JP2000239543A - Flame-retardant resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a flame-retardant resin composition flame-retarded without using any halogen-based flame retardant. SOLUTION: This composition is a flame-retardant resin composition comprising a thermoplastic resin and a flame retardant; the flame retardant is composed of a phosphorus-containing compound and a polyarylate-based resin or an aromatic epoxy resin. It may be that the flame-retardant resin composition comprises 0.1-100 pts.wt. of a flame retardant and 100 pts.wt. of a thermoplastic resin; and it may be that the flame retardant comprises 1-1,000 pts.wt. of a phosphorus-containing compound and a total 100 pts.wt. of a polyarylate-based resin and aromatic epoxy resin.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a thermoplastic resin,
The present invention relates to a flame-retardant resin composition containing a phosphorus-containing compound and a flame retardant composed of an aromatic polyol-based resin, a method for producing the same, and a molded article formed from the flame-retardant resin composition.

[0002]

2. Description of the Related Art Among thermoplastic resins, polyester resins such as polybutylene terephthalate and styrene resins have excellent mechanical properties, electrical properties, weather resistance, water resistance, chemical resistance and solvent resistance. Have. For this reason, it is used for various applications such as electric / electronic parts, mechanical mechanism parts, and automobile parts, and various improvements such as improvement of mechanical properties are being studied.

[0003] JP-A-55-73752 and JP-A-55-11544 disclose the moldability (warpage) of glass fiber-filled PBT by adding a polyarylate resin to polybutylene terephthalate (PBT). Are disclosed. Also, the Journal of
Applied Polymer Science, Vol. 29, 645
-659, 1979 (Journal of Applied Polymer
Science, vol.23, 645-659, (1979))
It is disclosed that high transparency can be obtained by adding an epoxy resin. However, as the field of use expands, flame retardancy is required for safety, but the flame retardancy of the above resin composition is insufficient.

[0004] As a method of imparting flame retardancy to a thermoplastic resin, a method of adding a flame retardant using a halogen compound or an antimony compound is generally known. For example, JP-A-63-150349 discloses that a mixed resin composed of a polyamide resin and nylon 66 is mixed with glass fiber, an organic halogen-based flame retardant, antimony trioxide, and an alkali metal or alkaline earth metal hydroxide. Disclosed is a flame-retarded resin composition. However, a halogen-based flame retardant may generate a large amount of a dioxin-based compound when decomposed by combustion, which is environmentally unfavorable. Therefore, a method of using a phosphorus-based compound, a nitrogen-containing compound, or the like as a non-halogen-based flame retardant to make it flame-retardant has been proposed.

Japanese Patent Application Laid-Open No. 64-14277 discloses a flame retardancy in which a thermoplastic resin (polypropylene) is added with a specific amount of a flame retardant comprising a silicone oil, a silicone resin, and a phosphorus-containing nitrogen compound (ammonium polyphosphate). A resin composition is disclosed. Japanese Patent Application Laid-Open No. 9-111059 discloses a flame-retardant resin composition in which a specific amount of a phenol resin, a phosphorus-containing compound (red phosphorus), and expandable graphite are mixed with a polyolefin resin. Also,
JP-A-10-195283 discloses a flame-retardant polyester resin composition obtained by combining a phosphoric acid ester having a specific structure with an appropriate amount of a specific compound (a novolak-type phenol resin and an oxide of iron, cobalt, nickel or copper). Is disclosed.

[0006] However, although non-halogen flame retardants do not contain harmful halogens, they are inferior in flame retardancy to halogen flame retardants, and therefore require a large amount of flame retardants. Addition of a large amount of a flame retardant causes bleed out and deterioration of the mechanical properties of the resin. Therefore, it is not possible to improve the mechanical properties together with the flame retardancy. For example, when expandable graphite is used in combination, the appearance during molding is significantly reduced. In particular, when a phosphoric acid ester is used as the phosphorus-containing compound, it causes bleed-out and a decrease in heat resistance.

As described above, it is difficult for the conventional method to impart flame retardancy without deteriorating the properties of the resin. Further, the above-mentioned flame retardant can make a specific resin flame-retardant, but cannot impart high flame retardancy to a wide range of thermoplastic resins.

[0008]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a flame-retardant resin composition which has been made flame-retardant without deteriorating the properties of the thermoplastic resin, and a method for producing the same.

Another object of the present invention is to provide a non-halogen-containing flame-retardant resin composition having a high level of flame retardancy even with a small amount of a flame retardant, and a method for producing the same.
Still another object of the present invention is to provide a molded article having improved flame retardancy.

[0010]

Means for Solving the Problems The present inventors have conducted intensive studies to achieve the above object, and as a result, by adding a specific non-halogen flame retardant to a thermoplastic resin, a high level of flame retardancy has been achieved. They found what they could do and completed the invention.

That is, a flame-retardant resin composition containing a thermoplastic resin and a flame retardant, wherein the flame retardant is at least one selected from a phosphorus-containing compound, a polyarylate resin and an aromatic epoxy resin. It is composed of resin. The flame retardant resin composition may contain 0.1 to 100 parts by weight of a flame retardant based on 100 parts by weight of the thermoplastic resin. The flame retardant may contain 1 to 1000 parts by weight of the phosphorus-containing compound based on 100 parts by weight of the total of the polyarylate resin and the aromatic epoxy resin.

The thermoplastic resins include olefin resins, acrylic resins, styrene resins, polyamide resins, polyester resins, polycarbonate resins, polyphenylene oxide resins, vinyl resins, and the like.
The polyester resin may be a polyalkylene arylate or a copolyester containing alkylene arylate as a main component. Further, the phosphorus-containing compound includes red phosphorus, (poly) phosphate, phosphate, and the like. The aromatic polyol component constituting the polyarylate resin may be a bisphenol. Epoxy resins include ether-based epoxy resins, ester-based epoxy resins, and amine-based epoxy resins. The flame-retardant resin composition may further contain, as a flame-retardant auxiliary, a resin having an aromatic ring having a hydroxyl group or an amino group in a main chain or a side chain, an aromatic polyamide, or the like. The flame-retardant resin composition may be used in combination with additives such as an organic nitrogen compound, a fluorine-based resin, a hindered phenol-based antioxidant, a phosphorus-based stabilizer, and a filler.

The present invention also includes a method for producing a flame-retardant resin composition by mixing a thermoplastic resin and a flame retardant, and a molded article formed from the flame-retardant resin composition.

[0014]

DESCRIPTION OF THE PREFERRED EMBODIMENTS [Thermoplastic resin] As the thermoplastic resin, various resins used for molding, for example,
Olefin resin, acrylic resin, styrene resin,
Examples thereof include a polyamide resin, a polyester resin, a polycarbonate resin, a polyphenylene oxide resin, and a vinyl resin.

(1) Olefin resin Examples of the olefin resin include ethylene, propylene, 1-butene, 3-methyl-1-pentene, 4-methyl-1-butene, 1-hexene and 1-octene. _Examples thereof include homo- or copolymers of α-olefins (particularly, α-C _2-10 olefins). As a preferred olefin-based resin, an ethylene unit is a main component (for example, 75 to 10).
0% by weight) as an ethylene-based resin (e.g., polyethylene, ethylene-propylene copolymer, ethylene- (meth) acrylic acid copolymer, etc.), and propylene unit as a main component (e.g., 75 to 100% by weight). Propylene-based resin (for example, polypropylene, propylene-ethylene copolymer, propylene- (meth) acrylic acid copolymer, etc.) and the like. The olefin-based resins can be used alone or in combination of two or more. Preferred olefin resins are crystalline olefin resins (particularly, propylene resins).

(2) Acrylic resin The acrylic resin includes, for example, (meth) acrylic acid,
(Meth) acrylic acid C such as methyl (meth) acrylate
_1-10 Alkyl ester, (meth) acrylamide, (meth) acrylonitrile and other (meth) acrylic monomer homo- or copolymer, or (meth) acrylic monomer and other copolymerizable monomer (For example, acrylonitrile-styrene copolymer, acrylonitrile-
Styrene- (meth) acrylate copolymer, etc.)
And so on. Preferred acrylic resins include poly (methyl) methacrylate, alkyl acrylate-methyl methacrylate copolymer, (meth) acrylic acid-styrene copolymer, methyl (meth) acrylate-styrene copolymer, and the like. Is mentioned. These acrylic resins can be used alone or in combination of two or more.

(3) Styrene resin As the styrene resin, for example, a homopolymer or a copolymer of a styrene monomer (eg, styrene, vinyltoluene, α-methylstyrene, chlorostyrene, etc.); And vinyl monomers (eg, α, β such as unsaturated nitriles such as acrylonitrile, (meth) acrylates, (meth) acrylic acid, maleic anhydride, etc.
-Monoolefinically unsaturated carboxylic acids or acid anhydrides or esters thereof); styrene-based graft copolymers, styrene-based block copolymers, and the like.

Preferred styrene resins are polystyrene (GPPS), styrene-methyl methacrylate copolymer, styrene- (meth) acrylic acid copolymer, styrene-maleic anhydride copolymer, styrene-acrylonitrile copolymer. (AS resin), impact-resistant polystyrene (HIPS) in which a styrene-based monomer is polymerized in a rubber component, a polystyrene-based graft or block copolymer, and the like. Examples of the polystyrene-based graft copolymer include copolymers obtained by graft-polymerizing at least a styrene-based monomer and a copolymerizable monomer onto a rubber component (for example, ABS resin obtained by graft-polymerizing styrene and acrylonitrile onto polybutadiene, acrylic rubber). AAS resin obtained by graft polymerization of styrene and acrylonitrile; ACS resin obtained by graft polymerization of styrene and acrylonitrile on chlorinated polyethylene; polymer obtained by graft polymerization of styrene and acrylonitrile on ethylene-vinyl acetate copolymer; styrene and acrylonitrile on ethylene-propylene rubber MBS resin obtained by graft polymerization of styrene and methyl methacrylate to polybutadiene,
Examples include resins obtained by graft-polymerizing styrene and acrylonitrile on a styrene-butadiene copolymer rubber.
As the block copolymer, a copolymer composed of a polystyrene block and a diene or olefin block (for example, styrene-butadiene-styrene (SBS))
Block copolymer, styrene-isoprene block copolymer, styrene-isoprene-styrene (SIS) block copolymer, hydrogenated styrene-butadiene-styrene (SEBS) block copolymer, hydrogenated styrene-
Isoprene-styrene (SEPS) block copolymer)
And the like.

(4) Polyamide Resin Polyamides include polyamides derived from diamines and dicarboxylic acids; polyamides obtained by using aminocarboxylic acids and, if necessary, diamines and / or dicarboxylic acids; lactams; Polyamides derived from co-use with diamines and / or dicarboxylic acids are included accordingly. Polyamides also include copolyamides formed by at least two different polyamide-forming components.

Examples of the diamine include trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, 2,2,4-trimethylhexamethylenediamine, 2,4,4-trimethylhexamethylenediamine, octamethylenediamine Aliphatic diamines such as phenylenediamine and metaxylylenediamine; and alicyclic diamines such as bis (4-aminocyclohexyl) methane and bis (4-amino-3-methylcyclohexyl) methane. One or more of these diamines can be used.

Examples of the dicarboxylic acid include C _4-20 aliphatic dicarboxylic acids such as glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid and octadecane diacid; dimerized fatty acids (dimer acid) ); Cyclohexane-1,4-dicarboxylic acid and cyclohexane-
Alicyclic dicarboxylic acids such as 1,3-dicarboxylic acid; aromatic dicarboxylic acids such as phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, and naphthalenecarboxylic acid;

Examples of the aminocarboxylic acid include C _4-20 aminocarboxylic acids such as aminoheptanoic acid, aminononanoic acid and aminoundecanoic acid. The lactam which can be used also amino acid one or two or more, for example, butyrolactam, Bibarorakutamu, caprolactam, capryl lactam, enantholactam, undecanolactam lactams include C _4-20 lactams such dodecalactam. These lactams can be used alone or in combination of two or more.

