JPH07133370A - Flame-retardant resin composition - Google Patents

Abstract

PURPOSE:To provide the title composition improved in flame retardancy and inhibited from increased specific gravity, lowered tensile properties, surface whitening and a prolonged duration of unquenched part after quenching by mixing a specified resin component with a specified metal hydroxide, specified red phosphorus and a specified carbon powder. CONSTITUTION:99-70wt.% synthetic resin having no oxygen in the molecular structure is mixed with 1-30wt.% synthetic resin having oxygen in the molecular structure and optionally a compatibilizer for a polymer alloy to obtain a resin component. 100 pts.wt. this component is mixed with 5-200 pts.wt. metal hydroxide having a BET specific surface area of 1-30m<2>/g and a mean secondary particle diameter of 0.1-107mum, 2-30 pts.wt. red phosphorus of a mean particle diameter of 1-50mum, and 1-50 pts.wt. carbon powder of a mean particle diameter of 1-10mum and a carbon component content of 70wt.% or above.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a flame retardant resin composition and a flame retardant. More specifically, when blended with synthetic resins that do not have oxygen atoms in the molecular structure, it significantly improves flame retardancy, increases specific gravity, decreases tensile properties, surface whitening phenomenon, and the fire residue retention time after extinction. TECHNICAL FIELD The present invention relates to a flame-retardant agent capable of providing a halogen-free flame-retardant resin composition in which the flame retardancy is suppressed, and a halogen-free flame-retardant resin composition containing the flame retardant agent.

[0002]

2. Description of the Related Art Since resins and synthetic resins such as rubber are themselves easily soluble, various disasters due to fire or the like are likely to occur. In order to prevent this, various proposals have been made to make these synthetic resins flame-retardant. As a flame-retardant resin composition, there has been proposed a resin composition in which an organic halide or a combination of the halide and antimony trioxide is mixed with a synthetic resin. However, this resin composition has problems that it corrodes a molding machine during processing, generates a large amount of smoke during a fire, and the smoke is toxic and corrosive.

As a solution to this problem, there has been proposed a resin composition containing a metal hydroxide such as aluminum hydroxide or magnesium hydroxide. In this case, there is a problem that a large amount of metal hydroxide such as 100 to 250 parts by weight must be mixed with 100 parts by weight of the synthetic resin. It has also been proposed to try to improve the flame retardancy by blending carbon black, red phosphorus, acrylic fiber and the like with synthetic hydroxides as a flame retardant auxiliary together with the metal hydroxide. However, this resin composition exhibits a flame retardant synergistic effect on synthetic resins containing oxygen atoms in the molecular structure, but exhibits flame retardancy on synthetic resins containing no oxygen atoms in the molecular structure. There is a problem that the effect of developing sex is insufficient.

The applicant of the present application discloses, in Japanese Patent Application No. 5-90748, metal hydroxides, red phosphorus and synthetic resins containing oxygen atoms in the molecular structure, and synthetic resins containing no oxygen atoms in the molecular structure. It was found that the flame retardancy could be significantly improved by blending with, and proposed. But even with this proposal,
Compared with a flame-retardant resin composition containing a halogen-based flame-retardant agent, a slightly inferior aspect of flame retardancy was observed, and in the case of hard plastics, thin products, and molded products of fine materials, there were insufficient points. .

[0005]

Since metal hydroxide has a weak flame-retarding effect per unit weight, there is a problem that sufficient flame retardancy is not expressed unless a large amount is added to synthetic resins. is there. Even in the case of a large amount of compound, flame-retardant can be achieved in a compound range showing sufficiently practical tensile properties in soft synthetic resins for electric wires and the like. However, in the case of synthetic resins which are a little harder than that, there is a problem that the large amount of compounding significantly reduces the strength such as tensile properties. In addition, a large amount of metal hydroxide added to synthetic resins causes problems such as increasing the specific gravity of the obtained flame-retardant resin composition molded article and increasing the surface whitening phenomenon of the molded article in a humid atmosphere. Occurs.

