WO2005052055A1

WO2005052055A1 - Flame resistant resin composition

Info

Publication number: WO2005052055A1
Application number: PCT/JP2004/017450
Authority: WO
Inventors: Akira Taniguchi; Satoshi Sakai; Tamayo Okamoto
Original assignee: Toyo Boseki Kabushiki Kaisha
Priority date: 2003-11-27
Filing date: 2004-11-25
Publication date: 2005-06-09
Also published as: JP2005154635A

Abstract

[PROBLEMS] To provide a flame resistant resin composition for use as an adhesive or a structural plastic, especially a mechanical part, electrical/electronic component or automobile part that not only exhibits excellent flame resistance without the use of halogenated flame retarders posing environmental problems but also inhibits the emission of corrosive gases at the time of molding and inhibits the emission of irritant gases, corrosive gases and black smoke at the time of combustion and that despite the addition amount less than that of conventional flame retarders, excels in flame resistance and mechanical properties/thermal stability. [MEANS FOR SOLVING PROBLEMS] There is provided a flame resistant resin composition characterized by comprising a polyester copolymer containing phosphorus in its molecule (A) and, per 100 parts by mass thereof, 1 to 300 parts by mass of flame retarder (B) obtained by reaction between a phosphoric acid compound and a triazine compound and 0 to 2000 parts by mass of, not containing phosphorus in the molecule, polyester and/or polycarbonate (C).

Description

Specification

Flame retardant resin composition

Technical field

The present invention relates to a thermoplastic resin composition using a non-halogen flame retardant, which has good flame retardancy and excellent opportunity strength.

Background art

[0002] Thermoplastic resins such as polyesters, polycarbonates, polyamides, and polyphenylene oxides take advantage of their excellent properties to make use of mechanical and mechanical components, electrical components, automobile components, office components, building materials, textile products, miscellaneous goods, and the like. In these applications, materials with high flame retardancy such as “V-0 in UL standard” as well as mechanical properties are required in these applications. Many.

[0003] In order to make a thermoplastic resin flame-retardant, conventionally, a halogen-based flame retardant, which is a halogen-based organic compound, or an antimony-based flame retardant, which is an antimony conjugate, is combined with the resin as a flame retardant. The method of doing is general. However, this method has the disadvantages that it can corrode molds and the like during molding with hydrogen halide generated by thermal decomposition and generate a large amount of black smoke and harmful halogen-containing gas when a fire occurs. I have. In addition, some reports point out the danger of generating dioxin as a thermal decomposition product of halogenated compounds, and the trend is to control the use of halogen compounds. Therefore, in recent years, in order to eliminate the adverse effects of these halogen-based flame retardants on the environment, it is strongly desired to use halogen-free flame retardants, that is, free flame retardants (also referred to as non-halogen flame retardants in this specification). Like that o

[0004] Halogen-free flame-retardant prescriptions include, for example, hydrous inorganic compounds such as magnesium hydroxide and aluminum hydroxide-pharmaceutical. However, it has the disadvantage that the mechanical properties are significantly reduced. A method using a red phosphorus-based flame retardant separately from these water-containing inorganic compounds is disclosed in Japanese Patent Application Laid-Open No. 10-298395, etc., but red phosphorus has excellent flame retardancy, pellets and molded products. There are problems such as coloring, poor handling, and gas generated from the flame retardant during processing. Patent Document 1: JP-A-10-298395

Further, a method using a phosphate ester-based flame retardant, ammonium phosphate, or a triazine-containing compound is disclosed in JP-B-51-39271, JP-B-55-50506, JP-A-53-18660, It is known from JP-A-60-33850 and JP-A-57-96039. However, in order to impart flame retardancy that does not always provide sufficient flame retardancy, a large amount must be added to the resin, and the smoke emission, mechanical properties, electrical properties, and economy can be satisfied. Things were powerful. In some cases, the generation of cracked gas is assisted, which causes problems such as hindering molding, contaminating a mold, and bleeding out of a flame retardant.

Therefore, flame-retardant dangling techniques based on copolymerization of phosphorus-dried products have been proposed in JP-A-53-128195, JP-A-63-150352, and the like. However, these technologies are based on the principle of the development of flame retardancy, in which the flame retardancy is imparted mainly by dripping of the melt of the resin composition during combustion. In this case, sufficient flame retardancy cannot be provided. Further, the thermal stability, heat resistance, and mechanical properties of phosphorus copolymers are reduced, so that the copolymer of these phosphorous conjugates could not be directly applied to molded articles. Further, Japanese Patent Application Laid-Open No. 2001-2932 discloses a method of blending an ammonium polyphosphate with a copolymer of a phosphorus compound, but does not provide sufficient mechanical properties. The generation of gas is not sufficiently suppressed. As described above, in the prior art, a flame-retardant resin composition that has high flame retardancy under halogen-free conditions and sufficiently satisfies the inherent characteristics of a thermoplastic resin has been proposed.