As the polyamide resin, nylon 4
6, nylon 6, nylon 66, nylon 610, nylon 612, nylon 11, nylon 12, and other aliphatic polyamides, aromatic dicarboxylic acids (eg, terephthalic acid and / or isophthalic acid) and aliphatic diamines (eg, hexamethylene diamine) ), Polyamides obtained from aliphatic dicarboxylic acids (eg, adipic acid) and aromatic diamines (eg, meta-xylylenediamine), aromatic and aliphatic dicarboxylic acids (eg, terephthalic acid and adipic acid) ) And an aliphatic diamine (for example, hexamethylene diamine). These polyamides can be used alone or in combination. Preferred polyamides include polyamides in which at least one of nylon 6, nylon 66, nylon 610, nylon 612, nylon 11, nylon 12, diamine component and dicarboxylic acid component is an aromatic compound.

(5) Polyester Resin Polyester resin is a homopolyester or copolyester obtained by polycondensation of a dicarboxylic acid component and a diol component, polycondensation of oxycarboxylic acid or lactone, or polycondensation of these components. It is.

As the dicarboxylic acid component, for example, aliphatic dicarboxylic acids (for example, having 6 to 40 carbon atoms such as adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, hexadecanedicarboxylic acid, and dimer acid) Dicarboxylic acid, preferably a dicarboxylic acid having about 1 to 14 carbon atoms), and alicyclic dicarboxylic acid (for example, having 8 to 12 carbon atoms such as hexahydrophthalic acid, hexahydroisophthalic acid, hexahydroterephthalic acid, and hymic acid). Dicarboxylic acids), aromatic dicarboxylic acids (e.g., phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acids such as 2,6-naphthalenedicarboxylic acid, 4,4'-diphenyldicarboxylic acid,
4,4′-diphenoxyether dicarboxylic acid, 4,
Dicarboxylic acids having about 8 to 16 carbon atoms such as 4'-diphenylmethanedicarboxylic acid and 4,4'-diphenylketonedicarboxylic acid, or derivatives thereof (for example, derivatives capable of forming esters such as lower alkyl esters and acid anhydrides) ). These dicarboxylic acid components may be used alone or in combination of two or more. further,
If necessary, a polycarboxylic acid such as trimet acid or pyromellitic acid may be used in combination.

Preferred dicarboxylic acid components include aromatic dicarboxylic acids such as terephthalic acid and naphthalenedicarboxylic acid.

Examples of the diol component include aliphatic alkylene diols (eg, ethylene glycol, trimethylene glycol, propylene glycol, 1,4-butanediol, 1,3-butanediol, neopentyl glycol, hexanediol, octanediol). , An aliphatic glycol having about 2 to 12 carbon atoms such as decanediol, preferably an aliphatic glycol having about 2 to 10 carbon atoms), a polyoxyalkylene glycol [the alkylene group has about 2 to 4 carbon atoms, Glycols having oxyalkylene units, such as diethylene glycol, dipropylene glycol, ditetramethylene glycol, triethylene glycol, tripropylene glycol, polytetramethylene glycol, etc.], alicyclic diols (eg, 1 4-cyclohexanediol,
1,4-cyclohexanedimethanol, hydrogenated bisphenol A, etc.), aromatic diols [for example, biphenol, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis- (4- (2-hydroxyethoxy) )
Phenyl) propane, xylylene glycol and the like]. These diol components may be used alone or in combination of two or more. Further, if necessary, a polyol such as glycerin, trimethylolpropane, trimethylolethane or pentaerythritol may be used in combination.

Preferred diol components include C _2-6 alkylene glycols (linear alkylene glycols such as ethylene glycol, propylene glycol and 1,4-butanediol), and oxyalkylene units having a repeating number of about 2 to 4. Polyoxyalkylene glycols [glycols containing poly (oxy-C _2-4 alkylene) units such as diethylene glycol], 1,4-cyclohexanedimethanol and the like are included.

Examples of the oxycarboxylic acid include oxycarboxylic acids such as oxybenzoic acid, hydroxynaphthoic acid, hydroxyphenylacetic acid, glycolic acid, and oxycaproic acid, and derivatives thereof.

Lactones include propiolactone, butyrolactone, valerolactone, caprolactone (for example,
_C3-12 alkyl lactones such as ε-caprolactone).

Preferred polyester resins include homopolyesters and copolyesters containing an alkylene acrylate such as alkylene terephthalate or alkylene naphthalate as a main component (for example, about 50 to 100% by weight, preferably about 75 to 100% by weight). , Polyalkylene terephthalate (for example, 1,4-cyclohexane dimethylene terephthalate (PCT), polyethylene terephthalate (PET), polypropylene terephthalate (PPT), polybutylene terephthalate (PBT)
Homopolyesters such as poly C _2-4 alkylene terephthalate) and polyalkylene naphthalate (eg, poly C _2-4 alkylene naphthalate such as polyethylene naphthalate and polybutylene naphthalate); alkylene terephthalate and / or alkylene naphthalate A copolyester containing a unit as a main component (for example, 50% by weight or more) is included. Particularly preferred polyester-based resins include polybutylene terephthalate-based resins containing a butylene terephthalate unit as a main component (for example, polybutylene terephthalate, polybutylene terephthalate copolyester). These polyester resins can be used alone or in combination of two or more.

In the copolyester, the copolymerizable monomers include C _2-6 alkylene glycols (eg, linear alkylene glycols such as ethylene glycol, propylene glycol and 1,4-butanediol), and repeating units. Having about 2 to 4 oxyalkylene units (eg, glycols containing poly (oxy-C _2-4 alkylene) units such as diethylene glycol), C _6-12 aliphatic dicarboxylic acids (adipic acid, pimelic acid) , Suberic acid, azelaic acid, sebacic acid, etc.) and aromatic dicarboxylic acids (phthalic acid, isophthalic acid, etc.).

The polyester resin may have not only a linear structure but also a branched chain structure, or may be crosslinked, as long as the melt moldability and the like are not impaired. Also,
It may be a liquid crystal polyester.

The polyester resin can be produced by a conventional method such as transesterification and direct esterification.

(6) Polycarbonate Resin The polycarbonate resin includes a dihydroxy compound,
Polymers obtained by reaction with phosgene or a carbonate such as diphenyl carbonate are included. The dihydroxy compound may be an alicyclic compound or the like, but is preferably a bisphenol compound.

As the bisphenol compound, bis (4
-Hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyphenyl) propane (bisphenol A), 2,
2-bis (4-hydroxy-3-methylphenyl) propane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) -3-methylbutane, 2,2-bis ( 4-hydroxyphenyl)
Hexane, 2,2-bis (4-hydroxyphenyl)-
Bis (hydroxyaryl) such as 4-methylpentane
C _1-6 alkane; bis (hydroxyaryl) C _4-10 cycloalkane such as 1,1-bis (4-hydroxyphenyl) cyclopentane, 1,1-bis (4-hydroxyphenyl) cyclohexane; 4,4 ′ -Dihydroxydiphenyl ether; 4,4'-dihydroxydiphenylsulfone;4,4'-dihydroxydiphenylsulfide;4,4'-dihydroxydiphenylketone, and the like.

Preferred polycarbonate resins include bisphenol A type polycarbonate.

(7) Polyphenylene oxide resin (polyphenylene ether resin) The polyphenylene oxide resin includes a homopolymer and a copolymer. As the homopolymer, poly (2,
6-dimethyl-1,4-phenylene) oxide (i.e., poly (2,6-dimethyl-1,4-phenylene ether)), poly (2-methyl-6-ethyl-1,4-phenylene) oxide, (2,6-di-n-propyl-1,4-phenylene) oxide, poly (2-ethyl-
6-isopropyl-1,4-phenylene) oxide, poly (2-methyl-6-hydroxyethyl-1,4-phenylene) oxide, poly (2-methyl-6-chloroethyl-1,4-phenylene) oxide, etc. No.

Examples of the polyphenylene oxide copolymer include an alkylphenol-modified benzeneformaldehyde resin block obtained by reacting a benzeneformaldehyde resin or an alkylbenzeneformaldehyde resin with an alkylphenol such as cresol or p-tert-butylphenol, and a polyphenylene as a main structure. Examples include a modified polyphenylene oxide copolymer composed of an oxide block and a modified graft copolymer in which a styrene-based polymer is grafted on polyphenylene oxide or a copolymer thereof.

(8) Vinyl Resin As the vinyl resin, vinyl monomers (for example, vinyl esters such as vinyl acetate, vinyl propionate, vinyl crotonate, and vinyl benzoate; vinyl monomers containing chlorine (for example, Vinyl chloride); fluorine-containing vinyl monomers (for example, fluoroethylene, chloroprene, etc.); vinyl ketones such as methyl vinyl ketone and methyl isopropenyl ketone; vinyl ethers such as vinyl methyl ether and vinyl isobutyl ether; N-vinyl carbazole , Vinylamines such as N-vinylpyrrolidone), or a copolymer with another copolymerizable monomer.

Derivatives of the above-mentioned vinyl resins (for example, polyvinyl acetal such as polyvinyl alcohol, polyvinyl formal and polyvinyl butyral, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, etc.) can also be used.

(9) Other Resins Other resins include polyacetal resins, aliphatic polyketone resins (ketone resins); polyphenylene sulfide resins (for example, polyphenylene sulfide, polyphenylene sulfide ketone, polybiphenylene sulfide, polyphenylene sulfide sulfone) Polysulfone (eg, thermoplastic polysulfone, poly (ether sulfone), poly (4,4′-bisphenol ether sulfone, etc.); polyether ketone; poly (ether ether ketone); thermoplastic polyurethane-based resin (eg, tri A polymer obtained by reacting a diisocyanate compound such as a diisocyanate with the glycol and / or the diamine, and a segment such as polytetramethylene glycol; Thermoplastic elastomer; polyoxybenzylene; thermoplastic elastomer, and the like.

These polymer compounds may be used alone or in combination of two or more.

Preferred thermoplastic resins include styrene resins, polyamide resins, polyester resins which may be liquid crystal polyesters, polycarbonate resins,
Polyphenylene oxide-based resins, polyphenylene sulfide-based resins, vinyl-based resins, and the like, more preferably, polyester-based resins, polycarbonate-based resins, polyamide resins, styrene-based resins, and polyphenylene oxide-based resins, particularly PBT-based resins, PBT
Polymer alloy containing a PBT-based resin (for example, 50-90% by weight, preferably 60-8%
0% by weight).

The number average molecular weight of the above thermoplastic resin is
It is not limited to a
For example, 5 × 10^Three~ 200 × 10^Four, Preferably 1
× 10 ^Four~ 150 × 10^Four, More preferably 1 × 10^Four
~ 100 × 10^FourYou can choose from a range of degrees. Also heat
When the plastic resin is a polyester resin, the number average molecular weight
Is, for example, 5 × 10^Three~ 100 × 10^Four, Preferably 1
× 10^Four~ 70 × 10^Four, More preferably 1.2 × 10
^Four~ 30 × 10^FourDegree.

[Flame Retardant] In the present invention, the flame retardant is composed of a phosphorus-containing compound and at least one resin selected from a polyarylate resin and an aromatic epoxy resin, so that a wide range of thermoplastic resins can be obtained. Thus, high flame retardancy can be imparted without deteriorating its properties.

(Phosphorus-Containing Compound) Examples of the phosphorus-containing compound include organic phosphorus compounds (monomer-type organic phosphorus compounds, polymer-type organic phosphorus compounds, etc.) and inorganic phosphorus compounds.