The surface whitening phenomenon means that when a molded product of a flame-retardant resin composition containing a metal hydroxide is left in the air or water for a long time, the compounded metal hydroxide reacts with carbonate ions. Then, it becomes a metal carbonate, which bleeds on the surface of the molded product to whiten the surface of the molded product. This phenomenon impairs the appearance of the molded product. The surface whitening phenomenon can be suppressed to some extent by surface-treating the surface of the metal hydroxide with an appropriate surface-treating agent, but it is not sufficiently satisfactory. Therefore, to prevent the surface whitening phenomenon,
It is important to reduce the amount of metal hydroxide compounded.
Further, by reducing the amount of the metal hydroxide compounded, it is possible to prevent the specific gravity of the molded product from increasing and the tensile properties from decreasing.

The inventors of the present invention, in the flame retardation of synthetic resins having no oxygen atom in the molecular structure, when using a metal hydroxide as the main flame retardant, use only red phosphorus as a flame retardant aid. By blending, the flame retardance is insufficient, and even if blending red phosphorus as a flame retardant aid and synthetic resins containing oxygen atoms in the molecular structure, the flame retardancy is insufficient. In view of the above, an effort was made to research and develop a flame retardant having a further significant flame retardant effect and a flame retardant resin composition containing the flame retardant. That is, the object of the present invention is to significantly improve the flame retardancy of synthetic resins having no oxygen atom in the molecular structure, suppress the deterioration of tensile properties, suppress the increase in specific gravity, and suppress the surface whitening phenomenon. Another object of the present invention is to provide a flame retardant which can be obtained, and a synthetic resin composition containing the flame retardant and having no oxygen atom in the molecular structure.

[0008]

The present invention is a resin comprising 99 to 70% by weight of synthetic resins having no oxygen atom in the molecular structure and 1 to 30% by weight of synthetic resins having an oxygen atom in the molecular structure. 100 parts by weight of components and 5 to 5 metal hydroxides
200 parts by weight, red phosphorus 2 to 30 parts by weight, carbon powder 1
A flame-retardant resin composition, characterized in that the flame-retardant resin composition comprises 50 to 50 parts by weight. Further, the present invention provides a metal hydroxide 100.
Parts by weight, red phosphorus 1 to 600 parts by weight, carbon powder 0.0
A flame retardant comprising 5 to 1000 parts by weight and 0.5 to 600 parts by weight of at least one synthetic resin having an oxygen atom in its molecular structure.

In order to make flame retardance of synthetic resins having no oxygen atom in the molecular structure, it is necessary to improve the flame retardance by blending only metal hydroxide and red phosphorus. I couldn't. However, the applicant of the present application has found that a flame retardant composed of a metal hydroxide, red phosphorus, and a synthetic resin containing an oxygen atom in its molecular structure significantly increases the flame retardancy of a synthetic resin containing no oxygen atom in its molecular structure. I found that it could be improved and proposed it. Then, the present inventors have found that when carbon powder is added to this flame retardant, the flame retardancy is further improved, and the present invention has been completed. Due to this flame retardancy improving effect, the resin composition containing the flame retardant of the present invention has an advantage that various properties such as retention of high tensile properties, suppression of increase in specific gravity, and reduction of surface whitening phenomenon are exhibited. ing. The flame retardant of the present invention cannot exhibit a high flame retardant effect even if it lacks one of the constituent components.

The compounding ratio of the synthetic resin having no oxygen atom in the molecular structure and the synthetic resin having an oxygen atom in the molecular structure used in the present invention is in the range of 99: 1 to 70:30. When the compounding ratio of the synthetic resin having an oxygen atom in the molecular structure exceeds the upper limit of the above range, the mechanical strength characteristics of the obtained synthetic resin composition deteriorate, which is not preferable. Further, if the compounding ratio of the synthetic resin is less than the lower limit of the above range, the flame retardancy of the obtained synthetic resin composition becomes insufficient, which is not preferable. That is, in the present invention, the compounding ratio of the synthetic resin having an oxygen atom in the molecular structure is an amount sufficient to improve the flame retardancy of the obtained synthetic resin composition, and the obtained flame-retardant synthetic resin composition. It is a range that does not reduce the mechanical strength of the product.

