JP2000038515A - Fire-retardant resin composition, preparation thereof, fire retardant for thermoplastic resin and fire retardant auxiliary for thermoplastic resin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition having a high fire retardance using a non-halogen fire retardant, and to provide a non-halogen fire retardant which imparts a high fire retardance to thermoplastic resins. SOLUTION: A fire-retardant resin composition is prepared by mixing a thermoplastic resin (A), a furfural-phenol resin (B) and a phosphorus compound (C). A fire retardant for thermoplastic resins comprises a furfural-phenol resin (B) and a phosphorus compound (C). A fire retardant auxiliary comprises a furfural-phenol resin (B).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition having excellent flame retardancy, a method for producing the same, and a flame retardant and a flame retardant auxiliary for a thermoplastic resin. More particularly, the present invention relates to a flame-retardant resin composition containing a halogen-free flame retardant and a flame-retardant auxiliary containing no halogen-based compound, and a method for producing the same.

[0002]

2. Description of the Related Art Conventionally, thermoplastic resins have been used in a wide range of applications because of their excellent moldability. However, in particular, when used as a product such as a household product, an electric product, an OA device, an automobile, or a building material, it is required to have flame retardancy. As a known method of making a thermoplastic resin flame-retardant, a method of blending a flame retardant can be mentioned. In many cases, a halogen compound is used as the flame retardant.

[0003]

When a halogen-based compound is used to make a thermoplastic resin flame-retardant, the effect of the flame-retardation is relatively large, but it is toxic or harmful in the event of a fire or incineration. Because of the emission of such substances, there are problems such as difficulty in rescue operations and fire fighting activities, and environmental pollution. In order to cope with such environmental problems, various attempts have been made to design a flame retardant that does not use a halogen-based compound, that is, a non-halogen-based flame retardant. It was extremely difficult to find anything.

[0004] In recent years, as a method of making a thermoplastic resin flame-retardant using a non-halogen compound, Japanese Patent Application Laid-Open No. 8-16554 has been proposed.
JP 06 discloses a method in which a phenol novolak resin and melamine phosphate are used in combination, but the flame retardancy is improved, but the improvement effect is not satisfactory. The present invention is intended to solve these conventional problems, and an object thereof is to provide a resin composition having excellent flame retardancy using a non-halogen flame retardant,
Another object of the present invention is to provide a non-halogen flame retardant capable of imparting excellent flame retardancy to a thermoplastic resin.

[0005]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies on flame retardancy using a non-halogen compound of a thermoplastic resin, and as a result, phenol which has been conventionally used as an auxiliary agent of a phosphorus-based flame retardant has been studied. It has been found that by using a furfural phenol resin instead of a novolak resin and using a phosphorus compound in combination with the furfural phenol resin, the present invention has been completed. That is, the present invention provides a flame-retardant resin composition characterized by comprising a furfural phenol resin (B) and a phosphorus compound (C) mixed with a thermoplastic resin (A), and a method for producing the same.
The present invention relates to a flame retardant for a thermoplastic resin containing a furfural phenol resin (B) and a phosphorus compound (C), and a flame retardant auxiliary consisting of a furfural phenol resin (B).

[0006]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The thermoplastic resin (A) as a base polymer in the flame-retardant resin composition of the present invention is not particularly limited, and various known resins can be used. Polyolefin resins; Polystyrene resins; Polyphenylene ether resins; Polycarbonates; Polyesters such as polyethylene terephthalate and polybutylene terephthalate; Resins such as polyphenylene sulfide; these may be used alone or in combination of two or more. it can. Among these, at least one selected from the group consisting of polyolefin-based resins, polystyrene-based resins, and polyphenylene ether-based resins is preferable. The polyolefin resin used in the present invention is not particularly limited, and various known resins can be used. Among them, polyethylene resin and polypropylene resin are preferable.