Among the above organic phosphorus compounds, the monomer type organic phosphorus compounds include phosphate esters, phosphite esters, phosphine oxides (such as triphenylphosphine oxide and tricresylphosphine oxide). Examples of the phosphate include aliphatic phosphates [tri C _1-10 alkyl esters such as trimethyl phosphate, triethyl phosphate, tripropyl phosphate, triisopropyl phosphate, tributyl phosphate, and triisobutyl phosphate; Di-C _1-10 alkyl esters such as dimethyl phosphate, diethyl phosphate, dipropyl phosphate, dibutyl phosphate, di (2-ethylhexyl) phosphate; mono-C _1-10 alkyl phosphates], aromatics Phosphate ester [triphenyl phosphate, tricresyl phosphate,
Trixylyl phosphate, diphenylcresyl phosphate, tri (isopropylphenyl) phosphate, diphenylethyl cresyl phosphate, and other tri-C _6-20 aryl phosphates], aliphatic-aromatic phosphates (methyl phosphate) Diphenyl, phenyldiethyl phosphate, etc.).

Examples of the phosphite include aromatic phosphites (tri-C _6- phosphite such as triphenyl phosphite, tricresyl phosphite, trixylyl phosphite, and diphenylcresyl phosphite). ₂₀ Phosphorous acid such as aryl phosphites (trimethyl phosphite, triethyl phosphite, tripropyl phosphite, triisopropyl phosphite, tributyl phosphite, triisobutyl phosphite, etc.) Tri C _1-10 alkyl ester; di C _1-10 phosphite such as dimethyl phosphite, diethyl phosphite, dipropyl phosphite, dibutyl phosphite
Alkyl esters; phosphite mono-C _1-10 alkyl esters, etc.), aliphatic-aromatic phosphites (for example,
Diphenyl methanephosphonate, aryl esters of alkyl phosphonic acids such as diethyl methanephosphonate, etc.).

The monomer type organic phosphorus compound also includes a hypophosphite, a phosphonocarboxylate, a nitrogen-containing phosphate and the like which may be substituted by an alkyl group or an aryl group.

As the polymer type organic phosphorus compound,
A condensate of the monomer type organic phosphorus compound can be used. The condensate may have a repeating unit represented by the following formula (1).

[0052]

Embedded image

(Wherein, R ^{1 to} R ⁴ represent an aryl group which may have a substituent, Z represents an arylene group.
In the formula (1), examples of the aryl group represented by R ^{1 to} R ⁴ include a C _6-20 aryl group such as phenyl and naphthyl, and a substituent of the aryl group is methyl. And an alkyl group such as an ethyl group. Also, C _6-20 of Examples of the arylene group, phenylene, naphthylene group
And an arylene group.

The condensate represented by the above formula (1) includes
For example, resorcinol bis (diphenyl phosphate), resorcinol bis (dicresyl phosphate), resorcinol bis (dicylyl phosphate), hydroquinone bis (diphenyl phosphate), hydroquinone bis (dicresyl phosphate), hydroquinone bis (dicylyl phosphate), bisphenol- A bis (diphenyl phosphate), bisphenol-A bis (dicresyl phosphate), bisphenol-A bis (dicylyl phosphate) and the like can be mentioned.

Further, the polymer type organic phosphorus compound is
It may be a phosphoric acid ester of a polymer having a hydroxyl group (such as a phenol resin). As the phosphoric acid ester of such a polymer, for example, the following formula (2)
And a polymer having a structural unit represented by

[0056]

Embedded image

(In the formula, R ⁵ and R ⁶ represent an aryl group which may have a substituent.) The aryl group is a C _6-20 aryl group, particularly a phenyl group, a methylphenyl group, a dimethylphenyl group. And the like. Examples of the substituent of the aryl group include an alkyl group such as a methyl group and an ethyl group.

Further, the polymer type organic phosphorus compound also includes polyphosphinicocarboxylic acid esters and polyphosphonamides. Examples of the polyphosphonamide include a polymer having a structural unit represented by the following formula (7).

[0059]

Embedded image

(Wherein, R ¹⁹ represents an alkyl group, a cycloalkyl group, an aryl group, or an aralkyl group, and R ²⁰ represents an alkylene group, an arylene group, or an aralkylene group.
²¹ and R ²² are the same or different and each represent a hydrogen atom, an alkyl group, or an aryl group. R ²¹ and R ²² may be directly connected to form a ring.) The inorganic phosphorus compound includes, for example, red phosphorus, phosphate, and the like. In addition to orthophosphoric acid,
Also included are phosphorous acid, polyphosphoric acid (such as metaphosphoric acid and pyrophosphoric acid), and polyphosphorous acid (such as metaphosphoric acid and pyrophosphorous acid). Examples of the salt include an alkali metal salt (such as a lithium salt, a sodium salt, and a potassium salt), an alkaline earth metal salt (such as a magnesium salt and a calcium salt), a salt of a Group 3B metal of the periodic table (such as an aluminum salt), and an ammonium salt. Can be illustrated. The salt also includes an amine salt, for example, a guanidine salt or a salt of a triazine compound (eg, a melamine salt, a melem salt, etc.).

The inorganic phosphorus compound may be a phosphorous acid, a hypophosphorous acid, a phosphonocarboxylic acid, a phosphinic carboxylic acid (for example, 3-methylphosphinic acid) which may be substituted with an alkyl group or an aryl group. Metal salts of acids such as propionic acid, 3-phenylphosphinicopropionic acid), and nitrogen-containing phosphoric acid.

Preferred phosphates are the salts of polyphosphoric acids, especially ammonium polyphosphate and melamine polyphosphate.

Preferable phosphorus-containing compounds include phosphoric acid esters (such as aliphatic phosphoric acid esters and aromatic phosphoric acid esters), inorganic phosphorus compounds (such as polyphosphates such as ammonium polyphosphate, and red phosphorus). And aromatic phosphate esters.

Red phosphorus has a high flame-retardant effect, and the effect can be obtained with a small amount, so that it can be made flame-retardant without impairing the properties of the resin (for example, mechanical properties and electrical properties). As the red phosphorus, those which have been subjected to a stabilization treatment (stabilized red phosphorus) are usually preferably used. In particular, red phosphorus that is not pulverized and has not been pulverized without forming a pulverized surface having high reactivity with water and oxygen on the surface of the red phosphorus, and the surface of the red phosphorus is a resin (for example, a thermosetting resin). Red phosphorus coated with a single resin or a combination of two or more types with a functional resin, a thermoplastic resin), a metal, a metal compound (for example, a metal hydroxide, a metal oxide, or the like) is preferable.

As the thermosetting resin, a phenol resin,
Melamine-based resins, urea-based resins, alkyd resins, unsaturated polyester resins, epoxy resins, silicone-based resins, and the like.Examples of thermoplastic resins include polyester-based resins, polyamide-based resins, acrylic resins, and olefin-based resins. No. Examples of the metal hydroxide include aluminum hydroxide, magnesium hydroxide, calcium hydroxide, zinc hydroxide, titanium hydroxide, and the like.Examples of the metal oxide include aluminum oxide, magnesium oxide,
Examples include zinc oxide, titanium oxide, zirconium oxide, copper oxide, iron oxide, molybdenum oxide, tungsten oxide, manganese oxide, and tin oxide.

Further, as a method for coating and stabilizing the surface of red phosphorus with a metal, a metal (iron, nickel, copper, aluminum, zinc, manganese,
(Tin, titanium, zirconium, etc.) or an alloy thereof. Another method for coating the surface of red phosphorus is to treat the red phosphorus with a solution of a metal salt (a salt of aluminum, magnesium, zinc, titanium, copper, silver, iron, nickel, etc.) and apply a metal phosphorus compound to the surface of the red phosphorus. Methods of forming and stabilizing are also included.

In particular, a method in which red phosphorus is finely divided without forming a crushed surface on the surface of red phosphorus is used, and a film of a metal component (metal hydroxide or metal oxide) and a film of a resin are combined to form a plurality of layers. Red phosphorus which is coated with a coating of a metal component and which is multiply coated with a resin coating after coating with a coating of a metal component is preferred.
These stabilized red phosphorus are excellent in heat stability and hydrolysis resistance, and the generation of phosphine by the decomposition reaction in the presence of moisture or at high temperature is extremely low. And from the viewpoint of safety when producing molded articles.

The preparation of these stabilized red phosphorus is described in
JP-A-229806, JP-A-3-295956, JP-A-2-2099991, JP-A-1-150
No. 309, Japanese Patent Application Laid-Open No. 62-21704, Japanese Patent Application Laid-Open No. 52-125489, EP 296501 A1 and EP 249723 A2 can be referred to.

As the red phosphorus, stabilized red phosphorus can usually be used in the form of powder. The average particle size of the stabilized red phosphorus is, for example, 0.01 to 100 μm, preferably 0.1 to 100 μm.
To 50 μm, and more preferably about 0.1 to 30 μm. Further, the average particle size is 0.01 to 5 μm, preferably 0.05 to 4.8 μm, and more preferably 0.1 to 5 μm.
You may use the fine red (for example, fine spherical etc.) stabilized red phosphorus which is about 4.8 micrometers.

Further, the stabilized red phosphorus may be treated with a surface modifier such as an epoxy compound, a silane compound, a titanate compound, and a chromium compound.

The stabilized red phosphorus may be used alone or in combination of two or more. For example, red phosphorus having a different coating treatment, red phosphorus having a different particle size, or the like can be used in any combination.

(Polyarylate resin) The polyarylate resin has the following formula (8) [-O-Ar-OC (O) -AC (O)-] (8) (where Ar is aromatic A represents an aromatic group, an alicyclic group,
Or an aliphatic group. A compound having a structural unit represented by ()) can be used.

Such a polyarylate resin is prepared by a melt polymerization method, a solution polymerization method, a transesterification method (eg, an acetate method, a phenyl ester method, etc.), an acid chloride method, a direct method, or a polyaddition method. It can be produced using a polymerization method or an interfacial polymerization method.

The polyarylate resin comprises an aromatic polyol component and a polycarboxylic acid component (such as an aromatic polycarboxylic acid component, an aliphatic polycarboxylic acid component, and an alicyclic polycarboxylic acid component).

As the aromatic polyol (monomer),
Usually, diols such as monocyclic aromatic diols and polycyclic aromatic diols, or reactive derivatives thereof [for example, salts of aromatic polyols (sodium salt, potassium salt, etc.), esters of aromatic polyols (acetate esters) And the like, and silyl-protected aromatic polyols (such as trimethylsilylated forms).

As the monocyclic aromatic diol, for example,
Benzenediol (resorcinol, hydroquinone,
m-xylylene glycol, p-xylylene glycol, etc.), and an aromatic ring diol having about 6 to 20 carbon atoms such as naphthalene diol.

Examples of the polycyclic aromatic diol include bis (hydroxyaryl) s (bisphenols), for example,
4,4′-dihydroxybiphenyl, 2,2′-biphenol, bis (hydroxyaryl) alkane [for example, bis (hydroxyphenyl) methane (bisphenol F), bis (hydroxyphenyl) ethane (for example,
Bis (hydroxyaryl) C _1-6 alkane such as bis (hydroxyphenyl) propane (eg, bisphenol A)], bis (hydroxyaryl) cycloalkane [eg, bis (hydroxyphenyl) cyclohexane, etc. Bis (hydroxyaryl) C _3-12 cycloalkane, etc.],
And bis (hydroxyaryl) carboxylic acids [for example, bis (hydroxyaryl) C _2-6 carboxylic acids such as bis-4,4- (hydroxyphenyl) butanoic acid]. Other polycyclic aromatic diols include compounds having a bis (hydroxyaryl) skeleton,
For example, di (hydroxyphenyl) ether, di (hydroxyphenyl) thioether, di (hydroxyphenyl) ketone, di (hydroxyphenyl) sulfoxide,
Bis (C _1-4 alkyl-substituted hydroxyphenyl) alkane [eg, bis (3-methyl-4-hydroxyphenyl) methane, bis (3-methyl-4-hydroxyphenyl) propane, bis (3,5-dimethyl-4) -Hydroxyphenyl) methane, bis (3,5-dimethyl-4-hydroxyphenyl) propane, etc.], terpene diphenols (for example, 1,4-di (C _1-4 alkyl-substituted hydroxyphenyl) -p-menthane, etc.) ) Is also included.