As synthetic resins having no oxygen atom in the molecular structure, polypropylene, ethylene-propylene copolymer, high density polyethylene, low density polyethylene, ultra high molecular weight polyethylene, ultra low density polyethylene, linear low density Polyethylene, butadiene resin, ethylene-propylene-diene rubber (EPDM), isoprene rubber, butadiene rubber, butyl rubber, methylpentene resin, acrylic rubber-acrylonitrile-styrene copolymer resin (A
AS resin), acrylonitrile-styrene copolymer resin (AS resin), acrylonitrile-butadiene-styrene copolymer resin (ABS resin), polystyrene resin, methacrylic resin, ethylene methyl methacrylate resin, styrene-butadiene rubber (SBR resin), melamine resin Etc. are illustrated.

Examples of the synthetic resins having an oxygen atom in the molecular structure used as one component in the flame retardant in the present invention are as follows. Ethylene-vinyl-acetate resin (EVA), ethylene-ethyl-acrylate resin (E
EA), polyvinyl butyral resin (PVB), polyvinyl alcohol resin (PVA), olefin- or vinyl-based synthetic resins such as ethylene-acrylic acid copolymer resin, acetic acid fibrin resin, polyurethane resin, polyamide resin, polyacetal resin, poly Arylate resin, polyethylene terephthalate resin, polybutylene terephthalate resin, polyether sulfone resin, polyphenylene ether resin, diallyl phthalate resin, polycarbonate resin, polyphenylene oxide resin, polyphenylene sulfide resin, polyimide resin, phenol resin, epoxy resin, polyether ketone resin, Silicone resin, silicone rubber, etc.

The compatibility between synthetic resins having an oxygen atom in the molecular structure and synthetic resins having no oxygen atom in the molecular structure is poor, and the mechanical strength of the halogen-free flame-retardant resin composition of the present invention is A polymer alloy compatibilizer may be added when the surface appearance may be deteriorated. As the polymer alloy compatibilizer, polystyrene-polyimide block copolymer, polystyrene-polymethyl methacrylate block copolymer, polystyrene-polyethylene block copolymer, polystyrene-polyethyl acrylate graft copolymer, polystyrene-polybutadiene graft copolymer, polypropylene-ethylene-
Examples thereof include propylene-diene rubber graft copolymer, polypropylene-polyamide graft copolymer, polyethyl acrylate-polyamide graft copolymer, carboxylated polyethylene, MAH-modified polypropylene, MAH-modified EPR and the like.

The metal hydroxide used in the present invention is a hydroxide of a divalent or trivalent metal such as aluminum hydroxide, magnesium hydroxide and calcium hydroxide. These may be natural products or synthetic products. Further, these metal hydroxides may be double hydroxides in which metal atoms such as nickel, manganese, copper, zinc and iron are in solid solution. These metal hydroxides have a BET specific surface area of 1 to 30 m ² / g, preferably 1 to 10 m ² / g, and an average secondary particle diameter of preferably 0.1 to 10 μm, more preferably 0.2. ~ 3
Those having a thickness of μm are preferably used from the viewpoints of workability of the compounded synthetic resin, mechanical strength of the obtained molded product, and surface appearance.

