KR0184768B1 - Flame retardant thermoplastics resin composition - Google Patents

Abstract

The present invention, (A) 0 to 95% by weight polyethylene resin; (B) 0 to 95% by weight of a polyethylene copolymer; (C) 1 to 20% by weight; (D) 0-60% by weight of magnesium hydroxide and / or aluminum trihydroxide; (E) 0.1 to 10% by weight of silicate and / or aluminum hydroxide silicate; And (F) 0.05 to 3% by weight of teflon resin, and a flame retardant polyethylene-based resin composition, and a flame retardant product prepared therefrom, which provides a flame retardant and economical resin composition and flame retardant product.

Description

Thermoplastic Flame Retardant Resin Composition

The present invention relates to a resin composition comprising a flame retardant synergist for the flame retardant is very excellent, yet improved mechanical properties and a flame retardant product prepared using the same.

In recent years, the use of flame-retardant products has been demanded due to an increasing number of lives and property damages caused by fires such as communication cables and buildings caused by carelessness and electric leakage. In order to increase the safety of the information industry and reduce the occurrence of fire, flame retardant and flame retardant technologies of information, electronic and electric related products are urgently needed. In particular, development of flame-retardant products of polyethylene-based resins, which are mainly used for electric products such as electric wires, cables, and electric cords, is required.

Polyethylene includes low density (LDPE), ultra low density (VLDPE or ULDPE), linear low density (LLDPE), medium density (MDPE), high density (HDPE) polyethylene, and ultra high molecular weight polyethylene (UHMWPE), which is mainly used as a reinforcing fiber of composite materials. have. In addition, various polyethylene copolymers are produced, and representative examples thereof include ethylene vinyl acetate (EVA), ethylene vinyl alcohol, and ethylene acrylic acid (EEA) copolymer. Polyethylene-based polymers are general purpose polymers having various uses such as cables and wire coverings, various covers for electrical products, films for agricultural and packaging, extrusion rods, blow molding containers, and the like.

Meanwhile, halogen-based flame retardants, which have been used as flame retardants in the past, prohibit the use of some halogen-based flame retardants, which have been a problem in the Netherlands and Germany because of toxic gases generated during combustion. In addition, when halogen-based flame retardants and halogenated polyethylene are used, hydrogen halides generated during resin processing and molding cause problems such as mold corrosion, resin decomposition, and coloring, and are not advantageous in terms of physical properties and price. Commonly used flame retardant technologies of polyethylene include inorganic flame retardants (magnesium hydroxide (Mg (OH) ₂ ) or aluminum trihydroxide (Al (OH) ₃ )) in addition to halogenated polyethylene or halogen-based flame retardants. Phosphorus-based flame retardants There is a method using one or two or more flame retardants, but it is known that there is a problem that the physical properties are degraded by excessive use (Japanese Patent Laid-Open No. 51-27461,54-21379,63-56544, 64-132645, etc.) . On the other hand, the relationship between the flame retardant and the flame retardant synergist is known a combination of halogen flame retardant, antimony trioxide (Sb ₂ O ₃ ), phosphorus flame retardant and nitrogen compounds, and also known synergistic effects (S.Steward) , Plastics Compounding, 17 (1), 31 (1994)).

However, in the conventionally known technique, zinc borate is used as a flame retardant enhancer of enemy, but there is a disadvantage in that the flame retardant synergistic effect is relatively small (Japanese Patent Laid-Open No. 59-74138). In addition, phenolic resin has been used as a fire retardant synergist, but a large amount of more than 8% is required.

Accordingly, an object of the present invention is to solve the problems of the prior art to provide a polyethylene-based resin and a flame retardant product prepared therefrom which can produce a product having excellent flame retardancy and improved mechanical properties and economic efficiency even with a small amount of flame retardant.

In the present invention, as a flame retardant, as a new flame retardant as an adjuvant to the polyethylene or polyethylene copolymer using red phosphorus and magnesium hydroxide, red and aluminum trihydroxide, red and magnesium hydroxide and aluminum trihydroxide, or sole alone, it is conventionally used as an inorganic filler. When the included hydroxide silicate or aluminum hydroxide silicate is included, a relatively expensive flame retardant can be reduced to produce a flame retardant polyethylene resin having excellent flame retardancy and improved various physical properties at low cost.

Specifically, the present invention,

(A) 0 to 95 wt% polyethylene resin;

(B) 0 to 95% by weight of a polyethylene copolymer;

(C) 1 to 20% by weight;

(D) 0-60% by weight of magnesium hydroxide and / or aluminum trihydroxide;

(E) 0.1 to 20% by weight of silicate and / or aluminum hydroxide silicate; And

(F) 0.05 to 3% by weight of teflon resin, flame-retardant polyethylene-based resin composition, and a flame-retardant product prepared therefrom.