Patent Document 2: Japanese Patent Publication No. 51-39271

Patent Document 3: Japanese Patent Publication No. 55-50506

Patent Document 4: JP-A-53-18660

Patent Document 5: JP-A-60-33850

Patent Document 6: JP-A-57-96039

Patent Document 7: JP-A-53-128195

Patent Document 8: JP-A-63-150352

Patent Document 9: Japanese Patent Application Laid-Open No. 2001-2932 Disclosure of the invention

Problems to be solved by the invention

[0006] The present invention provides excellent flame retardancy as a structural plastic / adhesive resin, particularly for machine parts, electric / electronic parts, and automobile parts without using environmentally hazardous halogen-based flame retardants. The generation of corrosive gas during molding processing that suppresses the occurrence of irritating gas, corrosive gas, and black smoke during combustion is suppressed, and the amount of addition is smaller than conventional flame retardants. It is an object of the present invention to provide a flame-retardant resin composition having excellent flame retardancy, mechanical properties and heat stability.

Means for solving the problem

[0007] The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, have reached the present invention.

That is, the present invention relates to (B) 100 parts by mass of a polyester copolymer containing phosphorus in a molecule, and (B) 1 to 300 parts by mass of a flame retardant obtained by a reaction of a phosphoric acid compound and a triazine compound. And (C) a flame-retardant resin composition comprising 0 to 2000 parts by mass of a thermoplastic resin.

In a particularly preferred embodiment, the flame retardant (B) obtained by reacting the phosphoric acid compound with the triazine compound is at least one kind selected from melamine phosphate, melamine pyrophosphate and melamine polyphosphate. And a flame-retardant resin composition. Further, the present invention is a molded article obtained by molding the flame-retardant resin composition.

The invention's effect

[0008] The resin composition according to the present invention provides a flame-retardant resin composition having excellent moldability, corrosive gas upon combustion, mechanical properties, and thermal stability without using a halogen-based flame retardant, It has an excellent effect on the environment and cost reduction during disposal and recycling.

BEST MODE FOR CARRYING OUT THE INVENTION

[0009] The (A) polyester copolymer containing phosphorus in the molecule used as a component of the flame-retardant resin composition of the present invention is not particularly limited as long as phosphorus is chemically bonded to the polyester. However, the structural unit represented by the following general formula (1) is replaced with a polymer side chain or Polyester copolymers contained in the polymer main chain are preferred

[0010] [Formula 2]

(R, R, and R represent a halogen-free monovalent or divalent organic residue.)

one two Three

As the polyester copolymer (Α) containing the structural unit represented by the general formula (1) in a polymer side chain or a polymer main chain, for example, a phosphorus compound described in JP-A-09-235480 is used. The way you like. In particular, a method in which a dicarboxylic acid having phosphorus in the molecule represented by the following general formula (2) is used as a copolymer component is preferred in terms of a high molecular weight and a polyester copolymer obtained.

[0012] [Formula 3]

Patent Document 10: JP-A-09-235480

[0013] Specific examples of R and R include a hydrogen atom, charcoal such as methyl, ethyl, propyl, and fuel. It is a hydride group. R and R may be the same or different. R,

4 5 6

R is a hydrogen atom, such as methyl, ethyl, propyl, butyl, phenol, benzyl, 2-hydroxypropyl, 2-hydroxypropyl, 3-hydroxypropyl, 4-hydroxybutyl, 2-hydroxylethyloxethyl, etc. At least one of the forces, such as a hydrocarbon group or a hydroxy-substituted hydrocarbon group, is chemically bonded to the copolymerized polyester chain.

[0014] The dibasic acid component other than the polymerization component containing phosphorus in the molecule used for the polymerization of the polyester copolymer containing phosphorus in the molecule includes terephthalic acid, isophthalic acid, orthophthalic acid, 1,5 Aromatic dibasic acids such as naphthalic acid, 2,6 naphthalic acid, 4,4'-diphenyldicarboxylic acid, 2,2, diphenyldicarboxylic acid, 4,4, diphenyletherdicarboxylic acid, adipic acid, azelaine Acid, sebacic acid, 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 4-methyl-1,2-cyclohexanedicarboxylic acid, dimer acid And the like used for normal polyester resins such as aliphatic and alicyclic dibasic acids.