Further, the above metal hydroxide may be treated with a surface treatment agent, and preferable surface treatment agents are as follows. Higher fatty acids such as oleic acid and stearic acid or alkali metal salts thereof, vinylethoxysilane, vinyl-tris (2-methoxy) silane, gamma-methacryloxypropyltrimethoxysilane, gamma-aminopropyltrimethoxysilane, beta (3,
4-epoxycyclohexyl) ethyltrimethoxysilane, gamma-glycidoxy-propyltrimethoxysilane, gamma-mercaptopropyltrimethoxysilane and other silane coupling agents, isopropyltriisostearoyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate, Titanate coupling agents such as isopropyl tri (N-aminoethyl-aminoethyl) titanate and isopropyl tridecylbenzenesulfonyl titanate, aluminum coupling agents such as acetoalkoxyaluminum diisopropylate, orthophosphoric acid and stearyl alcohol Mono- or diesters of phosphoric acid partial esters such as acid or alkali metal salts thereof. The surface treatment agent is
A preferable amount is about 0.1 to 10 parts by weight per 100 parts by weight of metal hydroxide.

The red phosphorus used in the present invention has an average particle size of 1 to
It is preferably 50 μm, and may be surface-treated if necessary. The surface-treated red phosphorus includes olefin-coated red phosphorus, carboxylic acid polymer-coated red phosphorus, titanium oxide-coated red phosphorus, titanium aluminum condensate-coated red phosphorus, titanium-cobalt complex hydrated oxide-coated red phosphorus, and heat curing. A preferred example is a resin-coated red phosphorus. The carbon powder used in the present invention has an average particle size of about 1 n.
It is preferably m to 10 μm and has a carbon content of 70% by weight or more. For example, activated carbon, carbon black, graphite and the like that satisfy the above characteristics are available.

When the metal hydroxide, red phosphorus and carbon powder are blended with the synthetic resin, they may be powdery or granulated. The granulated product is more preferable in consideration of the work environment, workability, productivity and the like. The metal hydroxide content is 100% by weight, which is 99 to 70% by weight of synthetic resins having no oxygen atom in the molecular structure and 1 to 30% by weight of synthetic resins having oxygen atom in the molecular structure. 5 to 200 parts by weight, preferably 5 to 150 parts by weight, and more preferably 1 to 100 parts by weight of a certain synthetic resin composition.
It is 0 to 120 parts by weight. The synthetic resin composition obtained when the content of the metal hydroxide is less than the lower limit of the above range,
The flame retardance is insufficient, and if it exceeds the upper limit, it becomes impossible to suppress the deterioration of tensile properties, the increase of specific gravity and the surface whitening phenomenon. The compounding amount of red phosphorus is 2 to 30 parts by weight, preferably 2 to 20 parts by weight, and more preferably 5 to 15 parts by weight with respect to 100 parts by weight of the synthetic resin composition. If it is less than the lower limit of the above range, the flame retardancy-imparting effect is poor. Even if stabilized red phosphorus is used, red phosphorus has a problem of phosphine generation during processing and combustion, and therefore it is preferable that it is as small as possible.
Further, commercially available stabilized red phosphorus has a large particle size of about 5 to 50 μm, and when blended in a large amount, it adversely affects the mechanical strength of the synthetic resin composition. Therefore, in the present invention, the maximum compounding amount is limited to the upper limit of the above range or less.

The amount of carbon powder blended is 1 to 50 parts by weight, preferably 3 to 100 parts by weight, based on 100 parts by weight of the synthetic resin composition.
15 parts by weight, more preferably 5 to 15 parts by weight. If it is less than the lower limit of the above range, the flame retardancy-imparting effect is poor, and if it is more than the upper limit, the mechanical strength and electrical insulation of the obtained molded product deteriorate, and the glowing becomes longer in the UL94VE flame retardancy test. It causes drawbacks. Therefore, in the present invention, the maximum compounding amount is limited to the upper limit of the above range or less. When the blending amount of carbon powder is small, color unevenness occurs at the gate portion of the obtained injection molded product and the appearance is deteriorated, but in the above range, a black molded product having a good appearance is obtained. The compounding method for forming the flame-retardant resin composition of the present invention is not particularly limited, and any means can be adopted as long as it can uniformly mix these. For example, after each component and other additives and fillers are mixed in advance, they are melt-kneaded using an open roll, a single or twin screw extruder, a Banbury mixer or the like. The method for molding the obtained flame-retardant resin composition is not particularly limited, and for example, injection molding, extrusion molding, blow molding, calender molding, compression molding and the like can be arbitrarily adopted.

