is used up to an equivalent amount of the polyvinyl chloride homopolymer depending on the use, but a small amount is preferable because it reduces the flame retardancy. In order to prevent a significant decrease in flame retardancy, a blending amount of 10% by weight or less with respect to the polyvinyl chloride homopolymer is preferable.

In addition to the main monomer vinyl chloride monomer, the polyvinyl chloride copolymer comonomer is not only vinyl halide comonomer, but also vinyl acetate other than vinyl halogen comonomer such as vinylidene chloride, vinyl bromide, vinylidene bromide, vinyl fluoride, vinylidene fluoride. , Methyl acrylate, methyl methacrylate, styrene, butadiene, butylene, isopropylene, propylene, ethylene, pentene, hexene, etc. , Potassium methallyl sulfonate, potassium styrene sulfonate, sodium acrylate, sodium methacrylate, potassium acrylate, potassium methacrylate, acrylic acid, methacryl Is the invention a polyvinyl chloride composition in which at least one is copolymerized dyeing imparting comonomers such.
When the dyeability-imparting comonomer is contained in at least 0.5% by weight of the polyvinyl chloride composition, dyeing is facilitated, which is preferable.

  The term “consisting of at least two kinds of polyolefin, polystyrene, and ABS resin” in the present invention means that the difference between the two kinds of capacity is within 5%. For example, even if the two are 20% by volume of HDPE and 19% by volume of LDPE, it means substantially the same capacity as used in the present invention. Examples of polyolefin include polyethylene such as HDPE, LDPE and LLDPE, and modified polyethylene. Polypropylene includes homopolymer and copolymer. Even if the polystyrene is a homopolymer, the tacticity may be different, and if the tacticity is different, it is treated as another type of polystyrene in the present invention. If the ABS resin has a different composition, it is handled as another type of ABS resin in the present invention.

In the present invention, flame retardant additives such as aromatic halogen compounds, phosphorus compounds, antimony trioxide, antimony pentoxide, and inorganic salts such as zinc oxide may be blended.

The vinyl chloride homopolymer used in the present invention is commercially available from Shin-Etsu Chemical Co., Ltd., Kaneka Co., Ltd. and the like. Copolymers of vinylidene chloride and vinyl chloride are emulsion polymerization copolymers composed of about 70% vinylidene chloride and 30% vinyl chloride, and suspension polymerization copolymers composed of about 80% vinylidene chloride and 20% vinyl chloride. Commercially available from Chemical and Solvey. Also, Kaneka Co., Ltd. sells a thermoplastic copolymer “Kane Vinyl M” (trade name) in which 5 to 10% of vinyl chloride and vinyl acetate are copolymerized. Copolymers using ethylene as a comonomer are also commercially available. Use of these copolymers is preferred because the polyvinyl chloride composition of the present invention and a molded product comprising the same can be produced without using any plasticizer.

The sodium allyl sulfonate, sodium methallyl sulfonate, sodium styrene sulfonate, potassium allyl sulfonate, potassium methallyl sulfonate, potassium styrene sulfonate, sodium acrylate, sodium methacrylate, potassium acrylate, potassium methacrylate are cations It becomes a dyeing functional group for dyes and is suitable for post-dyeing. In the case of artificial hair, if it can be dyed, it can be partially dyed in the same way as human hair, and the added value is high.

When polyvinyl chloride is used as a homopolymer, it is necessary to use a special extruder. However, as used in the present invention, when a plasticizer is blended with a homopolymer, it can be used in a processing machine such as an extruder that is usually used. Polyvinyl chloride is amorphous and does not have a melting point at which crystals melt. Even in the heated state with the addition of a plasticizer, it only softens and exhibits a thixotropic effect.