[0015] Glycol components other than the polymerization component containing phosphorus in the molecule used for the polymerization of the polyester resin containing phosphorus in the molecule include ethylene glycol, propylene glycol, 1,3-propanediol, and 2-methyl-1 1,3 butanediol, 1,2 butanediol, 1,3 butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl-1,5 pentanediol, neopentyl Glycol, ethylene glycol, dipropylene glycol, 2,2,4-trimethinolane 1,3 pentadiolone, cyclohexanedimethanol, neopentyl hydroxypivalate, ethylene oxide adduct of bisphenol A and propylene oxide With adduct, hydrogenated bisphenol A with ethylene oxide Kafun and Kajun with propylene oxasd, 1,9-nonanediol, 2-methyloctanediol, 1,10-dodecanediol, 2-butyl-2-ethyl-1,3-propanediol, tricyclodecanedimethanol And the like. Examples of the polyether polyol include those used for ordinary polyester resins such as polyethers such as polyethylene glycol, polypropylene glycol, and polytetramethylene glycol.

An aliphatic dicarbo having 2 carbon atoms (also described as C2) and 12 carbon atoms (also described as C12) Polyesters that also produce the aliphatic glycolic acid of C2-C12, such as polyethylene adipate, polytetramethylene adipate, polyethylene sebacate, polyneopentyl sebacate, polytetramethylene dodecanoate, polytetramethyleneaselate, polyhexamethylene Azelate, poly-ε-proprotatonone and the like. Further, a polyester polyether copolymer obtained by combining the above-mentioned polyester and polyether can also be shown.

[0017] The polyester copolymer containing (Α) phosphorus in the molecule used in the present invention may be contained at 0.05 to 3% by mass as a phosphorus atom in the resin, but is preferably 0.05 to 3% by mass. It is at least 1% by mass, more preferably at least 0.3% by mass. If the content is less than 0.05% by mass, sufficient flame retardancy cannot be obtained. If it exceeds 3% by mass, problems such as hydrolysis of the resin itself and deterioration of mechanical properties occur. Resin (Α) Although it is possible to obtain a certain level of flame retardancy by itself, in order to impart a high level of flame retardancy, a large amount of the phosphorus-containing compound must be copolymerized. Problems such as hydrolysis of itself and deterioration of mechanical properties occur. Therefore, in the present invention, by combining a flame retardant obtained by a reaction between a phosphoric acid compound and a triazine compound as the constituent component (Β), an effect more than simply adding phosphorus by the addition rule is obtained, The flame retardancy was able to be expressed more efficiently.

[0018] Phosphoric acid compounds constituting the flame retardant include phosphoric acid, orthophosphoric acid, phosphorous acid, hypophosphorous acid, metaphosphoric acid, pyrophosphoric acid, triphosphoric acid, tetraphosphoric acid, polyphosphoric acid (so-called condensation) Phosphoric acid). In particular, phosphoric acid, pyrophosphoric acid, and polyphosphoric acid are desirable because of their high effect as flame retardants.

Examples of the triazine-based compound constituting the flame retardant include a triazine-based compound that can react with the above-mentioned phosphoric acid-based compound such as melamine, melem, and melam. In particular, melamine is desirable because of its high effect as a flame retardant.

As the flame retardant (剤) obtained by reacting the phosphoric acid compound and the triazine compound used in the present invention, specifically, melamine phosphate, melamine pyrophosphate, and melamine polyphosphate are preferably used. .

(Β) The flame retardant obtained by the reaction of the phosphoric acid compound and the triazine compound used in the present invention is produced by a known method. The unreacted phosphoric acid compound or triazine compound may not be completely reacted, but may remain.

[0019] The form of the flame retardant (B) obtained by the reaction of the phosphoric acid compound and the triazine compound used in the present invention is not particularly limited, but a fine powdery form may be used in the present invention. It is preferred from the viewpoint of improving the mechanical strength and surface properties of a molded product obtained from the fat composition. Preferably, the powder has an average particle size of 100 m or less, more preferably 30 m or less, and still more preferably 10 μm or less.

[0020] (B) The amount of the flame retardant obtained by the reaction of the phosphoric acid compound and the triazine compound is 1 to 300 parts by mass per 100 parts by mass of the thermoplastic resin (A) containing phosphorus in the molecule. Part is effective. Preferably it is 2 to 200 parts by mass, more preferably 3 to 100 parts by mass. If the amount is less than 1 part by mass, no effect of improving flame retardancy is observed, and if it exceeds 100 parts by mass, resin properties such as heat resistance, mechanical properties, and surface appearance are hardly exhibited. As a result, it was possible to achieve both mechanical properties, heat resistance, and the like, which are inherent properties of the resin, and high flame retardancy. It is more preferable to use melamine phosphate, melamine pyrophosphate, melamine polyphosphate, etc. as (B) in order to more effectively develop flame retardancy, because of the combined effect of different flame retardant mechanisms of phosphorus and nitrogen. The result is obtained.