These aromatic polyols can be used alone or in combination of two or more. Preferred aromatic polyols include bisphenols, such as bis (hydroxyaryl) C _1-6 alkanes (eg, bisphenol A, bisphenol F, bisphenol AD, etc.).

The aromatic polyol may be used in combination with an aliphatic or alicyclic polyol. Examples of the aliphatic polyol include C _1-10 aliphatic polyols such as ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, and neopentyl glycol. Further, the aliphatic polyol includes C _3-10 such as 1,4-cyclohexanedimethanol.
An aliphatic polyol having an aliphatic ring is also included. Examples of alicyclic polyols include C, such as cyclohexanediol.
_3-10 alicyclic polyols.

Examples of the aromatic polycarboxylic acid (monomer) include dicarboxylic acids such as monocyclic aromatic dicarboxylic acid and polycyclic aromatic dicarboxylic acid, and reactive derivatives thereof [eg, aromatic polycarboxylic acid Halide (eg, aromatic polycarboxylic acid chloride), aromatic polycarboxylic acid ester (eg, alkyl ester, aryl ester), aromatic polycarboxylic anhydride, etc.].

Examples of the monocyclic aromatic dicarboxylic acid include those having about 8 to 20 carbon atoms, such as benzenedicarboxylic acid such as phthalic acid, isophthalic acid and terephthalic acid, and naphthalenedicarboxylic acid such as 2,6-naphthalenedicarboxylic acid. Aryldicarboxylic acid. The benzenedicarboxylic acid and naphthalenedicarboxylic acid (particularly,
Benzenedicarboxylic acid) may be substituted by one or two C _1-4 alkyl groups.

Examples of the polycyclic aromatic dicarboxylic acid include bis (arylcarboxylic acids) such as bisphenyldicarboxylic acid, bis (carboxyphenyl) methane, bis (carboxyphenyl) ethane, and bis (carboxyphenyl) propane. (Carboxyaryl) C _1-6
Alkanes; bis (carboxyaryl) C _3-12 cycloalkanes such as bis (carboxyphenyl) cyclohexane; bis (carboxyaryl) ketones such as bis (carboxyphenyl) ketone; bis (carboxyaryl) such as bis (carboxyphenyl) sulfoxide Sulfoxide; bis (carboxyaryl) ether such as bis (carboxyphenyl) ether; and bis (carboxyaryl) thioether such as bis (carboxyphenyl) thioether.

Preferred aromatic polycarboxylic acid components include:
Monocyclic aromatic dicarboxylic acids (particularly, benzenedicarboxylic acids such as phthalic acid, isophthalic acid and terephthalic acid), bis (carboxyaryl) C _1-6 alkanes and the like are included.

The aliphatic polycarboxylic acids (monomers) include aliphatic dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid,
Examples thereof include C _2-20 aliphatic dicarboxylic acids such as suberic acid, azelaic acid, sebacic acid, and dodecane diacid, and dicarboxylic acids having a C _3-10 aliphatic ring such as dicarboxymethylcyclohexane.

The alicyclic polycarboxylic acid (monomer) includes an alicyclic dicarboxylic acid, for example, a C _3-20 alicyclic dicarboxylic acid such as cyclohexanedicarboxylic acid.

Preferred polyarylate resins include polyarylate resins in which the aromatic polyol is a bisphenol, such as bisphenols (bisphenol A,
Polyesters of bisphenol AD, bisphenol F, etc.) and benzenedicarboxylic acid (isophthalic acid, terephthalic acid, etc.), bisphenols and bis (arylcarboxylic acid) s [for example, bis (carboxyphenyl) methane, bis (carboxyphenyl) ethane, And a bis (carboxyaryl) C _1-4 alkyl such as bis (carboxyphenyl) propane. These polyarylate resins can be used alone or in combination of two or more.

In addition to the aromatic diol and aromatic dicarboxylic acid, if necessary, the polyarylate resin may be aromatic triol or aromatic tetraol [for example,
1,1,2,2-tetrakis (hydroxyphenyl) ethane], an aromatic tricarboxylic acid, an aromatic tetracarboxylic acid, and the like.

Further, the terminal of the polyarylate resin may be blocked (bonded) with alcohols, carboxylic acids, etc. (particularly, monohydric alcohols, monovalent carboxylic acids, etc.). Examples of the monohydric alcohol that blocks the terminal of the polyarylate resin include, for example, monovalent aryl alcohols (monohydric alcohols which may be substituted with a C _1-10 alkyl group and / or a C _6-10 aryl group). Phenols such as phenol, o, m, p-cresol, dimethylphenol, o, m, p-ethylphenol, o, m, p
-N-propylphenol, o, m, p-isopropylphenol, o, m, pn-butylphenol, o,
m, p-sec-butylphenol, o, m, p-te
rt-butylphenol, o, m, p-phenylphenol, o, m, p-benzylphenol, cumylphenol, etc., monovalent alkyl alcohols (methanol, ethanol, n-propanol, isopropanol, butanol, pentanol, hexanol, C _1-20 alkyl mono-alcohols such as dodecyl alcohol, stearyl alcohol), aralkyl alcohols monohydric (benzyl alcohol, C _7-20 aralkyl monoalcohols such phenethyl alcohol), and the like.

Examples of the monovalent carboxylic acids that block (bond) the terminal of the polyarylate resin include monovalent aliphatic carboxylic acids (C, such as acetic acid, propionic acid and octanoic acid).
_1-20 aliphatic monocarboxylic acids), monovalent alicyclic carboxylic acids (C _4-20 alicyclic monocarboxylic acids such as cyclohexanecarboxylic acid), monovalent aromatic carboxylic acids (benzoic acid, toluic acid, o, m, p-tert-butylbenzoic acid, p-
C _7-20 aromatic monocarboxylic acids such as methoxyphenylacetic acid) and the like. The carboxylic acid is a monovalent aliphatic carboxylic acid substituted with an aromatic group such as phenylacetic acid (particularly, a C _1-10 aliphatic monocarboxylic acid substituted with a C _6-20 aromatic group). Is also good.

The polyarylate resin may be a polymer alloy with a resin other than the polyarylate resin, for example, polyethylene terephthalate, polycarbonate resin, polyamide and the like. The polymer alloy includes not only a simple mixture but also a polymer alloy obtained by a transesterification reaction or a polymer alloy containing a compatibilizer.

As the polyarylate resin constituting the flame retardant, a resin different from the polyester resin of the thermoplastic resin is used.

The number average molecular weight of the polyarylate resin thus obtained is, for example, 300 to 30 × 10 ⁴
Degree, preferably about 500 to 10 × 10 ⁴ , more preferably about 500 to 5 × 10 ⁴ .

(Aromatic Epoxy Resin) The aromatic epoxy resin includes an ether-based epoxy resin (for example, a bisphenol-type epoxy resin and a novolak-type epoxy resin), an amine-based epoxy resin using an aromatic amine component, and the like. .

The bisphenol constituting the bisphenol type epoxy resin is the same as the above bis (hydroxyaryl) s. Preferred bisphenol-type epoxy resins include glycidyl ethers such as bis (hydroxyaryl) C _1-6 alkanes, particularly bisphenol A, bisphenol AD and bisphenol F.
The bisphenol-type epoxy resin also includes the bisphenol glycidyl ether having a large molecular weight (that is, a phenoxy resin).

Novo constituting epoxy resin of novolak type
As a rack resin, an alkyl group (for example,
C_1-20Alkyl group, preferably methyl group, ethyl group, etc.
C _1-4Novolak which may be substituted by an alkyl group)
Resin (eg, phenol novolak resin, cresol
A novolak resin).

Preferred novolak epoxy resins include:
A glycidyl ether of a novolak resin optionally substituted with a C _1-2 alkyl group is included.

The aromatic amine component constituting the amine-based epoxy resin includes a monocyclic aromatic amine (aniline, toluidine, etc.), a monocyclic aromatic diamine (diaminobenzene, xylylenediamine, etc.), a monocyclic aromatic amine. Aliphatic amino alcohols (such as aminohydroxybenzene), polycyclic aromatic diamines (such as diaminodiphenylmethane), and polycyclic aromatic amines.

The number average molecular weight of the epoxy resin is, for example,
About 200 to 50,000, preferably 300 to 10,
It is about 000, more preferably about 400 to 6,000 (for example, about 400 to 5,000). The number average molecular weight of the phenoxy resin is, for example, 500 to 5
About 000, preferably 1,000 to 40,000
Degree, more preferably about 3,000 to 35,000.

Epoxy resins include amine curing agents (for example, aliphatic amines such as ethylenediamine, aromatic amines such as metaphenylenediamine and xylylenediamine), polyaminoamide curing agents, and acid and acid anhydride curing agents. It may be used after being cured by a curing agent such as. (Ratio of phosphorus-containing compound to polyarylate-based resin and epoxy resin) The amount of the phosphorus-containing compound used in the flame retardant is selected within a range that can provide flame retardancy, and the total amount of the polyarylate-based resin and epoxy resin The amount is about 1 to 1000 parts by weight, generally about 1 to 100 parts by weight, preferably about 5 to 80 parts by weight, more preferably about 10 to 60 parts by weight, per 100 parts by weight.

[Proportion of Use of Flame Retardant] The proportion of the flame retardant contained in the thermoplastic resin is not particularly limited as long as the properties of the resin are not impaired. About 0.1 to 100 parts by weight, preferably 1
It is about 80 parts by weight, more preferably about 5 to 60 parts by weight. If the amount of the flame retardant is less than 0.1 part by weight, it is difficult to make the flame retardant. If the amount exceeds 100 parts by weight, the mechanical strength of the resin is reduced.

[Additives] The flame-retardant resin composition of the present invention may contain, if necessary, various additives (for example, a flame-retardant auxiliary, another flame-retardant, an anti-dripping agent, an antioxidant). Etc.). The total content of the additives is, for example, 0.01 to 100 parts by weight of the thermoplastic resin.
About 50 parts by weight, preferably about 0.1 to 30 parts by weight,
More preferably, it is about 1 to 20 parts by weight.

[Flame retardant aid] Examples of the flame retardant aid include resins having an aromatic ring having a hydroxyl group or an amino group in the main chain or side chain, and aromatic nylon.

Examples of the resin having an aromatic ring in the main chain include a novolak resin and an aralkyl resin, and examples of the resin having an aromatic ring in a side chain include an aromatic vinyl resin.

(Novolak resin) The novolak resin has a repeating unit represented by the following formula.

[0105]

Embedded image

(Wherein R ⁷ represents a hydrogen atom, an alkyl group or an aryl group, and R ⁸ and R ⁹ are the same or different,
Represents a hydrogen atom, an alkyl group or an aryl group, and n represents an integer of 1 or more.) Examples of the alkyl group include C, such as methyl, ethyl, butyl, t-butyl, hexyl, octyl, nonyl, and dodecyl.
_Examples thereof include a _1-20 alkyl group, preferably a C _1-12 alkyl group.

Examples of the aryl group include C _6-20 such as phenyl, naphthyl, methylphenyl and ethylphenyl.
Aryl groups.