Various additives, fillers, etc. may be added to the flame-retardant resin composition of the present invention, and some of them are as follows. Antioxidant, UV absorber, metal deactivator, cross-linking agent, colorant, lubricant, curing agent, foaming agent,
Nucleator, acrylic fiber, glass fiber, milled glass fiber, glass powder, carbon fiber, inorganic fiber, aromatic polyamide fiber, metal fiber, metal flake, metal powder, ferrite, fibrous magnesium hydroxide, fibrous basic sulfuric acid Magnesium, magnesium oxide, calcium carbonate, talc, mica, clay, wollastonite, tin and its inorganic salts, anthracene, antimony oxide, lithopone.

The present invention will be described in more detail based on the following examples. In the following examples, parts and% mean parts by weight and% by weight, unless otherwise specified. The average secondary particle diameter, flame retardancy, specific gravity, tensile properties and acid resistance in each of the following examples were measured as follows. Average secondary particle size: Metal hydroxide and red phosphorus were made into an aqueous suspension of about 1% by weight, and then ultrasonically dispersed for 3 minutes. Immediately after that, Microtrac (manufactured by Nikkiso Co., Ltd.) ) Was measured. The average secondary particle diameter of the carbon powder is 10,000 times to 100,0.
It was measured by a transmission electron microscope photograph of 00 times. Flame retardance: measured by UL94VE method. Specific gravity: Measured according to JIS K7112. Tensile properties: Measured according to JIS K 7113. Polypropylene and ABS resin were measured using a No. 1 test piece at a test speed of 50 mm / min. Surface whitening phenomenon: Two 1 / 8-inch thick UL94VE test pieces were immersed in ion-exchanged water in 500 ml, and carbon dioxide was blown into the water and left for 24 hours at 24 ° C. for magnesium and The elution amount of aluminum was measured by an atomic absorption method. This test is an accelerated test when the test piece is left in the air or in water. The greater the elution amount of metal, the more the surface whitening phenomenon occurs,
The surface appearance is poor.

Examples 1 to 4, Comparative Examples 1 to 9 Impact-grade polypropylene, vinyl acetate content 20
% EVA resin, BET specific surface area 8 m ² / g, average secondary particle diameter 0.75 μm and coating amount in terms of stearic acid 2.
Magnesium hydroxide surface-treated to 5%, red phosphorus having an average secondary particle diameter of 13 μm, carbon powder and di-
Lauryl thio di propionate (hereinafter referred to as DLTP), pentaerythyl tetrakis [3- (3,5
-Di-tert-arylbutyl-4-hydroxyphenyl)
Propionate (Irganox 1010, manufactured by Ciba-Gaiki Co., Ltd.) was premixed at the compounding ratio shown in Table 1, and then melt-kneaded using a twin-screw extruder. The resulting kneaded product was injection molded at 230 ° C. to a thickness of 1/16 inch and 1 /
8 inch test piece was made, UL94VE flame retardant test,
Specific gravity measurement, tensile property test and surface whitening test were performed.
Table 2 shows the obtained test results.