[0021] Specific examples of the thermoplastic resin (C) of the present invention include polyester resin, polycarbonate resin, polyamide resin and the like. Specific examples of polyester resin include polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polycyclohexane dimethylene terephthalate, and polyethylene 1,2 bis (phenoxy) ethane-4,4 '. Copolymer polyesters such as dicanoleboxylate and the like, polyethylene isophthalate Z terephthalate, polybutylene terephthalate Z isophthalate, polybutylene terephthalate Z decane dicarboxylate and polycyclohexane dimethylene terephthalate Z isophthalate, etc. Can be In particular, polybutylene terephthalate, polybutylene naphthalate, polycyclohexane dimethylene terephthalate, polyethylene naphthalate, polyethylene terephthalate, and the like, which have well-balanced mechanical properties and moldability, can be preferably used. [0022] Specific examples of the polycarbonate include an aromatic polycarbonate, which is preferably an aromatic polycarbonate, and particularly an aromatic polycarbonate using bisphenol A as a main raw material.

Specific examples of polyamide resin include nylon 6, nylon 66, nylon MXD6, and the like.

[0023] The flame-retardant resin composition of the present invention may contain, if necessary, (C) a polyester, Z or polycarbonate which does not contain phosphorus in the molecule, within a range not to impair the object of the present invention. Can be. Component (C) is used in an amount of 0 to 2000 parts by mass, preferably 0 to 1000 parts by mass, and more preferably 0 to 1000 parts by mass, per 100 parts by mass of the polyester copolymer (A) containing phosphorus in the molecule. — 500 parts by weight. If the amount of the component (C) is too large, a resin composition having high flame retardancy cannot be obtained.

[0024] If necessary, the flame-retardant resin composition of the present invention may contain known antioxidants such as hindered phenol-based, sulfur-based, and phosphorus-based additives as long as the object of the present invention is not impaired. Agents, hindered amine-based, triazole-based, benzophenone-based, benzoate-based, nickel-based, salicyl-based light stabilizers, mold release agents, antistatic agents, lubricants, molecular regulators such as peroxides, metal deactivators And organic and inorganic nucleating agents, neutralizing agents, antacids, antibacterial agents, optical brighteners, fillers, flame retardants, flame retardant auxiliaries, and coloring agents including dyes and pigments. Additives can be added as needed.

[0025] Examples of the hindered phenol-based antioxidant which can be blended in the resin composition of the present invention include 3,5-di-tert-butyl-4-hydroxy-toluene and n-octadecyl-j8- (4 ' —Hydroxy— 3,5,5-di-tert-butylphenol) propionate, tetrakismethane, 1,3,5-trimethinole 2,4,6, -tris (3,5-di-tert-butyl-4-hydroxybenzyl) Benzene, canolecidium (3,5-di-tert-butyl-4-hydroxy-hydroxy-monoethyl-phosphate), triethylene glycol bis, 3,9 bis 2,4,8,10-tetraoxaspiroundecane, bis Glycol ester, tocopherol, 2,2, -ethylidenebis (4,6-dibutyltinolephenenole), N, N, 1-bishydrazine, 2,2, -oxamidobis, 1,1,3-tris (2 — Methyl-4-hydroxy-5t-butylphenyl) butane, 1,3,5-tris (3 ', 5'-di-butyl-4, -hydroxybenzyl) -S-triazine-2,4,6 (1H, 3H, 5H) —Trione, 1,3,5-tris (4t-butyl-3-hydroxy-1,2,6-dimethylbenzyl) isocyanurate , 3,5-di-tert-butyl-4-hydroxyhydrocinnamic acid triester di-1,3-, 5-tris (2-hydroxyethyl) -S-triazine-2,4,6 (1H, 3H, 5H) And so on.

[0026] Examples of the sulfur-based antioxidant that can be incorporated in the resin composition of the present invention include dilauryl 3,3,1-thiodipropionate and dimyristyl-3,3,3-thiodipropionate. Esters, distearyl 1,3,3,1-thiodipropionate, lauryl stearyl 1,3,3,1-thiodipropionate, dioctadecyl sulfide, pentaerythritol lutetra (j8-lauryl-thiopropionate) ) Esters and the like.