Hereinafter, the present invention will be described in detail.

In the composition of the present invention (A) component as low density (LDPE), ultra low density (VLDPE or ULDPE), linear low density (LLDPE), medium density (MDPE), high density (HDPE) polyethylene, and ultra high molecular weight polyethylene (UHMWPE) 1 type, or 2 or more types of resin which belongs can be used. The component (A) may be used in an amount of 0 to 95% by weight of the total resin composition, but more preferably 10 to 80% by weight, most preferably 20 to 50% by weight.

Examples of the polyethylene copolymer of component (B) include copolymers prepared using one or two or more comonomers of ethylene monomer and propylene, vinyl acetate, butyl acrylate, acrylic acid, ethyl acrylate and vinyl alcohol (EVA, EEA, EEA, etc.) can be used. The component (B) may be used in an amount of 0 to 95% by weight of the total resin composition, but more preferably 20 to 70% by weight, most preferably 30 to 60% by weight.

Component (A) and component (B) may be used alone, respectively, or by mixing one or more of each of the two components may be used so that both components are included in the composition of the present invention.

As an enemy of the component (C), the powder can be used directly or masterbatched with polyethylene and magnesium hydroxide, and the metal hydroxides (alumina hydroxide, magnesium hydroxide, Or zinc hydroxide) or titanium oxide or Zn and Ni compounds and / or thermosetting resins (melamine resins, phenol resins, polyester resins, or epoxy resins) and the like (Japanese Patent Laid-Open Nos. 61-11132 and 62-21704, EP 0052217) is used either directly or in combination with metal hydroxides or in masterbatches with resins. The smaller the average particle size of the droplet is, the more advantageous it is in terms of physical properties, and usually within 30 µm is appropriate, preferably 20 µm or less. The amount of the component (C) can be used in an amount of 1 to 20% by weight of the total resin composition, but more preferably 3 to 15% by weight, most preferably 5 to 12% by weight.

The component (D) uses magnesium hydroxide (Mg (OH) ₂ ) and / or aluminum trihydroxide (AL (OH) ₃ ) as a hydrate of an inorganic metal oxide, which is an inorganic flame retardant, and a part of the amount used is (A) or ( B) Resin of component and (C) Components of powder and masterbatch are prepared and used, and the remaining part is mixed well with resin, or the whole is mixed with resin etc. without masterbatch extruded or hopper and side feeding alone Can be added as In addition, an inorganic metal hydroxide treated with a silane or titanium coupling agent may be used to significantly improve the physical properties. The component (D) may be used in an amount of 0 to 60 wt% of the total resin composition, but more preferably 10 to 40 wt%, most preferably 15 to 30 wt%.

The silica hydroxide and / or aluminum hydroxide silicate as the component (E) of the present invention is used as a flame retardant synergist of the flame retardant. These components also serve as inorganic fillers or diluents, which relatively reduce the amount of resin. In other words, it plays a new role of causing a flame retardant synergism of the flame retardant in addition to the function as a known inorganic filler. Hydroxide silicates contain water among silica-based minerals, which include asbestos, diatomite, pyrophilite, perlite and talc. The average size of the particles is appropriately 0.1㎛ to 20㎛, preferably less than 2㎛ in terms of physical properties such as impact strength and elongation. Surface treatment of coupling agents (silane and titanate compounds) can also be used, in which case the physical properties are significantly improved. Aluminum hydroxide silicate is clay-based and contains water, which is kaoline or kaolinite. Substances classified as kaolin include kaolinite, nacrite, dickite, and halloysite, and post-processing such as double firing or semi-firing is more suitable. Particle sizes are advantageously more than 2 μm, and more suitable for surface treatment with a coupling agent when added in large quantities. The component (E) may be used in an amount of 0.1 to 10% by weight of the total resin composition, but more preferably 0.5 to 8% by weight, most preferably 1 to 5% by weight. The two kinds of inorganic compounds show excellent efficacy as a flame retardant increasing agent of a red flame retardant and bring advantages such as physical property improvement and cost reduction obtained by reducing the amount of flame retardant.

Component (F) of the present invention is a Teflon resin added as an anti drip agent, and its content and copolymer content are selected as the most suitable, so that the resin composition is 0.05 to 3.0% by weight, preferably 0.2 to 0.6% by weight, more preferably 0.3 to 0.5% by weight is added.

The flame retardant resin composition of the present invention may contain additives such as flame retardants, lubricants, antioxidants, fillers, impact modifiers, mold release agents, pigments, antistatic agents, processing aids, light stabilizers and the like in a range in which physical properties are not impaired.

