JP2002161211A - Flame-retardant resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a flame-retardant resin composition from which a molding having a good balance of flame retardancy, heat resistance and impact resistance is obtained. SOLUTION: This flame-retardant resin composition comprises (A) one or more selected from a polyester-based resin, a polystyrene-based resin, a polyamide-based resin, a polycarbonate-based resin and a polyphenylene ether- based resin and (B) a flame retardant. Both (B-1) a phosphinate and (B-2) phosphoric acid or its derivative are used together as the flame retardant (B).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a flame-retardant resin composition capable of obtaining a molded article having a good balance of flame retardancy, heat resistance and impact resistance.

[0002]

BACKGROUND OF THE INVENTION As non-halogen flame retardants for thermoplastic resins, organic phosphate esters such as triphenyl phosphate are well known. Satisfactory flame retardancy cannot be obtained even when used as a flame retardant in alloys that contain it. In addition to reducing the heat resistance of molded products due to plasticization, there is also a problem in terms of safety because flame-retardant gas is generated during processing. There is.

Red phosphorus, which is disclosed in Japanese Patent Application Laid-Open No. 10-298395, is widely used as a flame retardant because of its excellent flame retardant effect. However, coloring of pellets and molded articles, poor handling, and processing There is a problem that gas derived from the flame retardant is generated. Further, ammonium polyphosphate has a problem that it has poor flame retardancy and decomposes and absorbs moisture during processing.

JP-A-49-74736 describes the use of a metal phosphinate substituted with an alkyl group or an aryl group as a flame retardant. JP-A-9-241395 also exemplifies a metal phosphinate. Although they are excellent in flame retardancy, they have problems that the manufacturing process is rather complicated and costly, and that the molded product may be brittle because it is present as an inorganic substance in the resin.

An object of the present invention is to provide a flame-retardant resin composition which can solve the above-mentioned problems of the prior art such as flame retardancy, heat resistance, safety and the like.

[0006]

As a means for solving the above-mentioned problems, the present invention comprises (A) a thermoplastic resin and (B) a flame retardant, and (B) phosphine (B-1) as a flame retardant. Provided is a flame-retardant resin composition using an acid salt and (B-2) phosphoric acid or a derivative thereof in combination.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The thermoplastic resin (A) used in the present invention is not particularly limited, but (A-1)
Polyester resin, (A-2) polystyrene resin,
One or more selected from (A-3) a polyamide resin, (A-4) a polycarbonate resin, and (A-5) a polyphenylene ether resin are preferable.

The polyester resin (A-1) is a divalent or higher carboxylic acid component or a derivative thereof having an ester-forming ability, a divalent or higher valent alcohol component and / or a phenol component, or a derivative thereof having an ester-forming ability. Is a saturated polyester resin obtained by polycondensation by a known method.

As the polyester resin, polyethylene terephthalate, polybutylene terephthalate, polyhexamethylene terephthalate, polycyclohexane dimethylene terephthalate, polyethylene naphthalate,
One or more selected from polybutylene naphthalate and the like are included. Among these, polyethylene terephthalate and polybutylene terephthalate are particularly preferred because they have an excellent balance of performance such as moldability and heat resistance.

Examples of the polystyrene resin (A-2) include polymers of styrene and styrene derivatives such as α-substituted and nuclear-substituted styrene. Further, a copolymer mainly composed of these monomers and a monomer of a vinyl compound such as acrylonitrile, acrylic acid and methacrylic acid and / or a conjugated diene compound such as butadiene and isoprene is also included. For example, polystyrene,
Impact polystyrene (HIPS) resin, acrylonitrile-butadiene-styrene copolymer (ABS) resin,
An acrylonitrile-styrene copolymer (AS resin), a styrene-methacrylate copolymer (MS resin), a styrene-butadiene copolymer (SBS resin) and the like are included.