[0027] Examples of the phosphorus-based antioxidant that can be incorporated in the resin composition of the present invention include tris (mixed, mono- and dinolylphenyl) phosphite, and tris (2,3-di-t-butylphenyl). -Le) phosphite, 4,4, butylidene-bis (3-methyl-6-t-butylphen-ruzytridecyl) phosphite, 1,1,3-tris (2-methyl-4-ditridecylphosphite) -5 t-butylphenyl) butane, bis (2,4-zy t-butylphenyl) pentaerythritol di-phosphite, tetrakis (2,4-di-tert-butylbutyl) 4,4'-biphenylenephosphanite, bis (2 , 6-Di-tert-butyl-4-methylphenyl) pentaeristol diphosphite, 2,2, -ethylidenebis (4,6-di-tert-butylphenyl)-2-ethylhexylphos Aite, bis (2,4,6-di-butylbutyl) pentaerythritol-diphosphite, triphenylphosphite, diphenyldecylphosphite, didecylphenylphosphite, tridecylphosphite, trioctylphosphite, tridodecyl Examples include phosphite, trioctadecyl phosphite, trinolephenyl phosphite, and tridodecyl trithiophosphite.

[0028] Hindered amine light stabilizers that can be incorporated in the resin composition of the present invention include dimethyl succinate and 1- (2-hydroxyethyl) 4-hydroxy-2,2,6,6-tetramethylpi Polycondensate with perrosin, polyhexamethylene], bis (1,2,2,6,6-pentamethyl-4-piperidyl) ester of 2-n-butylmalonic acid, tetrakis (2,2,6,6-tetramethyl) — 4-piperidyl) -1,2,3,4-butanetetracarboxylate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, N, N, 1-bis (2,2 , 6,6-tetramethyl 4-pyridyl) hexamethylenediamine and 1,2-dibromoethane, polycondensate, polydecane, 1- 2, 2, 6, 6-tetromethylpiperidine, 8-benzylyl 7,7,9,9-tetramethyl-3-octyl-1,3,8-triazaspiroundecane 2,4-dione, 4-benzoyloxy 2, 2,6,6-tetramethylpiperidine, N, N-bis (3-aminopropyl) ethylenediamine-2,4-bis-6-chloro-1,3,5-triazine condensate.

Examples of the light stabilizer that can be added to the resin composition of the present invention include light stabilizers such as triazole, benzophenone, benzoate, nickel, and salicylic acid. Examples of light stabilizers such as triazole, benzophenone, benzoate, nickel, and salicylic acid are 2,2,2-dihydroxy-4-methoxybenzophenone, 2-hydroxy4n-otoxybenzophenone, and pt butylphenol salicylate. , 2,4-dibutyltinolefeninole 3,5-di-tert-butyl-4-hydroxybenzoate, 2- (2, -hydroxy-5,1-methylphenyl) benzotriazole, 2- (2'-hydroxy- 3 ', 5'-g-amyluphenyl) benzotriazole, 2- (2, -hydroxy-3,1-t-butyl-5,1-methylphenyl) -5-clozenbenzotriazole, 2- (2, -hydroxy-3,5,5, -Butyl t-butyl) -5 benzobenzotriazole, 2,5 bis-thiophene, nickel salt, 2-ethoxy-5 t-butyl 2, - E chill O hexa butyric acid bis - § - Lido 85- 90 mass ^_0/0 and 2 eth Kishi 5 t-butyl-2 'Echiru 4' t-butyl O hexa butyric acid Bisuanirido 10 one 15 mixture by weight ^_0/0, 2- (3,5-di-tert-butyl-2-hydroxyphenyl) benzotriazole, 2 ---- 2H-benzotriazole, 2-ethoxy-2'-ethyloxalic acid bisanilide, 2-benzotriazole, Bis (5-benzoyl 4-hydroxy-2-methoxyphenyl) methane, 2- (2'-hydroxy-5,1'-octylphenyl) benzotriazole, 2-hydroxy 4 i-one-year-old octoxybenzophenone, 2 —Hydroxy-4-dodecyloxybenzophenone, 2-hydroxy-4-octadecyloxybenzophenone and the like.

