JP2001261973A - Thermoplastic resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a thermoplastic resin composition excellent in flame retardance or heat resistance of a molded product without emitting gases derived from a flame retardant or without causing discoloration during the molding. SOLUTION: This thermoplastic resin composition comprises (A) a thermoplastic resin and (B) a phosphinate and the component (B) is selected from those represented by the following formulae (I) and (II), wherein n denotes an integer of >=1; M denotes an alkaline earth metal or the like; and R denotes a divalent organic group.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermoplastic resin composition from which a molded article having excellent flame retardancy and heat resistance can be obtained.

[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.

Japanese Patent Application Laid-Open No. 49-74736,
JP-A-124466 discloses that a phosphorus-containing compound is used to improve flame retardancy, but some of these compounds have a low decomposition temperature and are decomposed in the processing temperature range of polyester or polyamide. For this reason, it is difficult to industrially commercialize a polyester or polyamide alloy containing the phosphorus-containing compound.

[0005] An object of the present invention is to provide a thermoplastic resin composition which can solve the problems of flame retardancy, heat resistance and safety of the prior art as described above.

[0006]

The present invention comprises (A) a thermoplastic resin and (B) a phosphinate,
Provided is a thermoplastic resin composition wherein the component (B) is one or more selected from those represented by the following formulas (I) and (II).

[0007]

Embedded image

(Wherein, n is an integer of 1 or more, M is a salt-forming atom or organic group, and R is a divalent organic group.)

[0009]

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.

Examples of the polyester resin include 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,
Examples include acrylonitrile-styrene copolymer (AS resin), styrene-methacrylate copolymer (MS resin), and styrene-butadiene copolymer (SBS resin).

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-opened polymer of a cyclic lactam, a polycondensate of an aminocarboxylic acid and a copolymer comprising these components, specifically, nylon 6, poly-ω-undecanaamide (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.

Dihydric phenols include 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 is at least one selected from diallyl carbonate such as diphenyl carbonate, dialkyl carbonate such as dimethyl carbonate and diethyl carbonate, carbonyl halide such as phosgene, and haloformate 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 practically required mechanical strength to a molded article obtained from the composition. preferable.

Examples of the polyphenylene ether-based 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 a copolymer 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.

The component (A) includes (A-1) a polyester resin, (A-2) a polystyrene resin, and (A-
3) Use each polyamide resin alone or
It is preferable to use a combination of (A-1) a polyester resin and (A-2) a polystyrene resin or a combination of (A-3) a polyamide resin and (A-2) a polystyrene resin. The (A-2) polystyrene resin is preferably an ABS resin.

The mixing ratio (weight ratio) of these
(A-1) / (A-2) or (A-3) / (A-2)
Is preferably 100/0 to 5/95, more preferably 100/0 to 10/90, and still more preferably 100/0 to 0/90.
30/70. This range is preferable because both flame retardancy and physical properties of the molded article can be achieved at a high level.

The phosphinate of component (B) used in the present invention is one or more selected from those represented by the above general formulas (I) and (II).

In the general formulas (I) and (II), the atom or organic group forming the salt represented by M is preferably an alkaline earth metal, a transition metal, an amide group, an ammonium group, or a group derived from melamine. When M is the above atom or organic group, an effect is obtained that the composition is hardly decomposed during processing.

R is not particularly limited as long as it is a divalent organic group, but is preferably a C ₁ -C ₁₀ alkylene group or a phenylene group.

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

In the composition of the present invention, the mixing ratio of the components (A) and (B) is such that the component (B) is preferably 1 to 70 parts by weight, more preferably 5 to 100 parts by weight of the component (A). ６０60 parts by weight, more preferably 10-60 parts by weight. Within this range, the flame retardancy of the molded article is excellent, and a decrease in mechanical strength can be prevented.

The composition of the present invention may contain, if necessary, other components in a range that does not impair the object of the present invention. Other components include flame retardants other than those described above [aluminum hydroxide,
Hydrated metal flame retardants such as magnesium hydroxide, inorganic flame retardants such as antimony trioxide, etc.], anti-drip agents such as fluororesins, stabilizers against heat, light or oxygen (phenolic compounds, phosphorus compounds, etc.) Antioxidants; UV absorbers such as benzotriazole-based compounds, benzophenone-based compounds, and phenyl salicylate compounds; hindered amine-based stabilizers and heat stabilizers such as tin compounds and epoxy compounds);
Examples include plasticizers, slidability improvers such as polydimethylsiloxane, lubricants, release agents, antistatic agents, coloring agents, glass fibers, carbon fibers, and various inorganic fibers.

The composition of the present invention can be used as a material for housings and chassis of OA equipment and electronic equipment.