The flame retardant resin composition of the present invention may be mixed with the additives if necessary, melt kneaded according to a conventional method, and then injected to prepare a flame retardant polyethylene resin product.

The following examples are provided to illustrate the invention and do not limit the scope of the invention.

Example 1

40% by weight linear low density polyethylene (LLDPE), 22% by weight phosphorus, 38% by weight magnesium hydroxide, 25% by weight linear low density polyethylene, 41% by weight ethylene vinyl acetate copolymer, 6.3% by weight, hydroxide Magnesium 25% by weight, 2% by weight of silicate hydroxide, mixed well with light stabilizer, lubricant, heat stabilizer, melt-trained in a twin-screw extruder to make pellets, dried well and injected to measure the physical properties in Table 1 Indicated.

Example 2

Ultra low density polyethylene (VLDPE) 40% by weight, 22% by weight, 38% by weight of magnesium hydroxide Master batch containing 65.8% by weight, ultra-low density polyethylene 6.5% by weight, 25% by weight magnesium hydroxide, 2% by weight silicate It was blended to%, mixed well with light stabilizer, lubricant, heat stabilizer and the like, melt-kneaded in a twin screw extruder to make pellets, and then dried and injected to measure the physical properties.

Example 3

40% by weight linear low density polyethylene (LLDPE), 22% by weight red phosphorus, 38% by weight magnesium hydroxide, 25% by weight linear low density polyethylene, 41% by weight ethylene vinyl acetate copolymer, 6.8% by weight redox Magnesium is mixed in an amount of 26% by weight and 2% by weight of silicate, and mixed well with a light stabilizer, a lubricant, and a heat stabilizer. The mixture is melt-kneaded in a twin screw extruder, made into pellets, dried well, and injected. The specific properties are shown in Table 1. It was.

Comparative Example 1

40% by weight linear low density polyethylene, 22% by weight phosphorus, 38% by weight magnesium hydroxide, 25% by weight linear low density polyethylene, 41% by weight ethylene vinyl acetate copolymer, 6.3% by weight, 27% magnesium hydroxide It was blended to%, mixed well with light stabilizer, lubricant, heat stabilizer and the like, melt-kneaded in a twin screw extruder to make pellets, and then dried and injected to measure the physical properties.

Comparative Example 2

Using a masterbatch containing 40% by weight ultra low density polyethylene, 22% by weight, 38% by weight of magnesium hydroxide, 65.8% by weight of ultra low density polyethylene, 6.5% by weight, 27% by weight of magnesium hydroxide, light stabilizer, lubricant After mixing well with a heat stabilizer and the like, melt-kneading in a twin screw extruder to make pellets, drying them well, and injecting them to measure physical properties.

(1) UL 94V rating was measured according to the regulations of the Underwriters Laboratory.

(2) The sum of the time it takes for each of the five specimens to burn down twice after 10 seconds of burning each time (10 times in total).

(3) Measured according to ASTM D 638.

(4) Measured according to ASTM D 149.

(5) Measured according to ASTM D 3638.

As can be seen from Table 1, it can be seen that the flame retardant synergist is added (Examples 1, 2 and 3) is certainly superior in flame retardancy compared to the one not added (Comparative Examples 1, 2). In addition, in the case of Example 3, the combustion test results close to incombustibility that do not burn at all. In fact, the UL94V test did not catch fire even if burning four times for 10 seconds with a flame three times higher than the fire, and it was confirmed that it had a fire extinguishing function to prevent the rise of gas flame.

Claims (5)

(A) 0 to 95% by weight of polyethylene resin; (B) 0 to 95% by weight of a polyethylene copolymer; (C) 1 to 20% by weight; (D) 0-60% by weight of magnesium hydroxide and / or aluminum trihydrate; (E) 0.1 to 10% by weight of silicate and / or aluminum hydroxide silicate; And (F) 0.05 to 3% by weight of teflon resin; flame-retardant polyethylene resin composition comprising a. The resin composition of Claim 1 containing 1 or more types of said (A) component, and 1 or more types of (B) components. According to claim 1, wherein the resin of the component (A) of low density (LDPE), ultra low density (VLDPE), linear low density (LLDPE), medium density (MDPE), high density (HDPE) polyethylene and ultra high molecular weight polyethylene (UHMWPE) 1 or more types of resin are used, The resin composition characterized by the above-mentioned. The copolymer prepared by using one or two or more comonomers of propylene, vinyl acetate, butyl acrylate, acrylic acid, ethyl acrylate and vinyl alcohol as the polyethylene copolymer as the component (B). Resin composition characterized in that the use. A flame retardant polyethylene resin product prepared by injecting the thermoplastic flame retardant resin composition of claim 1.