The polyethylene resin used in the present invention is not particularly limited, and various known resins can be used.
For example, low density polyethylene, linear low density polyethylene, high density polyethylene, modified polyethylene and the like can be mentioned. The modified polyethylene is not particularly limited, and various known ones can be used. For example, ethylene- (meth) acrylic acid copolymer, ethylene- (meth)
Methyl acrylate copolymer, ethylene-ethyl (meth) acrylate copolymer, ethylene-vinyl acetate copolymer,
Examples include maleic anhydride-modified polyethylene, carboxylic acid-modified polyethylene, and the like. The polypropylene resin used in the present invention is not particularly limited, and various known resins can be used. Examples thereof include polypropylene and modified polypropylene. The modified polypropylene resin is not particularly limited, and various known ones can be used, and examples thereof include elastomeric resins such as an ethylene-propylene copolymer and an ethylene-propylene-diene copolymer.

The polystyrene resin used in the present invention is not particularly limited, and various known resins can be used. Examples thereof include styrene, α-substituted styrene such as α-methylstyrene, and styrene such as vinyltoluene. Derivative polymers are mentioned. Further, these monomers are mainly used, and copolymerizable monomers such as acrylonitrile, butadiene, isoprene and the like may be used. Specifically, styrene-acrylonitrile copolymer ( AS resin), styrene-butadiene random copolymer, ABS resin, styrene-butadiene-
Styrene block copolymer (SBS resin), styrene-
Isoprene-styrene block copolymer (SIS resin)
And the like.

The polyphenylene ether-based resin used in the present invention is not particularly limited, and various known ones can be used.
1,4-phenylene) ether, poly (2,6-diethyl-1,4-phenylene) ether, poly (2,6-dipropyl-1,4-phenylene) ether, poly (2-
Methyl-6-ethyl-1,4-phenylene) ether,
Poly (2-methyl-6-propyl-1,4-phenylene) ether, poly (2-ethyl-6-propyl-1,
4-phenylene) ether, (2,6-dimethyl-1,
A copolymer of (4-phenylene) ether and (2,3,6-trimethyl-1,4-phenylene) ether;
6-diethyl-1,4-phenylene) ether and (2,
Copolymer with 3,6-trimethyl-1,4-phenylene) ether, (2,6-dimethyl-1,4-phenylene) ether and (2,3,6-triethyl-1,4-phenylene) ether And the above polyphenylene ether-based resin modified with polystyrene at various styrene ratios.

In addition, the above polycarbonates; polyesters such as polyethylene terephthalate and polybutylene terephthalate; and resins such as polyphenylene sulfide are also used to improve the impact resistance, heat resistance and chemical resistance, because of the polyolefin resin, polystyrene resin and polyphenylene ether. It can be preferably blended with at least one resin selected from the group consisting of resin-based resins, especially modified polystyrene resin.

The furfural phenolic resin (B) of the present invention, when used in combination with a phosphorus compound (C) described later, has a flame retardancy to a thermoplastic resin (A) prepared by blending it as a flame retardant. It has the function and function to give.
That is, the furfural phenol resin (B) of the present invention has an action and a function as a flame retardant auxiliary agent that can form a flame retardant in combination with the phosphorus compound (C). As the furfural-phenol resin (B), various known ones can be used. Furfural phenol resin is
The molar ratio of phenols and furfural to furfural / phenols is 0.3-3, preferably 0.3-2.
The mixture is charged into a reaction vessel at a mixing ratio such that the catalyst is added, and the mixture is heated, and the water is distilled off for 1 to 4 hours, preferably 2 to 4 hours.
The reaction can be carried out for a period of time, neutralized, and then distilled under reduced pressure to remove the remaining water and unreacted phenols (Japanese Patent Application Laid-Open No. 8-234423).
And Arora, P.A. B. , Patel,
V. S. & Patel, S.M. R. , Brit. Poly
m. J. , 1987, 19, 429-433).
The catalyst used here is not particularly limited, and various commercially available catalysts can be used. For example, oxalic acid, hydrochloric acid, sulfuric acid, acetic acid, phosphoric acid, nitric acid, toluenesulfonic acid, sodium hydroxide, potassium hydroxide,
Examples thereof include calcium hydroxide, magnesium hydroxide, barium hydroxide, sodium carbonate, potassium carbonate, ammonia, and triethylamine. The phenols used here are not particularly limited, and various known phenols can be used. For example, phenol, cresol,
Xylenol, ethylphenol, propylphenol, butylphenol, amylphenol, nonylphenol, phenylphenol, phenylphenolether, phenoxyphenol, styrenated phenol,
Hydroquinone, resorcinol, dihydroxydiphenyl ether, dihydroxydiphenyl, bis (hydroxyphenyl) butane, dihydroxydiphenylsulfone, dihydroxydiphenylketone, dihydroxydiphenylmethane, bis (hydroxyphenyl) propane,
Methylene bis (ethyl tertiary butyl cresol) and mixtures thereof.