Further, the polystyrene resin may include a styrene copolymer in which a carboxyl group-containing unsaturated compound for improving compatibility with the polyamide resin is copolymerized. The styrenic copolymer in which the carboxyl group-containing unsaturated compound is copolymerized is a carboxyl group-containing unsaturated compound and optionally other monomers copolymerizable therewith in the presence of the rubbery polymer. Is a copolymer obtained by polymerizing Specific examples of the components include: 1) In the presence of a rubbery polymer obtained by copolymerizing a carboxyl group-containing unsaturated compound, a monomer containing an aromatic vinyl monomer as an essential component or aromatic vinyl and a carboxyl group-containing unsaturated compound. A graft polymer obtained by polymerizing a monomer containing a saturated compound as an essential component, and 2) a graft polymer containing an aromatic vinyl and a carboxyl group-containing unsaturated compound as essential components in the presence of a rubbery polymer. Graft copolymer obtained by copolymerization of a monomer, 3) a rubber-reinforced styrene resin in which a carboxyl group-containing unsaturated compound is not copolymerized, a carboxyl group-containing unsaturated compound, and aromatic vinyl as essential components. 4) A mixture of the above 1) and 2) and a copolymer containing a carboxyl group-containing unsaturated compound and aromatic vinyl as essential components; 5) The above 1) and 2) ), 3), 4) and aromatic vinyl There is a mixture with a copolymer as an essential component.

In the above 1) to 5), styrene is preferable as the aromatic vinyl, and acrylonitrile is preferable as the monomer copolymerized with the aromatic vinyl. The content of the carboxyl group-containing unsaturated compound in the component (A) is preferably 0.1 to 8% by weight, more preferably 0.2 to 7% by weight.

As the polyamide resin (A-3),
Polyamide resin formed from diamine and dicarboxylic acid and their copolymers, specifically, nylon 66, polyhexamethylene sebacamide (nylon 6.10), polyhexamethylene dodecanaamide (nylon 6.12) ,
Polydodecamethylene dodecanamide (nylon 121
2), polymethaxylylene adipamide (nylon MXD
6), polytetramethylene adipamide (nylon 46)
And mixtures and copolymers thereof; nylon 6/66, 6
Nylon 66 / 6T (6) having a T component of 50 mol% or less
T: polyhexamethylene terephthalamide), nylon 66 / 6I having a 6I component of 50 mol% or less (6I: polyhexamethylene isophthalamide), nylon 6T / 6I
/ 66, copolymers such as nylon 6T / 6I / 610; polyhexamethylene terephthalamide (nylon 6T),
Polyhexamethylene isophthalamide (nylon 6
I), copolymers such as poly (2-methylpentamethylene) terephthalamide (nylon M5T), poly (2-methylpentamethylene) isophthalamide (nylon M5I), nylon 6T / 6I, and nylon 6T / M5T. In addition, copolymer nylon such as amorphous nylon may be used. Examples of the amorphous nylon include polycondensates of terephthalic acid and trimethylhexamethylenediamine.

Further, a ring-opening polymer of a cyclic lactam, a polycondensate of an aminocarboxylic acid and a copolymer comprising these components, specifically, nylon 6, poly-ω-undecanamide (nylon 11), poly- Aliphatic polyamide resins such as ω-dodecanamide (nylon 12) and copolymers thereof, copolymers with polyamides comprising diamines and dicarboxylic acids, specifically nylon 6T / 6, nylon 6T
/ 11, nylon 6T / 12, nylon 6T / 6I / 1
2, nylon 6T / 6I / 610/12 and the like, and mixtures thereof.

Examples of the polycarbonate resin (A-4) include those obtained by reacting a dihydric phenol with a carbonate precursor by a well-known solution method or melting method.

The dihydric phenol includes 2,2-bis (4-hydroxyphenyl) propane (bisphenol A), bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2 -Screw (4
-Hydroxy-3,5-dimethylphenyl) propane,
2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, 2,2-bis (4-hydroxy-3-
Methylphenyl) propane, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl)
One or more selected from sulfones and the like are included. Of these, bis (4-hydroxyphenyl) alkane-based ones are preferred, and bisphenol A is particularly preferred.

The carbonate precursor includes at least one selected from diallyl carbonates such as diphenyl carbonate, dialkyl carbonates such as dimethyl carbonate and diethyl carbonate, carbonyl halides such as phosgene, and haloformates such as dihaloformate of dihydric phenol.

The number average molecular weight of the polycarbonate resin is not particularly limited, but is preferably in the range of about 17000 to 32000 in order to impart a practically required mechanical strength to a molded article obtained from the composition. preferable.

Examples of the polyphenylene ether resin (A-5) include the following homopolymers and copolymers.