Glycerin fatty acid (C8—C22; hereinafter, referred to as fatty acid! /, Where n is the number of carbon atoms in the alkyl group is also abbreviated to Cn) as an antistatic agent that can be added to the resin composition of the present invention. Esters, sorbitan fatty acid (C8-C22) esters, propylene glycol fatty acid (C8-C22) esters, sucrose fatty acid (C8-C22) esters, mono (di- or tri) steryl citrate, pentaerythritol fatty acids (C8-C22) — C 18) ester, trimethylolpropane fatty acid (C8—C18) S, polyglycerin fatty acid (C8—C22) ester, poly Polyoxyethylene (20 mol) glycerin fatty acid (C12-C18) ester, oilyoxyethylene (20 mol) sorbitan fatty acid (C12-C18) ester, polyethylene glycol fatty acid (C8-C22) ester, polyoxyethylene fatty alcohol (C12-C18) C20) ether, polyoxyethylene (4--50 mol) alkyl (C4 or more) phenyl ether, N, N-bis (2-hydroxyethyl) fat (C8-C18) amine, fatty acid and diethanolamine Condensation products, non-ionic surfactants such as polyoxypropylene polyoxyethylene block polymers, polyethylene glycol and polypropylene glycol, alkyl (C10-C20) sulfonates (Na, K, ΝΗ), and alkyl naphthalene sulfonic acids Salt (Na), Soji

Four

Anionic surfactants such as dimethyldialkyl (C4-C16) sulfone succinate, alkyl (C8-C20) sulfate salts (Na, K, ΝΗ), and fatty acid (C8-C22) salts (Na, K, ΝΗ)

4 4

And auxiliaries, zwitterionic surfactants such as diasyl (C8-C18) sarcosinate, and other auxiliaries such as polyatalylic acid and its sodium salt.

[0031] Lubricants that can be incorporated into the resin composition of the present invention include hexylamide, otatylamide, stearylamide, oleylamide, erucylamide, ethylenebisstearylamide, laurylamide, behylamide, and methylenebisstearyl. C3-30 saturated or unsaturated aliphatic amides such as amide and ricinolamide and derivatives thereof; C3-30 saturated or unsaturated aliphatic esters and derivatives thereof such as butyl stearate and isobutyl stearate Commercially available silicone release agents Silicone conjugates such as silicone oil and silicone gum; commercially available fluorine-based release agents; and fluorine-based compounds such as tetrafluoroethylene.

[0032] The metal deactivator that can be incorporated into the resin composition of the present invention includes 3-N'-salicyloylamine 1,2,4 triazole, salicylaldehyde, salicylhydrazine, Ν, Ν 1,1-bis-hydrazine, oxalyl bis-1,9,10-dihydro-9-oxa 10-phosphaphenanthrene 10 oxide, 3,4,5,6-dibenzo-1,2 oxafosphan 2-oxo, tris-phenylphosphite , 2, 2'-brown oxamido-bis and the like.

[0033] The nucleating agents that can be blended in the resin composition of the present invention include 1,3,2,4-dibenzylidene-sorbitol, 1,3,2,4-dizye (ρ-methyl-benzylidene) ) Sorbitol, 1,3,2,4-di- (p-ethyl-benzylidene) sorbitol, 1,3,2,4-di- (2,4, -dimethyl-benzylidene) sorbitol, 1,3-p-chlorobe Benzylidene 2,4—p—methyl rubenylidene-sorbitol, 1,3,2,4-di- (p-propyl-benzylidene) sorbitol, aluminum mono-hydroxyzyg p—t butyl benzoate, Butylphenol) phosphate, sodium—2,2-methylene-bis- (4,6-di-tert-butylbutylphenol) phosphate, talc, sodium benzoate, lithium—2,2-methylenebis (4, 6-g-butylbutyl) phosphate and the like.

[0034] Examples of the neutralizing agent and antacid which can be incorporated in the resin composition of the present invention include lithium stearate, 1,2-hydroxylithium stearate, sodium stearoyl lactate, sodium stearate, and stearic acid. Potassium, lithium behenate, lithium montanate, sodium behenate, sodium montanate, calcium stearyl lactate, calcium behenate, calcium montanate, stearic acid donium, cadmium laurate, ricinoleic acid domium, barium naphthenate, Barium 2-ethylhexoate, barium stearate, barium 2-ethylhexoate, calcium stearate, calcium laurate, calcium ricinoleate, strontium stearate, stearic acid dumbbell, lauric acid dumbbell, ricin Higher fatty acids such as zinc stearate, zinc 2-ethylhexoate, zinc stearate, dibasic lead stearate, lead naphthenate, tin stearate, aluminum stearate, magnesium stearate, alkali or alkali of alkyl lactic acid Earth metal salts, basic magnesium · aluminum · hydrated hydroxy 'carbonate · hydrate (nodulated talcite), basic zeolite, epichlorohydrin and bisphenol A polymer, epoxidized soybean oil, Epoxy dung fat-esterified monoesters, epoxy danialicyclic alicyclic fatty acid esters, polycarboimides, isocyanate compounds and the like can be mentioned. Further, in order to further increase the flame retardancy, a known low molecular weight flame retardant can be added.