The above furfural phenol resin (B)
Is preferably 0.5 to 100 parts by weight, more preferably 50 parts by weight or less, particularly preferably 10 parts by weight or less based on 100 parts by weight of the thermoplastic resin (A). If the furfural phenolic resin (B) is less than 5 parts by weight, the effect of improving flame retardancy tends to decrease,
If the amount is more than 100 parts by weight, other properties tend to deteriorate.

In the present invention, the phosphorus compound (C) is essential. By using the phosphorus compound (C) in combination with the furfural phenol resin (B), a remarkable flame retardant effect can be obtained in the thermoplastic resin (A) obtained by blending these compounds as a flame retardant. The phosphorus compound (C) is not particularly limited, and various known compounds can be used. Among these, at least one selected from the group consisting of red phosphorus, phosphate esters and melamine phosphate is preferred. The red phosphorus used in the present invention is not particularly limited, and various known ones can be used. For example, commercially available red phosphorus embodiments include:
Red phosphorus surface-treated with a synthetic resin such as red phosphorus microencapsulated with a thermosetting resin such as a phenolic resin; and a master batch of inorganic hydrate and red phosphorus. Further, the phosphate ester used in the present invention is not particularly limited, and various known ones can be used. For example, trimethyl phosphate, triethyl phosphate, tripropyl phosphate, tributyl phosphate, tripentyl phosphate, trihexyl phosphate, tricyclohexyl phosphate,
Tri (2-ethylhexyl) phosphate, tributoxyethyl phosphate, trioleyl phosphate, triphenyl phosphate, tricresyl phosphate,
Trixylenyl phosphate, dimethylethyl phosphate, methyldibutylphosphate, ethyldipropylphosphate, hydroxyphenyldiphenylphosphate, tris (isopropylphenyl) phosphate,
Tris (o-phenylphenyl) phosphate, tris (p-phenylphenyl) phosphate, trinaphthylphosphate, cresyldiphenylphosphate, xyenyldiphenylphosphate, diphenyl (2-ethylhexyl) phosphate, di (isopropylphenyl) phenylphosphate, o -Phenylphenyl dicresyl phosphate, dibutyl phosphate, monobutyl phosphate, di-2-ethylhexyl phosphate, monoisodecyl phosphate, 2-acryloyloxyethyl acid phosphate, 2-methacryloyloxyethyl acid phosphate, diphenyl-2-
Acryloyloxyethyl phosphate, diphenyl-
Examples include 2-methacryloyloxyethyl phosphate and condensates thereof. Furthermore, the melamine phosphate used in the present invention is not particularly limited, and various known melamine phosphates can be used. For example, MPP-
A (manufactured by Sanwa Chemical Co., Ltd.) and P-7202 (manufactured by Sanwa Chemical Co., Ltd.).