Examples of the homopolymer include poly (2,6-dimethyl-1,4-phenylene) ether, poly (2-methyl-6-ethyl-1,4-phenylene) ether and poly (2,6-diethyl). -1,4-phenylene) ether,
Poly (2-ethyl-6-n-propyl-1,4-phenylene) ether, poly (2,6-di-n-propyl-)
1,4-phenylene) ether, poly (2-methyl-6)
-N-butyl-1,4-phenylene ether), poly (2-ethyl-6-isopropyl-1,4-phenylene) ether, poly (2-methyl-6-hydroxyethyl-1,4-phenylene) ether and the like Among them, poly (2,6-dimethyl-1,4-phenylene) ether is preferable.

The copolymer is a copolymer having a phenylene ether unit as a main constituent unit, and is composed of a monomer (for example, 2,6-dimethylphenol) forming the homopolymer and another phenol. Copolymers, such as 2,
Copolymer of 6-dimethylphenol and 2,3,6-trimethylphenol, 2,6-dimethylphenol and o
And cresol, and a copolymer of 2,6-dimethylphenol with 2,3,6-trimethylphenol and o-cresol.

(A) As the thermoplastic resin, (A-1)
A resin containing at least 50% by weight of a polyester resin and / or (A-3) a polyamide resin is preferable, and 60% by weight
Those containing the above are more preferable, and the remainder can be selected from the other thermoplastic resins described above.

(A) As the thermoplastic resin, (A-1)
A resin containing at least 70% by weight of the polyester-based resin and / or (A-2) polystyrene-based resin is preferable, a resin containing at least 60% by weight is more preferable, and the remainder can be selected from the other thermoplastic resins described above.

(A) As the thermoplastic resin, (A-3)
A resin containing at least 70% by weight of a polyamide resin and / or (A-2) a polystyrene resin is preferable, and 60% by weight
Those containing the above are more preferable, and the remainder can be selected from the other thermoplastic resins described above.

When (A-2) a polystyrene resin is used as the thermoplastic resin (A), an AS resin and / or an ABS resin are preferred.

Mixing ratio (weight ratio) in the above combination
Are (A-1) / (A-3), (A-1) / (A-2)
And (A-3) / (A-2) are preferably 100/0
５5/95, more preferably 100/0 to 10/90,
More preferably, it is 100/0 to 30/70. This range is preferable because flame retardancy, heat resistance and impact resistance can be maintained at a high level.

The flame retardant (B) used in the present invention is (B-
1) Phosphinates and (B-2) phosphoric acid or derivatives thereof.

(B-1) The phosphinate is one or two selected from those represented by the following general formulas (I) and (II).
The above are preferred.

[0029]

Embedded image

(Wherein, R ₁ and R ₂ are a hydrogen atom and a carbon number of 1)
An alkyl group having 1 to 16 carbon atoms, an alkyl group containing an ether bond having 1 to 16 carbon atoms, an aryl group, an aralkyl group, or a cycloalkyl group, R ₃ represents a divalent organic group, and n represents an integer of 1 or more. And M represent an atom or an organic group that forms a salt. R ₁ and R ₂ are alkyl groups having an average carbon number in the range of 1 to 10 in order to properly maintain the phosphorus content in the component (B-1) and enhance the effect of imparting flame retardancy. And an aralkyl group are preferred. R ₃ is not particularly limited as long as it is a divalent organic group, but includes an alkylene group having 1 to 10 carbon atoms, — (CH ₂ ) _m C ₆
H ₄ (CH ₂ ) _m- (m represents 0 or a number of 1 or more) is preferable.

The atom or organic group forming the salt represented by M in the general formulas (I) and (II) is selected from aluminum, calcium, amide group, annium group, alkylammonium group and groups derived from melamine. One or more are preferred. When M is the above atom or organic group, the flame retardant is less likely to be decomposed during the processing of the composition, and the flame retardancy is improved by the atom or organic group forming the salt represented by M during combustion. Such an effect cannot be obtained with a metal salt of sodium phosphinate.

When the phosphinates represented by the general formulas (I) and (II) are used in combination, the weight ratio of (I) / (II) is 10
/ 90 to 30/70.

(B-2) Phosphoric acid or a derivative thereof is 280
With a thermal decomposition residue at 99 ° C of 99% or more, ie, 280 ° C
In this case, those which hardly decompose are preferred, and phosphate esters are more preferred. Here, the residue after thermal decomposition at 280 ° C. is TG
A (thermogravimetric analyzer) under N ₂ atmosphere at 150 ° C.
After removing water and the like by holding for 10 minutes at 20 ° C. and raising the temperature to 280 ° C. at 20 ° C./min. The thermal decomposition residue amount (% by weight) is calculated by (residue amount / initial weight) × 100.