When a suitable amount of flaky or columnar fine particles having a large L / D is blended in the molten polymer, a thixotropic effect can be obtained and the apparent viscosity can be increased. Examples of the flaky fine particles include montmorillonite and bentonite. When these fine particles are a single layer, thixotropic curing can be imparted to the resin by kneading 0.5% by weight with respect to the total amount. In the present invention, these fine particles can also be blended.

When kneaded with thermoplastic polyvinyl chloride and another polymer that is phase-separated, a sea-island structure is formed, and the island component has a nearly spherical shape in order to minimize surface energy. Since L / D is small, the thixotropic effect cannot be obtained. Moreover, since these combinations are phase-separated, mechanical properties are impaired by the amount of the island component.

Mixing two equal amounts of phase-separated thermoplastic resins with these phase-separated thermoplastic polyvinyl chloride forms a minimal surface structure, as if blending an appropriate amount of flaky fine particles into the molten polymer, A thixotropy effect is obtained and the viscosity can be increased. Thixotropy means a state that does not flow unless a certain force is applied. In this case, the deterioration of mechanical properties is suppressed from the sea-island structure. The resin composition molded product of the present invention can confirm the expression of the special structure by observing the chlorine distribution with EPMA or the like.

Due to this thixotropic effect, the thermoplastic composition of the present invention can maintain a state where it does not drip despite a decrease in viscosity due to an increase in temperature during combustion. Although the present invention is a thermoplastic resin composition that is easy to mold, it can solve a seemingly contradictory problem that it does not drip during combustion.

The method for producing the polyvinyl chloride composition of the present invention can be produced using a general uniaxial, biaxial kneading extruder or the like. Moreover, it can manufacture using the injection molding machine etc. which have a suitable kneading part.
Since polyvinyl chloride lacks thermal stability during the production of the thermoplastic resin composition of the present invention, it is produced by blending an appropriate thermal stabilizer.
If necessary, additives such as lubricants, colorants, flame retardants, antibacterial agents, fungicides, and deodorants are blended.
Examples of the stabilizer include zinc oxide, zinc acetate mercaptotin heat stabilizer, maleate tin heat stabilizer, laurate tin heat stabilizer, hindered amine, hindered phenol, and the like. Metallic soap and polyethylene wax are used as lubricants. , Higher fatty acid-based, ester-based and higher alcohol-based lubricants.

Machines generally used for the production of the resin composition of the present invention in which the extruded product is an extruded product such as a fiber, film, sheet, injection molded product, pipe, etc. For example, if it is a fiber, a spinning machine, injection molding If it is a product, an injection molding machine may be used, and if it is a sheet, a T-die extruder may be used.
A flame retardant product in which a flame retardant is blended with a thermoplastic resin has a drawback of drip during combustion. The polyvinyl chloride composition of the present invention exhibits thixotropic properties and does not drip during combustion.

(Example 1) For injection molding with an injection molded product MI of 30, 25 parts by weight of commercially available polypropylene homopolymer and copolymer pellets, 50 parts by weight of “Kane Vinyl M1008” powder, and 0.5 parts by weight of hindered amine were added to a biaxial extruder. A fixed amount was supplied from a hopper, extruded in a shape at a maximum temperature of 180 ° C., rapidly cooled in water, and then cut with a cutter to produce resin composition compound pellets of the present invention. Using this pellet, an injection molding machine having a width of 12.5 mm, a length of 125 mm, and a thickness of 1.25 mm was produced at 190 ° C. using an injection molding machine. This combustion test sample was subjected to a combustion test according to the UL94 method. As a result, the fire extinguishing time was 3 seconds in the vertical test, no drip was observed, and the sample passed the V0 standard. Observation of the cut surface and each surface by EPMA showed a chlorine distribution in a layered manner, and it was confirmed that polyvinyl chloride was dispersed in the form of flakes. The LOI value for this sample was 33. The heat resistance (Vicat softening point) of this sample was almost the same as that of polypropylene.