Table 1 Synthetic Resins Metal Red Phosphorus Carbon Non-Oxygen-Containing Resin Oxygen-Containing Resin Hydroxide Powder Polypropylene EVA Resin Mg Hydroxide Example 1 92 8 70 10 8 Example 2 92 8 90 10 3 Example 3 95 5 70 10 8 Example 4 92 8 70 10 8 Example 5 9 8 8 70 10 8 Comparative Example 1 100 0 0 0 0 Comparative Example 2 100 0 210 0 0 Comparative Example 3 100 0 135 135 0 Comparative Example 4 92 8 135 135 0 Comparative Example 5 100 0 175 0 8 Comparative Example 6 92 8 8 Comparative Example 7 100 0 70 70 10 8 Comparative Example 8 100 0 0 10 8 Comparative Example 9 92 8 0 10 8 Note: Examples 1-2, Comparative Examples 5-9: Average secondary particle diameter 2
0 nm channel method carbon black Example 3: Thermal method carbon black having an average secondary particle diameter of 300 nm Example 4: Activated carbon having an average secondary particle diameter of 50 nm Example 5: Graphite fine powder having an average secondary particle diameter of 1 μm,

Table 2 Flame retardancy Specific gravity Tensile properties Surface whitening UL94VE Yield point Tensile elongation at break MgO elution amount 1/16 inch Strength Kgf / cm ² (%) (ppm) Example 1 V-0 1.26 220 70 1 Example 2 V-0 1.29 210 70 2 Example 3 V-0 1.25 220 100 1 Example 4 V-0 1.26 220 100 1 Example 5 V-0 1.26 220 150 1 Comparative example 1 Non-standard 0.90 280 700 0 Comparative example 2 V-0 1.54 160 5 30 Comparative example 3 V-2 The following 1.42 170 90 8 Comparative Example 4 V-0 1.44 180 30 8 Comparative Example 5 V-1 1.49 190 10 13 Comparative Example 6 V-1 1.43 190 15 10 Comparative Example 7 V-2 or less 1.25 210 150 1 Comparative Example 8 V-2 or less 0.99 280 80 0 Comparative Example 9 V-2 or less 1.00 280 80 0

The test piece of the example was more than the test piece of the comparative example.
Despite the significantly small amount of metal hydroxide compounded, the flame retardancy is greatly improved. Further, the specific gravity is low, the deterioration of tensile properties is small, and the surface whitening is suppressed. For example, comparing Comparative Examples 2 and 4 with the Examples, the Examples maintain the flame retardancy at V-0 level despite the drastic decrease of the metal hydroxide content. In addition, polypropylene is a light resin, and therefore many applications have been developed. The test pieces of the examples have a low specific gravity and are suitable for use in applications that take advantage of the above characteristics of polypropylene.

Example 6, Comparative Examples 10-12 Impact-grade ABS resin having a specific gravity of 1.06, EVA resin having a vinyl acetate content of 30%, magnesium hydroxide used in Example 1, red phosphorus having an average particle size of 5 μm The carbon-furnace method carbon black having an average secondary particle diameter of 60 nm was premixed at the compounding ratio shown in Table 3, and then melt-kneaded at 240 ° C. using a twin-screw extruder. Approximately 240
A 1 / 8-inch test piece was prepared by injection molding at ° C, and various characteristics were measured. The test results are shown in Table 4.

Table 3 Synthetic Resins Metal Red Phosphorus Carbon Non-oxygen-containing Resin Oxygen-containing Resin Hydroxide Powder ABS Resin EVA Resin Mg Hydroxide Example 6 92 8 10 10 8 Comparative Example 10 100 0 0 0 0 Comparative Example 11 100 0 140 0 0 Comparative Example 12 92 8 40 10 0 Note: 0.5 parts by weight of Irganox 1010 was used in Example 6 and Comparative Example. 10-12 blended, carbon powder uses carbon black by gas furnace method

Table 4 Flame retardancy Specific gravity Tensile properties Surface whitening UL94VE Yield point Tensile elongation at break MgO elution amount 1/16 inch Strength Kgf / cm ² (%) (ppm) Example 1 V-0 1.15 450 10 0.5 Comparative example 10 Non -standard 1.06 480 50 0 Comparative example 11 V-0 1.54 270 28 Comparative example 12 V-0 1.27 400 5 3 The test pieces of the examples were excellent in flame retardancy, and suppressed in increase in specific gravity, decrease in tensile properties and surface whitening, despite the small amount of metal hydroxide compounded. There is.