(B) In the flame retardant, (B-1) and (B
The blending ratio (weight ratio) of -2) is preferably 1/99 to 99/1, more preferably 5/95 to 95/5, and 20/99.
80-70 / 30 is more preferred.

The amount of the flame retardant (B) is preferably 1 to 70 parts by weight, more preferably 5 to 60 parts by weight, and still more preferably 1 to 100 parts by weight of the thermoplastic resin (A).
0 to 60 parts by weight. When the amount is 1 part by weight or more, the flame retardancy can be enhanced, and when the amount is 70 parts by weight or less, the molded article can be prevented from becoming brittle.

The composition of the present invention may further comprise (C) a flame-retardant auxiliary such as a nitrogen-containing compound having a triazine ring such as melamine, a metal oxide such as tin oxide or zirconium oxide, calcium hydroxide, dolomite or hydro- Metal hydroxides such as talcite, silicon-containing compounds such as branched silicones,
One or two or more selected from boron-containing compounds such as zinc borate, zinc metaborate, and barium metaborate, and fluorine-containing compounds such as polytetrafluoroethylene can be blended.

The amount of the flame retardant aid (C) is preferably 1 to 20 parts by weight, more preferably 1 to 15 parts by weight, and even more preferably 3 to 100 parts by weight of the thermoplastic resin (A).
１５15 parts by weight.

The composition of the present invention may contain other components, if necessary, in a range that does not impair the object of the present invention. Examples of the other components include stabilizers against heat, light or oxygen (phenolic compounds, Antioxidants such as phosphorus compounds; UV absorbers such as benzotriazole compounds, benzophenone compounds and phenyl salicylate compounds; heat stabilizers such as hindered amine stabilizers, tin compounds, epoxy compounds, etc.), plasticizers, polydimethyl Slidability improvers such as siloxane, lubricants, release agents, antistatic agents, coloring agents, glass fibers,
Various inorganic fibers such as carbon fiber and glass fiber are exemplified.

The molded article of the present invention is obtained by injection-molding the above flame-retardant resin composition, and can be used as a material for housings and chassis of OA equipment and electronic equipment.

[0040]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto. In the following Examples and Comparative Examples, the following components were used. (A-1) Component PEst: Polybutylene terephthalate (trade name: Duranex 2000) manufactured by Polyplastics Co., Ltd. (A-2) Component ABS: ABS resin: polybutadiene latex 40 having an average particle diameter of 0.3 μm. Styrene 74 in the presence of parts by weight
%, Acrylonitrile 26% monomer mixture 60
Parts were emulsion polymerized. The obtained graft copolymer latex is coagulated with sulfuric acid, neutralized with caustic soda, washed, filtered,
After drying, a powdery elastic graft copolymer was obtained. (A-3) Component PA: Nylon 6, number average molecular weight 12,000 (A-4) Component PPE: Polyphenylene ether resin (GE Specialit
y Chemicals Inc. BLENDEX HP820) (B-1) Component Phosphinate of the general formula (I): M = Ca, n = 2 (Use a product of Taihei Chemical Co., Ltd.) Phosphine of the general formula (II) Acid salt: M = Ca, R = phenylene, n = 2 (produced by the same method as in JP-A-11-124466) (B-2) Component PX200: 1,3-phenylenebis (2,6-dimethyl) Phenol phosphate), manufactured by Daihachi Chemical Industry Co., Ltd. (C) component Melamine isocyanurate: Melamine cyanurate MC610 (average particle size: about 1 μm) manufactured by Nissan Chemical Co., Ltd. Ammonium polyphosphate: Daihachi Chemical Industry Co., Ltd. Other components glass fiber: Short fiber glass filler (trade name: ECS03T) manufactured by Nippon Electric Glass Co., Ltd. was used.