(Comparative Example 1) Injection molded product In the same manner as in Example 1, 25 parts by weight of the commercially available polypropylene homopolymer and copolymer pellets were changed to 50 parts by weight of the commercially available polypropylene homopolymer, and a combustion test sample was produced. This combustion test sample was subjected to a combustion test according to the UL94 method. As a result, drip started from the ignition in the vertical test, and V0 was incompatible.

Injection molded product (Comparative Example 2)
In the same manner as in Example 1, 15 parts by weight of the commercially available polypropylene homopolymer and copolymer pellets were changed to only 70 parts by weight (59% by volume) of the commercially available polypropylene homopolymer, and a combustion test sample was produced. This combustion test sample was subjected to a combustion test according to the UL94 method. As a result, it was not ignited in the vertical test, was not drip, was V0 compatible, but lacked heat resistance, and the Vicat softening point was polyvinyl chloride. Almost unchanged.

(Example 2) Extruded sheet In the same manner as in Example 1, 25 parts by weight of commercially available polystyrene homopolymer and copolymer pellets for MI having an MI of 30 and 50 parts by weight of “Kane Vinyl M” powder had an MI of 1 to 2 The resin composition sheet of the present invention having a thickness of 3 mm and a width of 10 cm is manufactured by the T-die method by changing only 30 parts by weight of commercially available polypropylene homopolymer and copolymer pellets and 40 parts by weight of “Kane Vinyl M” powder. did. A combustion test sample having a width of 12.5 mm and a length of 125 mm was cut out from this sheet and subjected to a combustion test according to the UL94 method. As a result, in a vertical test, the fire extinguishing time was 9 seconds, no drip was observed, and it passed the V0 standard. . Observation of the cut surface and each surface by EPMA showed a chlorine distribution in a layered manner, and it was confirmed that polyvinyl chloride was dispersed in the form of flakes. The LOI value for this sample was 28. The heat resistance (Vicat softening point) of this sample was almost the same as polystyrene.

(Example 3) Artificial hair In the same manner as in Example 1, 25 parts by weight of commercially available polypropylene homopolymer and copolymer pellets and 50 parts by weight of "Kane Vinyl M" powder were spun for MI of 30. For commercial use, we changed only 30 parts by weight of polypropylene homopolymer and copolymer pellets and 40 parts by weight of “Kane Vinyl M” powder. The artificial hair of the present invention, a single yarn thickness of 55 DTX, and a 700,000 DTX tow were produced. This artificial hair was ignited with a lighter, then self-extinguished and did not drip. The LOI value for this sample was 29.

(Comparative Example 4) Artificial hair In the same manner as in Example 3, only 35 parts by weight of commercially available polypropylene homopolymer and copolymer pellets for spinning with MI of 30 and 30 parts by weight of “Kane Vinyl M” powder were changed to a spinning machine. After spinning and drawing from a dumbbell-shaped nozzle at 180 ° C. by a conventional method, annealing was performed, and the obtained yarn was converged to produce an artificial hair of the present invention, a single yarn thickness of 55 DTX, and 700,000 DTX tow. The artificial hair did not self-extinguish after igniting with a lighter. The LOI value for this sample was 24.

  The resin composition of the present invention can be produced as an injection molded product, a sheet, a film, an electric wire covering material, etc. by a general-purpose production machine using a thermoplastic resin.

Claims (4)

A flame retardant three-component thermoplastic resin consisting of two types of polyolefin, polystyrene, and ABS resin with a polyvinyl chloride content of 35% by weight or more and less than 50% by volume. Polyvinyl chloride is dispersed in flaky form. Composition. The resin composition of claim 1, wherein the polyvinyl chloride is a mixture of a polyvinyl chloride homopolymer and a plasticizer, or a copolymer of vinyl chloride and a comonomer. The resin composition according to claim 1 or 2, wherein the polyvinyl chloride is 45% by weight or more. An injection-molded article, a sheet, a film, and a wire covering material comprising the resin composition according to claim 1.