Example 7, Comparative Examples 13 to 15 EEA with ultra low density polyethylene and ethyl acetate content of 20%
Resin, 1% surface treatment with isopropyltriisostearoyl titanate, BET specific surface area of 6 m ² / g, aluminum hydroxide having an average secondary particle diameter of 1.0 μm, red phosphorus having an average secondary particle diameter of 10 μm and average Secondary particle size 2
0 μm channel method carbon black was premixed at the compounding ratio shown in Table 5. This mixture was melt-kneaded at 160 ° C. with an open roll. The resulting kneaded product was subjected to a press molding machine at 160 ° C. at a thickness of 1/12 inch for a tensile test, a thickness of 1/8 inch for a specific gravity and surface whitening test, and a thickness of 1/16 inch. A test piece for flame retardancy test was prepared and subjected to each test. The measurement results are shown in Table 6.

Table 5 Synthetic Resin Metal Red Phosphorus Carbon Non-Oxygen-Containing Resin Oxygen-Containing Resin Hydroxide Powder Polyethylene EEA Resin Hydroxide Al Example 7 90 10 80 10 10 Comparative Example 13 100 0 0 0 0 Comparative Example 14 100 0 210 0 0 Comparative Example 15 90 10 90 90 10 0

Table 6 Flame retardance Specific gravity Tensile properties Surface whitening UL94VE Yield point Tensile elongation at break Al ₂ O ₃ elution amount 1/16 inch Strength Kgf / cm ² (%) (ppm) Example 7 V-0 1.33 110 700 0.01 or less Comparative Example 13 Nonstandard 0.90 165 800 800 0.01 or less Comparative Example 14 V-0 1.62 63 400 0.01 or less Comparative Example 15 V-2 or less 1.32 105 650 0.01 or less

The test piece of Example 7 has improved flame retardancy as compared with Comparative Example 15, and has suppressed increase in specific gravity and reduction in tensile properties. When aluminum hydroxide is used, the elution amount of aluminum is 0.02 as Al ₂ O _3.
It was 1 ppm or less, and the surface whitening phenomenon due to carbon dioxide did not occur.

[0032]

INDUSTRIAL APPLICABILITY According to the present invention, a flame retardant for a synthetic resin comprising a metal hydroxide, red phosphorus, carbon powder and synthetic resins having oxygen atoms in the molecular structure, and the flame retardant are blended. A flame retardant resin composition is provided. This flame retardant has a high flame retardant effect and can be applied to hard plastics without deteriorating the mechanical strength and appearance. It is also suitable for use in the field of thin and fine products where high flame retardancy is difficult.
Further, there is provided a flame-retardant resin composition having a low specific gravity and capable of obtaining a molded product having excellent mechanical strength and surface whitening resistance.

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[Procedure amendment]

[Submission date] March 22, 1994

[Procedure Amendment 1]

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[0002]

2. Description of the Related Art Since resins and synthetic resins such as rubber are flammable by themselves, various disasters due to fire or the like are likely to occur. In order to prevent this, various proposals have been made to make these synthetic resins flame-retardant. As a flame-retardant resin composition, there has been proposed a resin composition in which an organic halide or a combination of the halide and antimony trioxide is mixed with a synthetic resin. However, this resin composition has problems that it corrodes a molding machine during processing, generates a large amount of smoke during a fire, and the smoke is toxic and corrosive.