The novolak resin (particularly, random novolak resin) is generally obtained by reacting a phenol with an aldehyde. Phenols, such as phenol, p- or m- cresol, 3,5-xylenol, alkylphenols (e.g., t-butylphenol, p- octylphenol, C _1-20 alkylphenol such as nonylphenol), an aryl phenol (e.g., phenyl Phenol, benzyl phenol, cumyl phenol) and the like. These phenols may be used alone or in combination of two or more.

Examples of the aldehydes include aliphatic aldehydes such as formaldehyde, acetaldehyde and propionaldehyde, and aromatic aldehydes such as phenylacetaldehyde. Preferred aldehydes include formaldehyde.
Also, a condensate of formaldehyde such as paraformaldehyde can be used.

The condensation reaction of a phenol or oxybenzoic acid with an aldehyde is usually carried out in the presence of an acid catalyst. Examples of the acid catalyst include an inorganic catalyst (for example, hydrochloric acid, sulfuric acid, phosphoric acid, etc.) and an organic catalyst (p-toluenesulfonic acid, oxalic acid, etc.). The ratio of phenols and aldehydes is the former / latter = 1 / 0.5
About 1/1 (molar ratio).

In addition to the above-mentioned novolak resin (particularly, random novolak resin), in the present invention, a high ortho-novolak resin having an ortho / para ratio of 1 or more can be used as the novolak resin. The method of methylene bonding of the novolak resin is as follows: (1)
In some cases, the ortho-position is bonded to each other, (2) when the ortho-position is bonded to the para-position, and (3) when the para-position is bonded to each other.

The ortho / para ratio is defined as (the number of methylene bonds bonded in para positions: M _p ) and １ ／ of (the number of methylene bonds bonded in ortho and para positions: M _OP ). Means the ratio of the sum of (the number of methylene bonds bonded at the ortho positions: M _O ) and の of the number of methylene bonds bonded at the ortho position and the para position: M _OP . It is expressed as follows.

[0113] ortho / para ratio = (M _O + (1/2)
M _OP ) / (M _P + (１ ／) M _OP ) Specifically, for example, the ortho / para ratio can be calculated from the above formula from the number of methylene bonds obtained from ¹³ C-NMR spectrum measurement.

In particular, as the novolak resin of the present invention,
The ortho / para ratio is 1 or more, for example, 1 to 20 (especially 1
Novolak resin of about 15), that is, a so-called high ortho novolak resin is preferably used.

The novolak resin having an ortho / para ratio of 1 or more can be used, for example, in the presence of at least one catalyst selected from the group consisting of (1) metal salts, metal oxides, metal hydroxides and amine compounds, or further added. After the condensation reaction, a method of reacting a phenol with an aldehyde by adding an acid catalyst [for example, JP-A-55-90523, JP-A-57-51714, and JP-A-59-80418] Gazette, JP-A-62-230815, US411370
No. 0 publication], (2) phenols and aldehydes under pressure in a non-polar solvent (for example, aromatic hydrocarbons such as xylene, toluene and benzene, and alicyclic hydrocarbons such as cyclohexane). Reaction method [for example, JP-A-6-345837, Makromol. Chem.
182, 2973 (1981), etc.], and (3) a method of reacting phenols with aldehydes in the absence of a catalyst by strictly controlling the production method and conditions [for example, JP-A-10-1951]
58, JP-A-10-204139, etc.],
(4) A method of reacting a metal phenolate such as phenol magnesium bromide or magnesium methylate with an aldehyde in the above-mentioned nonpolar solvent [for example,
U.S. Pat. No. 4,097,463, Macromolecules, 17, 19
(1984)]. The ratio of phenols and aldehydes is the former / latter = 1 / 0.3-1
/ 1 (molar ratio).

Examples of the metal salt catalyst include polyvalent metal salts (for example, Zn, Mg) of organic acids (for example, aliphatic carboxylic acids such as acetic acid, naphthenic acid, and oxalic acid, and sulfonic acids such as methanesulfonic acid). , Mn, Cd, Ca, C
o, Pb, Cu, Ni, Al, etc.).

As the metal oxide and metal hydroxide,
For example, polyvalent metal oxide, polyvalent metal hydroxide (for example,
Zn, Mg, Mn, Cd, Ca, Co, Pb, Cu, N
i, oxides such as Al, hydroxides, etc.).

Examples of the amine compound include aliphatic amines (eg, dimethylamine, diethylamine, etc.).
Is mentioned.

These catalysts can be used alone or in combination of two or more.

The high-ortho novolak resin can be used even if the above-mentioned catalyst such as a metal salt, a metal oxide or a metal hydroxide remains, but it is necessary to reduce the amount of the remaining catalyst by treatment such as washing with water. Is desirable. The high orthonovolak resin obtained by the method (3) is
Since no catalyst is used, removal of the catalyst is not required, and this is a preferable high ortho novolak resin.

The above-mentioned phenols, dioxybenzenes, naphthols and bisphenols (for example,
Bisphenol, bisphenol-A, bisphenol-F, bisphenol-AD, bisphenol-S, bisphenol-sulfone, etc., alkylbenzenes (eg, toluene, ethylbenzene, xylene, mesitylene, etc.), anilines, furfurals, ureas (eg, Co-condensates with urea, melamine anamin, acetoguanamine, benzoguanamine, etc.) can also be used.

In addition, some or all of the phenolic hydroxyl groups of the novolak resin (random novolak resin and high ortho novolak resin) are converted to phosphorus compounds (for example, phosphoric acid, phosphorous acid, phosphate ester, phosphite ester, phosphorous ester). Selected from phosphoric acid compounds and phosphorous acid compounds such as acid chlorides and phosphites, and boron compounds (such as boric acid compounds such as boric acid, borate esters and borate chlorides) A modified novolak resin modified with at least one kind (for example, a phosphate-modified novolak resin, a boric acid-modified novolak resin, etc.) can also be used.
The hydroxyl group of the novolak resin is usually modified as a phosphate or borate.

Preferred novolak resins include phenol formaldehyde novolak resin, alkylphenol formaldehyde resin (for example, t-butylphenol formaldehyde novolak resin, p-octylphenol formaldehyde resin), co-condensates thereof, and mixtures thereof.

The number average molecular weight of the novolak resin (random novolak resin and high ortho novolak resin) is not particularly limited, and is, for example, 300 to 5 × 10 ⁴ , preferably 300 to 1 × 10 ⁴ , more preferably 300 to 80.
00 (especially 300 to 5000).

(Aralkyl Resin) The aralkyl resin used in the present invention has a structural unit represented by the following formula (3).

[0126]

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(Wherein, Ar represents an aromatic group, R ¹⁰ and R ¹¹ are the same or different and represent an alkylene group, R ¹² represents a hydrogen atom or an alkyl group. X represents a hydroxyl group, an amino group, or The aromatic group represented by Ar is an aromatic group having 6 to 20 carbon atoms, for example, a phenylene group (o-phenylene group, m-substituted amino group).
-Phenylene group, p-phenylene group), naphthylene group and the like, preferably phenylene group (particularly p-phenylene group).

Examples of the alkylene group represented by R ¹⁰ and R ¹¹ include a C _1-4 alkylene group such as a methylene group, an ethylene group, a propylene group and a butylene group, preferably a C _1-2 alkylene group.

R¹²Examples of the alkyl group represented by
, Ethyl, butyl, t-butyl, hexyl, octyl
C such as le, nonyl, dodecyl_1-20Alkyl group, preferred
Kuha C _1-4And an alkyl group.

The N-substituted amino group represented by X includes a mono- or di-C _1-4 alkylamino group, for example, a dimethylamino group and a diethylamino group.

As the aralkyl resin, an aniline aralkyl resin in which X is an amino group may be used, but a phenol aralkyl resin having a hydroxyl group is often used. Preferred phenol aralkyl resins include R ¹⁰
And a resin in which R ¹¹ is a methylene group, Ar is a phenylene group, R ¹² is a hydrogen atom, and has a p-xylene-substituted phenol represented by the following formula as a repeating unit.

[0132]

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The aralkyl resin is generally represented by the following formula (4)
And phenols or anilines. When phenols are used, phenol aralkyl resins can be obtained, and when anilines are used, aniline aralkyl resins can be obtained.

YR ¹⁰ -Ar-R ¹¹ -Y (4) (in the formula, Y represents an alkoxy group, an acyloxy group, a hydroxyl group or a halogen atom. Ar, R ¹⁰ and R ¹¹ are the same as described above). In (4), the alkoxy group represented by Y includes a methoxy, ethoxy, propoxy, butoxy group, etc.
_1-4 alkoxy groups are included. The acyloxy group includes an acyloxy group having about 2 to 5 carbon atoms, such as an acetoxy group. The halogen atom includes chlorine, bromine, iodine and the like.

As the compound represented by the above formula (4),
For example, xylylene glycol C _1-4 alkyl ethers (p- xylylene glycol dimethyl ether, p- etc. xylylene glycol diethyl ether) aralkyl ethers such as, p- xylylene-.alpha.,. Alpha .'- dichloride, p- xylylene-.alpha. And aralkyl halides such as α'-dibromide.

Examples of the phenols include phenol, alkylphenol (eg, cresol, xylenol, t-butylphenol, octylphenol,
Nonylphenol C _1-20 alkyl phenol) and the like, such as. These phenols may be used alone or in combination of two or more.

As the anilines, for example, aniline,
Alkyl anilines (eg, toluidine, xylidine,
C _1-20 alkyl anilines such as octyl aniline and nonyl aniline), and N-alkyl anilines (for example,
N, N-dimethylaniline, N, N- N-C _1-4 alkyl anilines, such as diethylaniline) and the like. These anilines may be used alone or in combination of two or more.

The ratio of the compound of the above formula (4) to phenols or anilines is, for example, the former / latter = 1/1
To about 1/3 (molar ratio), preferably 1/1 to 1/2.
It is about 5 (molar ratio).

The reaction of the compound of the formula (4) with phenols or anilines may be carried out in the presence of a catalyst or in the absence of a catalyst. For example, when an aralkyl ether is used as the compound of the formula (4), the reaction can be performed in the presence of a catalyst, and when an aralkyl halide is used, the reaction can be performed in the absence of the catalyst.

Examples of the catalyst include Friedel-Crafts catalysts such as dimethyl sulfate, diethyl sulfate, tin chloride and aluminum chloride.

The above reaction can be carried out in the presence or absence of a solvent. The reaction temperature is, for example, 50 to
The temperature is about 250 ° C, preferably about 100 to 230 ° C. When aralkyl halides are used as the reactants, the reaction temperature may be lower than the above temperature, for example,
The temperature may be about 50 to 150 ° C, particularly about 70 to 130 ° C.

In the above reaction, in addition to phenols and / or anilines, aldehydes (for example,
Aliphatic aldehydes such as formaldehyde, acetaldehyde and propionaldehyde; aromatic aldehydes such as benzaldehyde and phenylacetaldehyde; oxybenzoic acids (eg, p-oxybenzoic acid; methyl p-oxybenzoate; ethyl p-oxybenzoate) P-oxybenzoic acid alkyl ester, etc.), oxybenzenes (dioxybenzene, trioxybenzene, etc.), naphthols (for example, 1-naphthol, 2-naphthol, 1,6-dihydroxynaphthalene, 2,7-dihydroxy Naphthalene, hydroxynaphthoic acid, hydroxynaphthoic acid alkyl ester, etc.), bisphenols (for example, biphenol, bisphenol-A, bisphenol-F, bisphenol-AD, bisphenol-S, Phenol-sulfone, etc., alkylbenzenes (eg, toluene, ethylbenzene, xylene, mesitylene, etc.), anilines, furfurals, ureas (eg, urea, melamine, guanamine, acetoguanamine, benzoguanamine, etc.) may be used in combination. Good.