Examples 1 to 3 and Comparative Examples 1 to 3 Compounding ratios shown in Table 1 [Components (A-1) to (A-4) are indicated by weight%. Others are expressed in terms of parts by weight based on 100 parts by weight of component (A)]. After mixing other than glass fibers using a tumbler, the mixture was melt-kneaded using a twin-screw extruder and pelletized. The cylinder temperature was 250 ° C., and the glass fibers were mixed from the side feed in the middle of the extruder. The obtained pellets were injection-molded at a cylinder temperature of 250 ° C. and a mold temperature of 60 ° C., and the obtained molded products were evaluated. Table 1 shows the results. (1) Flame retardancy Evaluated using a test piece having a thickness of 1/8 inch in accordance with the UL94 test method. (2) Heat resistance (degree of plasticization) For an injection molded piece having a thickness of 1/4 inch, AST
Load deflection test based on MD648-82 (1.82
MPa) to determine HDT (deflection temperature under load). (3) Impact resistance For injection molded pieces having a thickness of 1/4 inch, AST
An Izod impact test (using a notched sample) based on MD256 was performed, and the Izod impact strength was evaluated. (4) Manufacturing stability The presence or absence of foaming during injection molding was observed, and those without foaming were rated as ○, and those with foaming were rated as x.

[0042]

[Table 1]

As is clear from Table 1, the molded articles obtained from the compositions of Examples 1 to 3 had a good balance of flame retardancy, heat resistance and impact resistance. On the other hand, Comparative Examples 1 to 3
Since it did not contain the component (B-1) or the component (B-2), either property was inferior. In Comparative Example 3, a decomposition gas originating in ammonium polyphosphate was generated, and foaming occurred. Further, the amount of the residue of thermal decomposition at 280 ° C. of this ammonium polyphosphate was less than 99% by weight.

[0044]

The flame-retardant resin composition of the present invention has flame-retardant properties,
A molded article having a good balance of heat resistance and impact resistance can be obtained.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4J002 BC031 BC032 BC061 BC062 BC071 BC072 BN151 BN152 BP011 BP012 CF051 CF052 CF061 CF062 CF071 CF072 CF081 CF082 CG011 CG012 CH071 CH072 CL011 CL012 CL031 CL032 CN021 CN031

Claims (11)

[Claims] 1. A flame retardant containing (A) a thermoplastic resin and (B) a flame retardant, and (B-1) a phosphinate and (B-2) phosphoric acid or a derivative thereof are used in combination as the flame retardant. Flame retardant resin compositions. 2. The method according to claim 1, wherein (A) the thermoplastic resin is one or more selected from polyester resins, polystyrene resins, polyamide resins, polycarbonate resins and polyphenylene ether resins. Flammable resin composition. 3. The flame-retardant resin according to claim 1, wherein (A) the thermoplastic resin contains at least 50% by weight of (A-1) a polyester resin and / or (A-3) a polyamide resin. Composition. 4. The flame-retardant resin according to claim 1, wherein (A) the thermoplastic resin contains at least 70% by weight of (A-1) a polyester resin and / or (A-2) a polystyrene resin. Composition. 5. The flame-retardant resin according to claim 1, wherein (A) the thermoplastic resin contains at least 70% by weight of (A-3) a polyamide resin and / or (A-2) a polystyrene resin. Composition. 6. The flame-retardant resin composition according to claim 2, wherein (A-2) the polystyrene resin is an AS resin and / or an ABS resin. 7. The method according to claim 1, wherein (B-1) the phosphinate is one or two or more selected from those represented by the following general formulas (I) and (II). 2. The flame-retardant resin composition according to 1. Embedded image (Wherein, R ₁ and R ₂ are a hydrogen atom, an alkyl group having 1 to 16 carbon atoms, an alkyl group containing an ether bond 1 to 16 carbon atoms, an aryl group, an aralkyl group, a cycloalkyl group, R ₃ is It represents a divalent organic group, n represents an integer of 1 or more, and M represents an atom or an organic group forming a salt.) 8. The method according to claim 1, wherein M in the general formulas (I) and (II) is one or more selected from aluminum, calcium, an amide group, an ammonium group, an alkylammonium group and a group derived from melamine. 8. The flame-retardant resin composition according to any one of items 1 to 7. (B-2) The phosphoric acid or its derivative is 280
The residue obtained by thermal decomposition at 99 ° C is 99% or more.
8. The flame-retardant resin composition according to any one of items 1 to 7. 10. Further, (C) a nitrogen-containing compound, a metal oxide, a metal hydroxide, a silicon-containing compound,
1 selected from a boron-containing compound and a fluorine-containing compound
Or (A) a thermoplastic resin 100
The flame-retardant resin composition according to any one of claims 1 to 9, wherein 1 to 20 parts by weight of (C) a flame-retardant aid is blended with respect to parts by weight. 11. A molded article obtained by injection molding the flame-retardant resin composition according to any one of claims 1 to 10.