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As a solution to this problem, there has been proposed a resin composition containing a metal hydroxide such as aluminum hydroxide or magnesium hydroxide. In this case, there is a problem that a large amount of metal hydroxide such as 100 to 250 parts by weight must be mixed with 100 parts by weight of the synthetic resin. It has also been proposed to try to improve the flame retardancy by blending carbon black, red phosphorus, acrylic fiber and the like with synthetic hydroxides as a flame retardant auxiliary together with the metal hydroxide. The effect of carbon black on the flame retardant aid is shown in JP-B-57-10898, and the effect of acrylic fiber on the flame retardant aid is shown in JP-B-2-2656969, and the effect of the flame retardant aid is small. It was a thing. When the flame retardant aid is red phosphorus, it shows a sufficient synergistic effect of developing flame retardancy for synthetic resins containing oxygen atoms in the molecular structure, but it does not affect synthetic resins containing oxygen atoms in the molecular structure. On the other hand, there is a problem that the flame retardant effect is insufficient.

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When the metal hydroxide, red phosphorus and carbon powder are blended with the synthetic resin, either a powder product or a granulated product may be used. The granulated product is more preferable in consideration of the work environment, workability, productivity and the like. The compounding amount of the metal hydroxide is 99 to 50% of synthetic resins having no oxygen atom in the molecular structure.
5 to 200 parts by weight, preferably 5 to 150 parts by weight, relative to 100 parts by weight of the synthetic resin composition, which is a total of 70% by weight and 1 to 30% by weight of synthetic resins having oxygen atoms in the molecular structure. Parts, more preferably 10 to 120 parts by weight. The synthetic resin composition obtained when the amount of the metal hydroxide compounded is less than the lower limit of the above range, the flame retardance is insufficient, and when the upper limit is exceeded, the tensile properties decrease, the specific gravity increases,
It becomes impossible to suppress the surface whitening phenomenon. The amount of red phosphorus is 2 to 3 with respect to 100 parts by weight of the synthetic resin composition.
The amount is 0 parts by weight, preferably 2 to 20 parts by weight, more preferably 5 to 15 parts by weight. If it is less than the lower limit of the above range, the flame retardancy-imparting effect is poor. Even if stabilized red phosphorus is used, red phosphorus has a problem of phosphine generation during processing and combustion, and therefore it is preferable that it is as small as possible. Further, commercially available stabilized red phosphorus has a large particle size of about 5 to 50 μm, and when blended in a large amount, it adversely affects the mechanical strength of the synthetic resin composition. Therefore, in the present invention, the maximum compounding amount is limited to the upper limit of the above range or less.

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[0027] The test pieces of the examples are excellent in flame retardancy, and suppress increase in specific gravity, decrease in tensile properties, and surface whitening, despite the small amount of metal hydroxide compounded.

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Example 7, Comparative Examples 13 to 15 EEA with ultra low density polyethylene and ethyl acetate content of 20%
Resin, 1% surface treatment with isopropyltriisostearoyl titanate, BET specific surface area of 6 m ² / g, aluminum hydroxide having an average secondary particle diameter of 1.0 μm, red phosphorus having an average secondary particle diameter of 10 μm, and average Secondary particle size 2
0 nm channel method carbon black was premixed at the compounding ratio shown in Table 5. This mixture was melt-kneaded at 160 ° C. with an open roll. The resulting kneaded product was subjected to a press molding machine at 160 ° C. at a thickness of 1/12 inch for a tensile test, a thickness of 1/8 inch for a specific gravity and surface whitening test, and a thickness of 1/16 inch. A test piece for flame retardancy test was prepared and subjected to each test. The measurement results are shown in Table 6.

Claims (2)

[Claims] 1. A resin component 100 comprising 99 to 70% by weight of a synthetic resin having no oxygen atom in its molecular structure and 1 to 30% by weight of a synthetic resin having an oxygen atom in its molecular structure.
Parts by weight, 5 to 200 parts by weight of metal hydroxide, and red phosphorus 2
A flame-retardant resin composition comprising -30 parts by weight and 1-50 parts by weight of carbon powder. 2. 100 parts by weight of metal hydroxide and 1 red phosphorus
To 600 parts by weight, 0.05 to 1000 parts by weight of carbon powder, and 0.5 to 600 parts by weight of at least one kind of synthetic resin having an oxygen atom in the molecular structure.