Further, as the aralkyl resin, at least a part of the hydroxyl group or amino group represented by X is
Phosphorus compounds (for example, phosphorus-based acids such as phosphoric acid, phosphorous acid, organic phosphonic acid, and organic phosphinic acid, and anhydrides, halides, salts, or esters thereof), and boron compounds (for example, boric acid) Aralkyl resin modified with at least one selected from boric acids such as organic boronic acid and organic borinic acid, and anhydrides, halides, salts or esters thereof (for example, phosphoric acid-modified) Phenol aralkyl resins, phosphoric acid-modified aniline aralkyl resins, boric acid-modified phenol aralkyl resins, boric acid-modified aniline aralkyl resins, etc.) can also be used. The hydroxyl group of the aralkyl resin is usually modified as a phosphoric acid ester or a boric acid ester, and the amino group is usually modified as a phosphoric acid amide or a boric acid amide.

The softening point of the aralkyl resin thus obtained is, for example, about 40 to 160 ° C., preferably 5 to 160 ° C.
The temperature is about 0 to 150 ° C, more preferably about 55 to 140 ° C.

The aralkyl resin may be cured or modified as required. Curing or modification can be usually performed by a conventional method such as methylene crosslinking with a polyamine (such as hexamethylenetetramine) and epoxy crosslinking with an epoxy compound (such as a polycyclic epoxide).

Furthermore, the aralkyl resin may be modified with an elastomer, if necessary. Elastomer modification can be performed chemically with an elastomer such as synthetic rubber or polyolefin (polyisobutylene, polyethylene, etc.).

Among the aralkyl resins, the phenol aralkyl resin is trade name “Mirex” (Mitsui Chemicals, Inc.)
"Xylok" (Albright & Wil)
son) or "Sumilite Resin" (Sumitomo Durez). The aniline aralkyl resin is available under the trade name “ANILIX” (manufactured by Mitsui Chemicals, Inc.).

(Aromatic Vinyl Resin) As the aromatic vinyl resin, for example, a resin having a structural unit represented by the following formula (5) can be used.

[0149]

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[0150] (wherein, R ¹³ is a hydrogen atom or a C _1-3 alkyl group, R ¹⁴ represents an aromatic ring, n represents 1 to 3 of an integer) In the equation (5), preferably C _1-3 Examples of the alkyl group include a methyl group. Also, as the aromatic ring,
For example, a C _6-20 aromatic ring such as a benzene and naphthalene ring can be mentioned. Note that the aromatic ring includes a substituent (for example, a hydroxyl group; an alkyl group such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, and t-butyl group); an alkoxy group such as methoxy, ethoxy, and propoxy group. Etc.).

In the formula (5), the hydrogen atom of the hydroxyl group is a metal ion, a silyl group or an alkoxy group,
It may be protected by an organic group (protecting group) such as an alkyl group, an alkanoyl group and a benzoyl group.

A resin obtained from such a derivative has, for example, a structural unit represented by the following formula (6).

[0153]

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(Wherein, R ¹³ is the same as above. R ¹⁵ is —O
H, —OSi (R ¹⁶ ) ₃ and —OM (M is a metal cation,
OR ¹⁶ and OCOR ¹⁶ , wherein R ¹⁶ is a carbon atom, 1 to 5
Or an alkyl group or an aryl group). N is an integer of 1 to 3. In the above formula, M may be either a monovalent alkali metal cation (eg, sodium, lithium, potassium), or a divalent alkaline earth metal cation (eg, magnesium, calcium) or a transition metal cation.

The substituent R ^{15 in the} above formula may be located at any one of the ortho, meta and para positions. Further, in addition to the substituent R ¹⁵ , the pendant aromatic ring may be a C _1-4
May be substituted with an alkyl group.

The aromatic vinyl resin includes a homo- or copolymer of an aromatic vinyl monomer having a hydroxyl group corresponding to the structural unit (5), a copolymer with another copolymerizable monomer, and the like. It is.

As the aromatic vinyl monomer, for example,
Examples include hydroxyl group-containing aromatic vinyl monomers such as vinyl phenol, dihydroxystyrene, and vinyl naphthol.

Other copolymerizable monomers include, for example,
(Meth) acrylic monomer [(meth) acrylic acid,
(Meth) acrylates (for example, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate , Etc.), (meth) acrylamide, (meth) acrylonitrile, etc.], styrene-based monomers (eg, styrene,
Vinyltoluene, α-methylstyrene, chlorostyrene, vinylnaphthalene, vinylcyclohexane, etc.),
Polymerizable polycarboxylic acids (fumaric acid, maleic acid, etc.),
Maleimide monomers (such as phenylmaleimide) and diene monomers (isoprene, 1,3-butadiene, 1,4-
Hexadiene, dicyclopentadiene, etc.), vinyl monomers (for example, vinyl esters such as vinyl acetate and vinyl propionate); vinyl ketones such as methyl vinyl ketone and methyl isopropenyl ketone; vinyl ethers such as vinyl isobutyl ether and vinyl methyl ether Nitrogen-containing vinyl monomers such as N-vinylcarbazole, N-vinylpyrrolidone and N-vinylimidazole). One or more of these copolymerizable monomers can be used.

The ratio of the vinyl monomer to the copolymerizable monomer is, for example, 10/90 to 100/0 (% by weight), preferably 30/70 to 100/0 (% by weight), and more preferably 50/50 to 100/0 (% by weight). It is about 100/0 (% by weight).

Preferred aromatic vinyl resins are vinylphenol homopolymer (polyhydroxystyrene), especially p-hydroxystyrene.
-A vinylphenol homopolymer.

The number average molecular weight of the aromatic vinyl resin is not particularly limited, and is, for example, 300 to 50 × 10 ⁴ , preferably 400 to 30 × 10 ⁴ , more preferably 500 to 50 × 10 ⁴ .
It can be selected from a range of about 5 × 10 ⁴ .

(Aromatic Nylon) As the aromatic nylon used in the present invention, a compound having a unit represented by the following formula can be used.

[0163]

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(Wherein, R¹⁷And R¹⁸Are the same or different
Thus, selected from aromatic, alicyclic, or aliphatic units,
And at least one contains an aromatic ring. R^{twenty three}And R
^{twenty four}Are the same or different and are a hydrogen atom, an alkyl group, or
Indicates an aryl group. Also, R^{twenty three}And R ^{twenty four}Is directly connected to form a ring
Aromatic nylon is derived from diamine and dicarboxylic acid.
A polyamide to be derived, comprising a diamine component and
At least one of the rubonic acid components is aromatic or
Is a polyamide which is an alicyclic compound; aromatic aminocarbo
Acid, optionally diamine and / or dicarboxylic acid
Polyamides obtained in combination are included. Aromatic Niro
Contains at least two different polyamide-forming components
Also included are copolyamides formed by In addition, flame retardant
As the aromatic nylon constituting the auxiliary agent, the thermoplastic nylon
Different kinds of resins are used from polyamide resins.
You.

Examples of the diamine include phenylenediamine, diaminotoluene, 2,4-diaminomesitylene, 3,5-diethyl-2,6-diaminotoluene, and xylylenediamine (particularly, metaxylylenediamine, paraxylylenediamine ), Bis (2-aminoethyl) benzene, biphenylenediamine, 4,4-diaminoethylbiphenyl, diaminodiphenylmethane, 4,4′-
Diaminoethyldiphenylmethane, bis (4-amino-
3-methylphenyl) methane, 3,3'-dichloro-
Aromatic diamines such as 4,4'-diaminodiphenylmethane and 1,4-naphthalenediamine and their N-
Substituted aromatic diamines; alicyclic diamines such as 1,3-cyclopentanediamine, 1,4-cyclohexanediamine, bis (4-amino-3-methylcyclohexyl) methane; trimethylenediamine, tetramethylenediamine, pentamethylenediamine , Hexamethylenediamine, 2,2,4-trimethylhexamethylenediamine,
Examples thereof include aliphatic amines such as 2,4,4-trimethylhexamethylenediamine and octamethylenediamine.
One or more of these diamines can be used. As the diamine, aromatic diamine (particularly, xylylenediamine, N, N'-dialkyl-substituted xylylenediamine)
It is preferred to use

Examples of the dicarboxylic acid include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecandioic acid, dodecandioic acid, hexadecandioic acid, and octadecane. _C2-20 aliphatic dicarboxylic acids such as diacid; aromatic dicarboxylic acids such as phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, and naphthalenedicarboxylic acid; cyclohexane-1,4-dicarboxylic acid and cyclohexane-
Alicyclic dicarboxylic acids such as 1,3-dicarboxylic acid; dimerized fatty acids (eg, dimer acid);
One or more of these dicarboxylic acids can be used.
As the dicarboxylic acid, it is preferable to use an aliphatic dicarboxylic acid (particularly, adipic acid).

Examples of the aromatic aminocarboxylic acid include phenylalanine, tyrosine, anthranilic acid, aminobenzoic acid and the like. One or more aminocarboxylic acids can be used.

As the aromatic nylon, a condensate with lactam and / or α, ω-aminocarboxylic acid may be used as long as the properties of the flame retardant are not impaired. Lactams include C _3-12 lactams such as propionlactam, butyrolactam, valerolactam, and caprolactam (such as ε-caprolactam); and α, ω-aminocarboxylic acids include 7-aminoheptanoic acid and 10-aminodecanoic acid. No.

As other accessory components of the aromatic nylon,
Monobasic acids (eg, acetic acid, propionic acid, caproic acid, nicotinic acid, etc.), monoamines (eg, ethylamine, butylamine, benzylamine, etc.), dibasic acids (eg, adipic acid, sebacic acid, terephthalic acid, isophthalic acid) , Cinchomeronic acid, etc.), diamines (eg, tetramethylene diamine, hexamethylene diamine, etc.) and lactams can be used as the viscosity modifier.

Examples of the aromatic nylon include polyamides in which the diamine component is an aromatic compound (for example, polyamides or copolyamides containing xylylenediamine as the diamine component), aromatic diamines and α, ω-C _4-12 dicarboxylic acids. (Eg, polyamide obtained from adipic acid and meta-xylylenediamine (MXD
6), polyamide obtained from suberic acid and meta-xylylenediamine, polyamide obtained from adipic acid and para-xylylenediamine (PMD6), polyamide obtained from suberic acid and para-xylylenediamine, adipic acid and N, Polyamides obtained from N'-dimethylmetaxylylenediamine, polyamides obtained from suberic acid and N, N'-dimethylmetaxylylenediamine, polyamides obtained from adipic acid and 1,3-phenylenediamine, adipic acid , A polyamide obtained from adipic acid and meta-xylylenediamine and para-xylylenediamine, a polyamide obtained from adipic acid and meta-xylylenediamine and para-xylylenediamine, and adipic acid and meta-xylylenediamine and N, N'-dimethylmet-xylylene diamine Amine obtained from amine Polyamide, polyamide obtained from 4,4′-diaminobiphenylene and adipic acid, etc.). Preferred aromatic nylons are
Aromatic diamine (especially xylylenediamine) and α, ω
And polyamides obtained from C _6-12 aliphatic dicarboxylic acids (especially MXD6). These polyamides can be used alone or in combination.

The number average molecular weight of the aromatic nylon is not particularly limited, and is, for example, 300 to 5 × 10 ⁴ , preferably 5 to 5 × 10 ⁴ .
00 to 1 × 10 ⁴ , more preferably 500 to 8000
(Particularly, 500 to 5000).

The flame-retardant resin composition of the present invention may contain another flame retardant. Other flame retardants include, for example, nitrogen-containing flame retardants, sulfur-containing flame retardants, silicon-containing flame retardants, alcohol-based flame retardants, inorganic flame retardants (metal oxides,
Metal hydroxide).