[0035] By adding a fibrous, Z or granular filler to the flame-retardant resin composition of the present invention, strength, rigidity, heat resistance, etc. can be greatly improved. In addition, the drip of the resin melt during combustion can be further suppressed.

Specific examples of such a filler include glass fiber, carbon fiber, metal fiber, aramide fiber, asbestos, potassium titanate whisker, wollastonite, glass flake, and glass beads. , Talc, my strength, clay, calcium carbonate, barium sulfate, titanium oxide, and aluminum oxide, magnesium oxide, silicon oxide, calcium oxide, chromium oxide (trivalent), iron oxide, zinc oxide , Silica, diatomaceous earth, alumina fiber, antimony oxide, norium ferrite, strontium ferrite, oxidized beryllium, pumice, oxides such as pumice balloons, magnesium hydroxide, hydrated aluminum, basic magnesium carbonate, etc. Basic substances or hydroxides of magnesium, magnesium carbonate, calcium carbonate, barium sulfate, ammonium sulfate, calcium sulfite, calcium sulphite, dolomite, dawsonite, etc., calcium sulfate, barium sulfate, ammonium sulfate, sulfurous acid (Sulfite) such as calcium and basic magnesium sulfate, sodium silicate, magnesium silicate , Aluminum silicate, potassium silicate, calcium silicate, montmorillonite, glass balloon, silicates such as bentonite, kaolin (porcelain), perlite, iron powder, copper powder, lead powder, aluminum powder, molybdenum sulfide, boron fiber, silicon carbide fiber , Brass fiber, lead zirconate titanate, zinc borate, aluminum borate, barium metaborate, calcium borate, sodium borate and the like. In particular, chopped strand type glass fibers are preferably used.

Example

Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited thereto. The materials used in the examples and the methods for measuring the evaluation items are as follows. Parts and% in the examples are based on mass unless otherwise specified.

(Reduced viscosity of polyester)

Dissolve in a mixed solvent of phenol / tetrachloroethane = 6/4 (mass ratio) according to JIS K7390, measure at 30 ° C using an Ubbelohde viscometer, and calculate the reduced viscosity (η / C).

sp

Value.

(Phosphorus Content in Thermoplastic Resin Containing Phosphorus in Molecule)

The phosphorous content in the thermoplastic resin was measured by X-ray fluorescence. Shows the measurement conditions of X-ray fluorescence.

Equipment name; Scanning X-ray fluorescence spectrometer ZSXIOOe X-ray tube manufactured by Rigaku Denki Kogyo Co., Ltd .; Rh (rhodium) X-ray output 50kV, 50mA

Spectroscopy ^ LiF

Wire type Κ α

With sample rotation

[0038] (Bending strength, flexural modulus)

It was measured according to ISO-178.

(Flame retardance)

The flame retardancy was evaluated based on Subject 94 (UL94) standardized by Underwriters' Laboratories (UL) in the United States, using a test piece with a length of 125 mm, a width of 12.5 mm and a thickness of 1.6 mm. evaluated. Flame retardance levels decrease in the order of V-0> V-1> V-2> fail.

In addition to the flammability level specified in UL94, the total combustion time of the flammability evaluation was measured 10 times in total with 5 test pieces in UL94 measurement and used as an index of flammability. . In addition, when the combustion did not stop and continued to burn, it was indicated as "total combustion".

Further, the dripping property of the molten resin during combustion was measured by the following index. The number of flames that drip after a total of 10 flames stipulated in UL94 was taken as a parameter of the drip property. This indicates that the closer to 0, the higher the flame retardancy in which dripping during combustion is suppressed.

[0039] (Bleed-out property)

A 3 mm-thick plate was aged at 60 ° C and 95% RH for 7 days, and the surface of the molded product was observed. Here, bleed-out is a phenomenon in which a part of the compound in the composition exudes to the surface of a molded article.

<Synthesis of Thermoplastic Resin Containing Phosphorus in Molecule (A): Phosphorus Copolymerized Polyester> Phosphorus is produced by a direct weight method using terephthalic acid, ethylene glycol, and a compound represented by the following (3) as raw materials. A copolyester contained in the molecule was obtained. The reduced viscosity of the obtained copolyester containing phosphorus in the molecule was 0.69, and the phosphorus content was 0.60% by mass.