[0033]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. In the following Examples and Comparative Examples, the following components were used. (A) Component PEst: Polybutylene terephthalate (trade name: Juranex 2000) manufactured by Polyplastics Co., Ltd. PEst: Polyethylene terephthalate (Mitsubishi Rayon, Diamond Night MA) PC: Polycarbonate [manufactured by Teijin Chemicals Ltd.] Polycarbonate (trade name Panlite L1225) was used] PA: Nylon 6, number average molecular weight 12,000 PA: Nylon 66 (Ube Nylon 2020B, manufactured by Ube Industries, Ltd.) ABS: ABS resin: polybutadiene latex having an average particle diameter of 0.3 μm Styrene 74 in the presence of 40 parts by weight
%, A monomer mixture 60 consisting of 26% acrylonitrile
Parts were emulsion polymerized. The obtained graft copolymer latex is coagulated with sulfuric acid, neutralized with caustic soda, washed, filtered,
DPE was dried to obtain a powdery elastic graft copolymer. PPE: polyphenylene ether resin (GE Specialit
y Chemicals Inc. BLENDEX HP820) (B) Component Phosphinate of the general formula (I): M = Ca, n = 2 (Use a product of Taihei Chemical Co., Ltd.) Phosphinate of the general formula (II) : M = Ca, R = phenylene, n = 2 (produced by the same method as in JP-A-11-124466) (Comparative component) Na dimethylphosphinate (JP-A-49-124)
Red phosphorus: Red phosphorus flame retardant (trade name: Nova Red 120) manufactured by Rin Kagaku Kogyo Co., Ltd. (Phosphorus content: 90% by weight or more) Ammonium polyphosphate: Large Hachi Chemical Industry Co., Ltd. Triphenyl phosphate: Daihachi Chemical Industry Co., Ltd. Anti-drip agent: Mitsui Dupont Fluorochemicals Co., Ltd. trade name Teflon 6-J was used.

Examples 1 to 7 and Comparative Examples 1 to 4 The raw materials shown in Table 1 were mixed by a tumbler, melt-kneaded by an extruder, cooled, and pelletized by a cutter to obtain each composition. For each composition, the presence or absence of discoloration of the pellet,
The presence or absence of gas during processing, flame retardancy, and heat resistance were tested by the following methods. Comparative Example 1 cannot be molded, and Comparative Example 3
Foamed during molding. (1) Presence or absence of discoloration of pellets The appearance of pellets of each composition was visually observed to determine whether or not the composition was colored dark red. (2) Presence or absence of gas generation during processing Whether or not gas (a gas derived from a flame retardant) was generated when each composition was extruded at 260 ° C. was confirmed with a phosphine gas detector tube (manufactured by Gastec Corporation). did. (3) Flame retardancy In accordance with the UL94 test method, evaluation was performed using a test piece having a thickness of 1/8 inch. (4) Heat resistance (degree of plasticization) For injection molded pieces 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), and heat resistance was evaluated based on the following criteria. ：: The degree of decrease is less than 20 ° C. compared to the value of HDT of the composition excluding the flame retardant. ×: The degree of decrease is 20 ° C. or more than the value of HDT of the composition excluding the flame retardant.

[0035]

[Table 1]

[0036]

The composition of the present invention does not generate gas or coloration derived from the flame retardant during molding and processing, and the resulting molded article has excellent flame retardancy and heat resistance.

[Procedure amendment]

[Submission date] June 13, 2000 (2006.1.
3)

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] Claims

[Correction method] Change

[Correction contents]

[Claims]

Embedded image (In the formula, n is an integer of 1 or more, M is an atom or an organic group forming a salt, and R is a divalent organic group.)

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08L 71/12 C08L 71/12 77/00 77/00 F term (Reference) 4J002 BC03W BC03X BC04W BC04X BC05X BC06X BC07X BC08X BN14X BN15X BP01X CF00W CF05W CF06W CF07W CF08W CG00W CH07W CL00W CL01W CL03W CL05W EW136 FD010 FD030 FD050 FD060 FD070 FD130 FD136

Claims (6)

[Claims] 1. A composition comprising (A) a thermoplastic resin and (B) a phosphinic acid salt, wherein the component (B) has the following formula (I) or (I):
A thermoplastic resin composition which is one or more selected from those represented by I). Embedded image (In the formula, n is an integer of 1 or more, M is an atom or an organic group forming a salt, and R is a divalent organic group.) 2. The thermoplastic resin composition according to claim 1, wherein (A) the thermoplastic resin is at least one selected from a polyester resin, a polyamide resin, a polystyrene resin, a polycarbonate resin, and a polyphenylene ether resin. object. 3. The thermoplastic resin composition according to claim 1, wherein (A) the thermoplastic resin comprises (A-1) a polyester resin and (A-2) a styrene resin. 4. The thermoplastic resin composition according to claim 1, wherein (A) the thermoplastic resin comprises (A-3) a polyamide resin and (A-2) a polystyrene resin. 5. The thermoplastic resin composition according to claim 2, wherein the polystyrene resin comprises polystyrene and / or rubber-modified polystyrene. 6. Component (B) is a compound represented by the formula (I) or (II):
Is at least one member selected from the group consisting of alkaline earth metals, transition metals, amide groups, ammonium groups, and melamines, and R is at least one member selected from alkylenes having ₁ to ₁₀ carbon atoms and phenylene. A thermoplastic resin composition which is