Examples of the nitrogen-containing flame retardant include amines such as ureas, guanidines, and triazine compounds (for example, melamine, melam, melem, ammeline, melamine formaldehyde resin, guanamine, acetoguanamine, benzoguanamine, etc.), and triazine compounds. Salts of a compound with cyanuric acid or isocyanuric acid (the former: the latter (molar ratio) = 1: 1 to 1: 2 salts, such as melamine cyanurate, guanamine cyanurate, acetoguanamine cyanurate, benzoguanamine cyanurate and the like) ).

Examples of the sulfur-containing flame retardant include, in addition to the sulfuric acid ester, organic sulfonic acid, sulfamic acid, organic sulfamic acid, and salts, esters and amides thereof.

The silicon-containing flame retardants include (poly) organosiloxanes. Examples of the (poly) organosiloxane include monoorganosiloxanes such as dialkylsiloxane (eg, dimethylsiloxane), alkylarylsiloxane (phenylmethylsiloxane), diarylsiloxane, and homopolymers thereof (eg, polydimethylsiloxane, polyphenyl). Methylsiloxane) or a copolymer. Also,
As the (poly) organosiloxane, epoxy groups, hydroxyl groups, carboxyl groups, amino groups,
A modified (poly) organosiloxane having a substituent such as an ether group (for example, modified silicone) can also be used.

Examples of the alcohol-based flame retardant include polyhydric alcohols, oligomeric polyhydric alcohols, esterified polyhydric alcohols, substituted alcohols, and saccharides (monosaccharides, polysaccharides, etc.).

Among the inorganic flame retardants, examples of the metal oxide include molybdenum oxide, tungsten oxide, titanium oxide, zirconium oxide, tin oxide, copper oxide, zinc oxide, aluminum oxide, nickel oxide, iron oxide, and manganese oxide. , Antimony trioxide, antimony tetroxide, antimony pentoxide and the like. As metal hydroxide,
For example, aluminum hydroxide, magnesium hydroxide, tin hydroxide, and zirconium hydroxide are mentioned.

The inorganic flame retardants also include metal stannates (eg, zinc duzate, etc.), metal borates (eg, sodium borate, zinc borate, etc.), and expandable graphite. .

These other flame retardants can be used alone or in combination of two or more.

The content of the other flame retardant is, for example, about 0.01 to 50 parts by weight, preferably about 0.05 to 30 parts by weight, particularly 0.1 to 100 parts by weight of the thermoplastic resin.
It can be selected from a range of about to 20 parts by weight.

Further, the flame retardant resin composition of the present invention may contain an anti-dripping agent such as a fluororesin. With the anti-dripping agent, dripping of the fire and the melt during combustion can be suppressed. The fluorine-based resin composition includes a homo- or copolymer of a fluorine-containing monomer such as tetrafluoroethylene, chlorotrifluoroethylene, vinylidene fluoride, hexafluoropropylene, or perfluoroalkylvinyl ether; And a copolymer with a copolymerizable monomer such as acrylate. Examples of such a fluorine-based resin composition include homopolymers such as polytetrafluoroethylene, polychlorotrifluoroethylene, and polyvinylidene fluoride; tetrafluoroethylene-hexafluoropropylene copolymer,
Copolymers such as a tetrafluoroethylene-perfluoroalkylvinyl ether copolymer, an ethylene-tetrafluoroethylene copolymer, and an ethylene-chlorotrifluoroethylene copolymer are exemplified. These fluororesins can be used alone or in combination of two or more.

The fluororesin may be used in the form of particles. The average particle diameter is, for example, about 10 to 5000 μm.
Preferably it may be about 100 to 1000 μm, more preferably about 200 to 700 μm.

The content of the fluorine resin is, for example, based on 100 parts by weight of the total of the thermoplastic resin and the resin component (polyarylate resin, epoxy resin) constituting the flame retardant.
It can be selected from a range of about 0.01 to 10 parts by weight, preferably about 0.1 to 5 parts by weight, more preferably about 0.1 to 3 parts by weight.

Further, the flame-retardant resin composition of the present invention may contain an antioxidant or a stabilizer in order to stably maintain heat resistance for a long period of time. Examples of the antioxidant or stabilizer include phenol-based (such as hindered phenols), amine-based (such as hindered amines), phosphorus-based, sulfur-based, hydroquinone-based, and quinoline-based antioxidants.

The phenolic antioxidants include hindered phenols such as 2,2'-methylenebis (4-
Methyl-6-t-butylphenol), 4,4'-methylenebis (2,6-di-t-butylphenol), 4,
4'-butylidenebis (3-methyl-6-t-butylphenol), 2,6-di-t-butyl-p-cresol, 1,3,5-trimethyl-2,4,6-tris (3,5- Di-t-butyl-4-hydroxybenzyl)
Benzene, 1,6-hexanediol-bis [3-
(3,5-di-t-butyl-4-hydroxyphenyl)
Propionate], pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], triethylene glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxy) Phenyl) propionate], n-octadecyl-3
-(4 ', 5'-di-t-butylphenol) propionate, n-octadecyl-3- (4'-hydroxy-
3 ', 5'-di-tert-butylphenol) propionate, stearyl-2- (3,5-di-tert-butyl-4-)
(Hydroxyphenol) propionate, distearyl-3,5-di-t-butyl-4-hydroxybenzylphosphonate, 2-t-butyl-6- (3-t-butyl-
5-methyl-2-hydroxybenzyl) -4-methylphenyl acrylate, N, N'-hexamethylenebis (3,5-di-t-butyl-4-hydroxy-hydrocinnamamide), 3,9-bis {2- [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl} -2,4.
8,10-tetraoxaspiro [5,5] undecane,
4,4'-thiobis (3-methyl-6-t-butylphenol), 1,1,3-tris (2-methyl-4-hydroxy-5-t-butylphenol) butane and the like are included.

Of the hindered phenols,
For example, 1,6-hexanediol-bis [3- (3,
5-di -t- butyl-4-hydroxyphenyl) propionate] C _2-10 alkylene diol such as - bis [3
- (3,5-di - branched C _3-6 alkyl-4-hydroxyphenyl) propionate]; for example, triethylene glycol - bis [3- (3-t-butyl-5-methyl -
Di- or trioxy C _2-4 alkylene diol-bis [3-
(3,5-di-branched C _3-6 alkyl-4-hydroxyphenyl) propionate]; for example, C such as glycerin tris [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] _3-8 alkylenetriol-bis [3- (3,5-di-branched C _3-6 alkyl-
4-hydroxyphenyl) propionate];
Pentaerythritol tetrakis [3- (3,5-di-
and C _4-8 alkylenetetraol tetrakis [3- (3,5-di-branched C _3-6 alkyl-4-hydroxyphenyl) propionate] such as [t-butyl-4-hydroxyphenyl) propionate].

[0187] The amine-series antioxidant, a hindered amine, for example, tri- or tetra-C _1-3 alkyl piperidine or a derivative thereof [for example, 4-methoxy-2,2,
6,6-tetramethylpiperidine, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, 4-phenoxy-2,2,6,6-tetramethylpiperidine, etc.], bis (tri, tetra or penta C _1-3 alkylpiperidine) C _2-20 alkylenedicarboxylic acid ester [for example, bis (2,2,6,6-tetramethyl-4-piperidyl) oxalate, bis (2,2,6,6-tetramethyl- 4-piperidyl) malonate, bis (2,2,
6,6-tetramethyl-4-piperidyl) adipate,
Bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis (2,2,2
6,6-tetramethyl-4-piperidyl) terephthalate], 1,2-bis (2,2,6,6-tetramethyl-
4-piperidyloxy) ethane, phenyl-1-naphthylamine, phenyl-2-naphthylamine, N, N'-
Diphenyl-1,4-phenylenediamine, N-phenyl-N'-cyclohexyl-1,4-phenylenediamine and the like.

Examples of the phosphorus-based stabilizer (or antioxidant) include, for example, triisodecyl phosphite, trisnonylphenyl phosphite, diphenylisodecyl phosphite, phenyldiisodecyl phosphite, 2,2-methylenebis (4,6 -Di-t-butylphenyl) octyl phosphite, 4,4'-butylidenebis (3-methyl-6-t-butylphenyl) ditridecyl phosphite, tris (branched C _3-6 alkylphenyl) phosphite [for example, Tris (2,4-di-t-butylphenyl) phosphite, tris (2-t-butyl-4-methylphenyl) phosphite, tris (2,4-di-t-butyl)
Amylphenyl) phosphite, tris (2-t-butylphenyl) phosphite, tris [2- (1,1-dimethylpropyl) -phenyl] phosphite, tris [2,4- (1,1-dimethylpropyl) -Phenyl]
Phosphite etc.], bis (2-t-butylphenyl)
Phenyl phosphite, tris (2-cyclohexylphenyl) phosphite, tris (2-t-butyl-4-
Phenylphenyl) phosphite, bis (C _3-9 alkylaryl) pentaerythritol diphosphite [for example, bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite, bis (2,6-di- t
-Butyl-4-methylphenyl) pentaerythritol diphosphite, bis (nonylphenyl) pentaerythritol diphosphite, bis (nonylphenyl) pentaerythritol diphosphite and the like], triphenyl phosphate stabilizers (for example, 4-phenoxy -9-
α- (4-hydroxyphenyl) -p-cumenyloxy-3,5,8,10-tetraoxa-4,9-diphosphapiro [5,5] undecane, tris (2,4-di-t
-Butylphenyl) phosphate, etc.), diphosphonite-based stabilizers (for example, tetrakis (2,4-di-t-
Butylphenyl) -4,4'-biphenylenediphosphonite and the like. Phosphorus stabilizers are usually
It has a branched C _3-6 alkylphenyl group (particularly a t-butylphenyl group).

The hydroquinone-based antioxidants include, for example,
2,5-di-t-butylhydroquinone and the like, and quinoline-based antioxidants include, for example, 6-ethoxy-2,
2,4-trimethyl-1,2-dihydroquinoline and the like, and the sulfur-based antioxidants include, for example, dilauryl thiodipropionate, distearyl thiodipropionate and the like.

These antioxidants can be used alone or in combination of two or more. The content of the antioxidant is, for example, 0.01 to 100 parts by weight of the thermoplastic resin.
It can be selected from a range of 5 parts by weight, preferably 0.05 to 2.5 parts by weight, particularly about 0.1 to 1 part by weight.

When a polyester resin or a polycarbonate resin is used as the thermoplastic resin, the addition of an inorganic phosphorus compound further improves the thermal stability. As the inorganic phosphorus compound, for example, inorganic phosphoric acid (phosphoric acid,
Phosphorous acid, phosphonic acid, phosphinic acid, polyphosphoric acid,
Polyphosphorous acid, phosphonocarboxylic acid, nitrogen-containing phosphoric acid, etc.) and their acidic metal salts.

The acidic metal salts of inorganic phosphoric acid include, for example, inorganic hydrogen phosphate alkali metals (eg, NaH ₂ PO ₄ ,
Alkali metal hydrogen phosphates such as Na ₂ HPO ₄ , KH ₂ PO ₄ , and K ₂ HPO ₄ ), inorganic alkaline hydrogen phosphates (eg, CaHPO ₄ , Ca (H ₂ PO ₄ ) ₂ , MgH
_{PO 4, Mg (H 2 PO} 4) 2, hydrogen phosphate alkaline earth metals such as such), hydrogen inorganic aluminum phosphate (e.g., Al (H ₂ PO _4), etc. ₃₎ and the like.

Further, the thermoplastic resin composition of the present invention may be modified with a filler in order to further improve mechanical strength, rigidity, heat resistance, electrical properties and the like. The filler includes a fibrous filler and a non-fibrous filler (powder-like filler, plate-like filler, etc.).

Examples of the fibrous filler include glass fiber, asbestos fiber, carbon fiber, silica fiber, silica-alumina fiber, zirconia fiber, potassium titanate fiber, metal fiber, and high melting point organic fiber (for example, aliphatic or aromatic). Polyamide, aromatic polyester, fluorine resin, acrylic resin such as polyacrylonitrile, etc.).