The above-mentioned phosphorus compounds (C) can be used alone or in combination of two or more kinds, preferably 0.5 to 50 parts by weight, more preferably 10 parts by weight, based on 100 parts by weight of the thermoplastic resin. Parts by weight or less, particularly preferably 5 parts by weight or less. Phosphorus compound (C)
If it is less than 0.5 part by weight, the effect of improving flame retardancy tends to decrease, and if it exceeds 50 parts by weight, other properties tend to decrease.

The inorganic hydrate (D) of the present invention is added for further improving the flame retardancy, and is not particularly limited, and various known ones can be used. For example, magnesium hydroxide, aluminum hydroxide, calcium hydroxide and the like can be mentioned. The inorganic hydrate (D) is used in an amount of 0 to 200 parts by weight based on 100 parts by weight of the thermoplastic resin (A).
Preferably, it is added in an amount of 10 parts by weight or more. In particular, when the thermoplastic resin (A) is a polyolefin resin such as polyethylene or polypropylene, the inorganic hydrate (D) is 1
If the amount is less than 0 parts by weight, the effect of improving flame retardancy tends to decrease.

Further, in the present invention, a substituted or unsubstituted phenol resin such as novolak or resol used in a known flame-retardant resin composition; a phosphorus-containing polyphenol or the like, as long as the effects of the present invention are not impaired. Modified polyphenols such as boron-containing polyphenols; boron-containing compounds such as boric acid and zinc borate; nitrogen-containing compounds such as melamine and derivatives thereof; organosiloxanes such as silicone oil and silicone resin; aluminum silicate; sodium silicate; Silicon-containing compounds such as silicon; antimony-containing compounds such as antimony trioxide, antimony tetroxide, (colloidal) antimony pentoxide, sodium antimonate, and antimony phosphate can be blended.

Further, in the present invention, various fillers, additives and the like can be blended as needed within a range not to impair the flame retardancy. Illustrative examples thereof include fluorine resin, asbestos, glass fiber, carbon fiber, ceramic fiber, metal fiber, aromatic polyamide fiber, potassium titanate whisker fiber, fibrous filler such as boron whisker fiber, mica, silica, Talc, clay, calcium carbonate, wallas night, glass beads, glass balloon,
Fillers such as glass flakes, lubricants, release agents, plasticizers,
Examples include light stabilizers, ultraviolet absorbers, antioxidants, heat stabilizers, antioxidants, and additives such as dyes and pigments. In addition, an impact strength improver, a compatibilizing component, and the like can be added.

The flame-retardant resin composition of the present invention comprises a thermoplastic resin (A) and a furfural / phenol resin (B), a phosphorus compound (C) and, if necessary, an inorganic hydrate (D). It is. As a specific compounding method, a mixture or a melt-kneaded product of a furfural-phenol resin (B), a phosphorus-based compound (C) and, if necessary, an inorganic hydrate (D) is mixed with the thermoplastic resin (A). A method of melt-kneading may be used. At the time of melt-kneading, various extruders, Banbury mixers, kneaders, rolls, etc., are used in the range of (A) to 150 ° C. to 300 ° C.
Each component such as (D) is kneaded. Each component can be kneaded together, and after kneading any components,
The remaining components can be added and kneaded. Further, a preferable kneading method is a method using an extruder, and as the extruder, a biaxial co-rotating extruder is particularly preferable.

[0019]

EXAMPLES Hereinafter, the present invention will be described in more detail by way of examples, but these are merely examples, and the present invention is not limited thereto.

Synthesis Example (Synthesis of Furfural / Phenol Resin) In a separable flask equipped with an air-cooling tube, a nitrogen inlet tube, a thermometer and a stirrer, 938.5 g of phenol, 958.5 g of furfural and 33.5 g of water were dissolved. 9.35 g of sodium hydroxide is charged and stirred. This is 12
After the temperature was raised to 5 ° C. and the reaction was carried out for 2 hours while distilling off water, 57.05 g of 20% sulfuric acid was added for neutralization. After this,
The reaction mixture was distilled under a reduced pressure of 10 mmHg until the temperature of the reaction mixture reached 180 ° C. to remove water, unreacted phenol and furfural. Thereafter, the reaction mixture was taken out into a vat, cooled and pulverized to obtain a furfural-phenol resin.