(Examples 1-3, Comparative Examples 1-4) The pre-dried raw materials are weighed according to the mixing ratio shown in Table 1 and melt-kneaded in a twin-screw extruder (PCM30, manufactured by Ikegai Iron Works Co., Ltd.) at a cylinder temperature of 270 ° C and a screw rotation speed of 50 rpm. After being extruded into a water bath in a strand shape and cooled, pellets of the resin composition were obtained. (The amount of gas generated at this time was visually observed and evaluated.) The obtained resin composition was subjected to an injection molding machine (manufactured by Toshiba Machine Co., Ltd., IS80) at a cylinder temperature of 270 ° C and a mold temperature of 40 ° C. Test pieces for various tests were molded at ° C for evaluation. Table 1 shows the evaluation results.

[Table 1]

[Table 2]

Kamidani fe i ratio ratio fef 14 ratio tei train 5 acid component

(A) Ingredient 100 100 100

Clickolic component EG ^w )

Phosphorus content 0-6 mass%

(B) component f

Bollin i melamine one 43 one one one

Component (C) ^{PET * 5) 137 100 100 -} - Boririn Shun Anmoniumu * ^'6 "- A - 27 one

―

Aromatic phosphorus ester * ⁷ ) 33 1-Melamine cyanurate * ⁸⁾ 27 Glass fiber 1 Ω 5 Q9 54

2.0 1.2 1.1 0.9 0,9 Flexural strength [MPa] 199 170 119 96 148

14 16 9 10 12 Flammability Total combustion V-2 V-1 vo V-1 Burning time 38 68 10 100 Number of drip 10/10 5/10 0/10 0/10 0/10 With bleed-out * None None Yes Some Yes No Gas generated during melting and kneading No Almost No Yes Yes Yes * 1) TPA: Terephthalic acid (Mizshima Aroma Co., Ltd.)

* 2) Compound 4: Compound represented by the following formula (3) (manufactured by Sanko Corporation)

* 3) EG: Ethylene glycol (Nippon Shokubai Co., Ltd.)

* 4) Melamine polyphosphate (DSM, Melapur (R) 200/70)

* 5) PET: polyethylene terephthalate (Toyobo Co., Ltd., reduced viscosity = 0.68)

* 6) Ammonium polyphosphate (Terage (R) C60, manufactured by Chisso Corporation)

* 7) Aromatic phosphate ester (PX-200, manufactured by Daihachi Chemical Industry Co., Ltd.)

* 8) Melamine cyanurate (MC440, manufactured by Nissan Chemical Industries, Ltd.)

* 9) Release agent (Hoechstwax (R) OP, manufactured by Clariant Japan KK)

[0045]

As is clear from Examples 13 and 14 and Comparative Examples 14 to 14, the resin composition of the present invention exhibited excellent flame retardancy by combining the components (A) and (B). Have. In addition, an excellent molded article with little bleeding gas generated during the melt-kneading was obtained. As shown in Comparative Examples 13 to 13, when the flame retardant was only the component (A), only melamine polyphosphate, or only the aromatic phosphate, sufficient flame retardancy was not obtained. In addition, when component (A) is combined with ammonium polyphosphate as a flame retardant and component (A) is combined with melamine cyanurate, if sufficient flame retardancy is obtained, the amount of gas generated during melt-kneading increases. And bleeding on the surface of the compact.

Industrial applicability

[0047] The present invention has the same flame retardancy and mechanical properties as thermoplastic resins containing a halogen-based flame retardant conventionally used, and has no environmental effects because it does not contain halogen. As a body, it can be used in a wide range of application fields, such as mechanical parts, electrical and electronic parts, and automotive parts, especially as structural plastics and adhesive resin, greatly contributing to the industrial world. .

Claims

The scope of the claims

[1] (A) 100 parts by weight of a polyester copolymer containing phosphorus in a molecule, (B) one 300 parts by weight of a flame retardant obtained by the reaction of a phosphoric acid compound and a triazine compound, C) A flame-retardant resin composition characterized by containing 0 to 2000 parts by mass of a thermoplastic resin.

[2] (Β) The flame retardant obtained by the reaction between the phosphoric acid compound and the triazine compound has at least one kind of neutral or selected from melamine phosphate, melamine pyrophosphate and melamine polyphosphate. The flame-retardant resin composition according to claim 1, wherein

[3] (Α) The polyester copolymer containing phosphorus in a molecule is a polyester copolymer containing a structural unit represented by the following general formula (1) in a polymer side chain or a polymer main chain. 3. The flame-retardant resin composition according to claim 1, wherein:

[Chemical 1]

(R, R, and R represent a monovalent or divalent organic residue containing no halogen.)

one two Three

[4] A molded article obtained by molding the flame-retardant resin composition according to any one of claims 13 to 13.