Example 1 100 parts by weight of ABS resin (registered trademark Psycolac LE, manufactured by Ube Sycon Co., Ltd.), and fine particles of red phosphorus microencapsulated with a synthetic resin (trade name: Novaled # 12)
0, manufactured by Rin Kagaku Kogyo Co., Ltd.) and 6.7 parts by weight of furfural / phenol resin synthesized according to the synthesis example, and kneaded with a roll at 190 ° C. 2 kneaded materials
The sheet was heated and pressed at 00 ° C. to obtain a sheet having a thickness of 1.6 mm (1/16 inch). 12.7mm width from this sheet
Was cut out and subjected to a flame retardancy test according to the standard of US UL-94. Table 1 shows the results.

Example 2 Polypropylene resin (hereinafter referred to as PP resin; trade name: J-Aroma SA510, Nippon Polyolefin Co., Ltd.)
5. parts by weight of red phosphorus microparticles (trade name: Nova Red # 120, manufactured by Rin Kagaku Kogyo Co., Ltd.) 1.5 parts by weight, furfural / phenol resin synthesized according to a synthesis example. 7 parts by weight and 100 parts by weight of aluminum hydroxide were blended, a test piece was prepared in the same manner as in Example 1, and a similar combustion test was performed. Table 1 shows the results.

Example 3 100 parts by weight of a polyethylene resin (hereinafter referred to as PE resin; trade name Petrocene 202, manufactured by Tosoh Corporation), red phosphorus microparticles microencapsulated with a synthetic resin (trade name: Nova Red # 120; (Rin Chemical Industry Co., Ltd.)
5 parts by weight, 6.7 parts by weight of furfural phenol resin synthesized according to the synthesis example, and aluminum hydroxide 10
0 parts by weight, a test piece was prepared in the same manner as in Example 1,
A similar combustion test was performed. Table 2 shows the results.

Example 4 Polyphenylene ether resin (hereinafter referred to as PPE resin; trade name: Zylon X0061, manufactured by Asahi Kasei Kogyo Co., Ltd.)
100 parts by weight, 1.5 parts by weight of red phosphorus microparticles (trade name: Nova Red # 120, manufactured by Rin Kagaku Kogyo KK) microencapsulated with a synthetic resin, 6.7 parts by weight of furfural phenol resin synthesized according to a synthesis example And a test piece was prepared in the same manner as in Example 1, and a similar combustion test was performed. Table 2 shows the results.

Comparative Example 1 A test piece was prepared in the same manner as in Example 1 except that no furfural / phenol resin was used, and a similar combustion test was performed. Table 1 shows the results.

Comparative Example 2 A test piece was prepared in the same manner as in Example 1 except that a phenol novolak resin (trade name: Tamanol 759, manufactured by Arakawa Chemical Industry Co., Ltd.) was used instead of furfural / phenol resin. Was subjected to a combustion test. Table 1 shows the results.

Comparative Example 3 A test piece was prepared in the same manner as in Example 2 except that a phenol novolak resin (trade name: Tamanol 759, manufactured by Arakawa Chemical Industry Co., Ltd.) was used instead of furfural / phenol resin. Was subjected to a combustion test. Table 1 shows the results.

Comparative Example 4 A test piece was prepared in the same manner as in Example 3 except that a phenol novolak resin (trade name: Tamanol 759, manufactured by Arakawa Chemical Industry Co., Ltd.) was used instead of the furfural-phenol resin. Was subjected to a combustion test. Table 2 shows the results.

Comparative Example 5 A test piece was prepared in the same manner as in Example 4 except that a phenol novolak resin (trade name: Tamanol 759, manufactured by Arakawa Chemical Industry Co., Ltd.) was used instead of furfural / phenol resin. Was subjected to a combustion test. Table 2 shows the results.

[0030]

[Table 1]

[0031]

[Table 2]

In the UL-94 standard, V-0
Indicates that after 10 seconds of indirect flame on the specimen, the framing or glowing on one specimen is within 10 seconds, and the total of the five specimens is within 50 seconds, and the surgical cotton 12 inches below the framing granules V-1 indicates that the flaming or glowing on one test piece was within 30 seconds after the indirect flame was applied to the test piece for 10 seconds, and the total of the five test pieces was within 250 seconds. Indicates that the surgical cotton 12 inches below does not burn in the framing granules, and V-2 is the same as V-1, but the surgical cotton 12 inches below the framing granules. Indicates a burning state.

[0033]

The flame-retardant resin composition of the present invention uses a furfural phenol resin and a phosphorus-based compound instead of a conventional phenol novolak resin or a phosphorus-based compound or other flame-retardant or flame-retardant auxiliary. Since it is used, it is a resin composition having excellent flame retardancy. Since the flame-retardant resin composition of the present invention has flame retardancy, it is particularly suitable as a molded product used for household goods, electric products, OA equipment, products such as automobiles, or building materials.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C09K 21/12 C09K 21/12 21/14 21/14 F term (Reference) 4H028 AA07 AA10 AA12 AA35 AA42 4J002 AA011 BB001 BC021 CC032 CF061 CF071 CH071 CN011 DA056 DE077 DE087 DE147 EW046 FD010 FD132 FD136 FD137

Claims (11)

[Claims] 1. A flame-retardant resin composition comprising a thermoplastic resin (A) and a furfural phenol resin (B) and a phosphorus compound (C). 2. A furfural phenol resin (B) 0.5 to 10 with respect to 100 parts by weight of the thermoplastic resin (A).
A flame-retardant resin composition comprising 0 parts by weight and 0.5 to 50 parts by weight of a phosphorus compound (C). 3. The thermoplastic resin (A) is blended with a mixture or melt-kneaded product of a furfural-phenol resin (B) and a phosphorus compound (C) and melt-kneaded. 3. The flame-retardant resin composition according to 1 or 2. 4. The flame retardant according to claim 1, wherein the thermoplastic resin (A) is at least one selected from the group consisting of a polyolefin resin, a polystyrene resin, and a polyphenylene ether resin. Resin composition. 5. The flame-retardant resin composition according to claim 1, wherein the phosphorus compound (C) is at least one selected from the group consisting of red phosphorus, a phosphate ester and melamine phosphate. object. 6. The flame retardant according to claim 1, wherein 0 to 200 parts by weight of the inorganic hydrate (D) is added to 100 parts by weight of the thermoplastic resin (A). Resin composition. 7. The flame-retardant resin composition according to claim 6, wherein the inorganic hydrate (D) is at least one selected from the group consisting of magnesium hydroxide, aluminum hydroxide and calcium hydroxide. 8. A mixture of a furfural phenol resin (B) and a phosphorus compound (C) or a melt-kneaded mixture with the thermoplastic resin (A), and the mixture is melt-kneaded. 6. The method for producing a flame-retardant resin composition according to any one of 1 to 5. 9. A mixture or a melt-kneaded mixture of a furfural-phenol resin (B), a phosphorus compound (C) and an inorganic hydrate (D) with the thermoplastic resin (A),
The method for producing a flame-retardant resin composition according to claim 6, wherein the composition is melt-kneaded. 10. A furfural / phenol resin (B)
And a flame retardant for a thermoplastic resin comprising a phosphorus compound (C). 11. Furfural phenol resin (B)
Flame retardant aid for thermoplastic resin.