Among the non-fibrous fillers, powdery and granular fillers include silica, quartz powder, glass beads, glass powder, milled fiber (eg, milled glass fiber), calcium silicate, aluminum silicate, kaolin, Silicates such as talc, clay, diatomaceous earth and wollastonite; metal oxides such as iron oxide, titanium oxide, zinc oxide and alumina; carbonates of metals such as calcium carbonate and magnesium carbonate; calcium sulfate and barium sulfate And metal powders such as silicon carbide.

Examples of the plate-like filler include mica, glass flake, various metal foils and the like.

Preferred fibrous fillers include glass fibers and carbon fibers. Preferred non-fibrous fillers include powdered or plate-like fillers, particularly glass beads, milled fibers, kaolin, talc, and mica. , And glass flakes.

Further, particularly preferable fillers include glass fibers having high strength and rigidity.

When a filler is used, the proportion of the filler in the flame-retardant resin composition is, for example, about 5 to 60% by weight, preferably about 5 to 50% by weight, and more preferably 5 to 35% by weight.
% By weight.

In using these fillers, it is desirable to use a sizing agent or a surface treatment agent if necessary.
Examples of such a sizing agent or a surface treatment agent include functional compounds, for example, epoxy compounds, silane compounds, titanate compounds and the like, preferably epoxy compounds and the like, particularly bisphenol A type or novolak type epoxy resins. .

The filler may have been subjected to convergence treatment or surface treatment with the sizing agent or surface treatment agent. Regarding the timing of the treatment, the treatment may be performed simultaneously with the addition of the filler,
It may be treated before addition.

The amount of the sizing agent or the surface treatment agent (particularly, the functional surface treatment agent) is 5% by weight or less, preferably about 0.05 to 2% by weight, based on the filler.

Further, the flame-retardant resin composition of the present invention may contain other additives according to the purpose. Other additives include stabilizers (ultraviolet absorbers, heat stabilizers, weather stabilizers, etc.), lubricants, release agents, colorants, plasticizers, nucleating agents, impact modifiers, sliding agents, and the like. .

The flame retardant of the present invention can make a resin highly flame retardant. By combining a phosphorus compound and at least one resin selected from a polyarylate resin and a specific epoxy resin, it is possible to effectively make a thermoplastic resin flame-retardant even in a small amount, and reduce bleed-out and heat resistance. I won't let you.

[Production Method of Flame-Retardant Resin Composition] The flame-retardant resin composition of the present invention may be a powder mixture or a molten mixture. Combustion aids, other flame retardants, anti-dripping agents, antioxidants,
It can be prepared by mixing a filler or other additives with a conventional method. For example, after mixing each component, kneading and extruding with a single-screw or twin-screw extruder to prepare pellets, a method of molding, once preparing pellets (master batch) having different compositions, and weighing the pellets in a predetermined amount A method of mixing (diluting) and subjecting to molding to obtain a molded article of a predetermined composition, a method of directly charging one or more of each component to a molding machine, and the like can be adopted. In addition, in the preparation of the composition used for the molded article, when part or all of the thermoplastic resin powder and other components (such as a flame retardant) are mixed and melt-kneaded, the dispersion of other components is reduced. It is advantageous to improve.

From the viewpoint of handling, a thermoplastic resin, a resin constituting a flame retardant (at least one resin selected from a polyarylate resin and an epoxy resin),
It is convenient to prepare a masterbatch by once melt-mixing at least two components selected from a compound containing phosphorus and a phosphorus-containing compound. In particular, when red phosphorus is used as the phosphorus-containing compound, a master batch is often prepared.
In addition, at least one of the components constituting the master batch is a resin component. When a masterbatch is constituted by a resin component, a part of the thermoplastic resin is often used for the masterbatch.

As the master batch, for example,
(1) a masterbatch composed of a part of a thermoplastic resin and a phosphorus-containing compound, (2) a masterbatch composed of a resin component constituting a flame retardant and a phosphorus-containing compound,
(3) A master batch composed of a resin component constituting a flame retardant, a thermoplastic resin, and a phosphorus-containing compound is exemplified.

The masterbatch may contain various additives, for example, a flame retardant aid, a fluororesin,
It may contain an antioxidant, a phosphorus stabilizer, a filler and the like.

[0209] The flame retardant resin composition can be produced by melt-mixing the master batch thus obtained, the thermoplastic resin and, if necessary, the remaining components.

The flame-retardant resin composition of the present invention can be melt-kneaded and molded by a conventional method such as extrusion molding, injection molding, compression molding, and the like. It can be used for various applications because it is excellent. For example, it can be suitably used for electric / electronic parts, mechanical mechanism parts, automobile parts and the like.

[0211]

In the present invention, a flame retardant composed of a phosphorus-containing compound and at least one resin selected from a polyarylate resin and a specific epoxy resin is used.
It is possible to make a thermoplastic resin flame-retardant without using a halogen-based flame retardant. Further, the flame retardant resin composition of the present invention,
Bleed-out can be suppressed, and mechanical properties can be maintained at a high level without using a special compound.

[0212]

The present invention will be described below in more detail with reference to Examples, but the present invention is not limited to these Examples.

The properties of the resin composition were evaluated by the following tests. (Flammability test) In accordance with UL94, the thickness of the test piece was set at 0.
Flammability was evaluated at 8 mm. (Forming appearance) Burning test specimen in a gear oven at 120 ° C
For 24 hours, and the appearance was evaluated. The evaluation criteria are shown below.

＝= Almost no bleed-out Δ = Slight bleed-out X = A large amount of bleed-out In Examples and Comparative Examples, the following thermoplastic resins and flame retardants were used.

[Thermoplastic Resin A] A-1: Polybutylene terephthalate (Duranex, intrinsic viscosity = 0.83, Polyplastics Co., Ltd.)
A-2: Polybutylene phthalate modified with 12.5 mol% isophthalic acid A-3: Polyethylene terephthalate (Velpet E
A-4: PBT elastomer (60% by weight of PBT segment, 40% by weight of poly (tetramethylene oxide glycol) terephthalate segment) A-5: PET liquid crystal polymer Polyethylene terephthalate and p-acetoxybenzoic acid Is melt-mixed to form a polyester telefragment by an acidolysis reaction, and then a polycondensation reaction is performed to increase the degree of polymerization of the liquid crystal polyester represented by the following formula:

[0216]

Embedded image

P / q / r = 80/20/20 (molar ratio) A-6: Polycarbonate (Panlite L1225, manufactured by Teijin Chemicals Ltd.) A-7: Nylon-6,6 (polyplastic nylon 66, poly A-8: ABS (styrene 41% by weight, acrylonitrile 14% by weight, butadiene 45% by weight) A-9: PBT resin blend 69 parts by weight of polybutylene terephthalate (A-1), poly ( 2,6-dimethyl-1,4-phenylene ether)
Dry blend resin pellets consisting of 23 parts by weight (intrinsic viscosity: 0.45) and 8 parts by weight of polystyrene (melt index (MI) = 5.5).

A-10: PBT resin blend 67 parts by weight of polybutylene terephthalate (A-1), poly (2,6-dimethyl-1,4-phenylene ether)
(Intrinsic viscosity: 0.45) 23 parts by weight, polystyrene (M
I = 5.5) 8 parts by weight, and polycarbonate (A-
6) Dry blend resin pellets consisting of 2 parts by weight.

A-11: PBT master batch 67 parts by weight of polybutylene terephthalate (A-1), poly (2,6-dimethyl-1,4-phenylene ether)
(Intrinsic viscosity: 0.45) 23 parts by weight, polystyrene (M
I = 5.5) 8 parts by weight, polycarbonate (A-6) 2
Parts by weight, pentaerythyl-tetrakis [3- (3,5
-Di-t-butyl-4-hydroxyphenyl) propionate (F-1) 0.5 part by weight and bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite (G- 2) 1 part by weight of 280 ° C. using a twin screw extruder [TEX30: manufactured by Japan Steel Works, Ltd.]
, And dried at 105 ° C. for 8 hours to obtain thermoplastic resin pellets (master batch).

A-12: PBT master batch 67 parts by weight of polybutylene terephthalate (A-1), poly (2,6-dimethyl-1,4-phenylene ether)
(Intrinsic viscosity: 0.45) 23 parts by weight, ABS (A-8)
8 parts by weight, 2 parts by weight of polycarbonate (A-6), pentaerythrityl-tetrakis [3- (3,5-di-t-
Butyl-4-hydroxyphenyl) propionate (F
-1) 0.5 parts by weight, bis (2,6-di-t-butyl-)
1 part by weight of 4-methylphenyl) pentaerythritol diphosphite (G-2) was mixed with a twin-screw extruder [TEX3
0: manufactured by Nippon Steel Works Co., Ltd.] at 280 ° C., and dried at 105 ° C. for 8 hours to obtain thermoplastic resin pellets (master batch).

[Flame retardant] (Phosphorus-containing compound B) B-1: Red phosphorus (Nova Excel 140, manufactured by Rin Kagaku Kogyo Co., Ltd.) B-2: Red phosphorus (Nova Excel F5, manufactured by Rin Kagaku Kogyo Co., Ltd.) B-3) Red phosphorus masterbatch Using a vented twin-screw extruder, prepared from red phosphorus (B-1) and polybutylene terephthalate (A-1).
-1) / (A-1) = 30/70 (weight ratio) red phosphorus masterbatch.

B-4: Red phosphorus master batch Prepared from red phosphorus (B-2) and polybutylene terephthalate (A-1) using a vented twin screw extruder (B
-2) / (A-1) = 30/70 (weight ratio) red phosphorus masterbatch.

B-5: Condensed phosphoric ester (PX-20)
B-6: ammonium polyphosphate (TERAGE C60, manufactured by Daihachi Chemical Industry Co., Ltd.)
B-7: Condensed phosphoric acid ester (PX-201, manufactured by Daihachi Chemical Industry Co., Ltd.) (Resin C: polyarylate resin or aromatic epoxy resin) C-1: Poly-4, 4'-diphenylene propane tele /
Isophthalate (Polyarylate U polymer U-10
C-2: poly-4,4'-diphenylenepropane isophthalate (prepared by melt polymerization of diphenylisophthalate and bisphenol-A) C-3: poly-1,3-phenylene Adipate (prepared by solution polymerization of adipic acid dichloride and resorcinol) C-4: Polyarylate resin alloy (Polyarylate U polymer P-1001, manufactured by Unitika Ltd.) C-5: Polyarylate resin alloy (Polyarylate) U-polymer U-8400, manufactured by Unitika Ltd.) C-6: Polyarylate resin alloy (polyarylate U-polymer AX-1500, manufactured by Unitika Ltd.) C-7: Bisphenol-A type epoxy resin (Epicoat 1004K, Yuka Shell Epoxy Co., Ltd.) C-8: Phenoxy resin (Phenothote Y) -50, manufactured by Toto Kasei Co., Ltd.) C-9: Novolak type epoxy resin (manufactured by Aldrich Co., Ltd.) [Flame retardant Aid D] D-1: Novolac resin (PR-53195, manufactured by Sumitomo Durez Co., Ltd.) D-2: Novolak resin (high ortho novolak HPN)
-X, manufactured by Sumitomo Durez Co., Ltd.) D-3: boric acid-modified novolak resin (PR-RX531)
01, manufactured by Sumitomo Durez Co., Ltd.) D-4: Phosphoric acid-modified novolak resin 100 parts by weight of novolak resin (D-1) are heated and melted.
Phosphoric acid-modified novolak resin obtained by adding 10 parts by weight of phosphoric acid over 1 hour while maintaining the temperature at 140 ° C., and further reacting at 150 ° C. for 2 hours. D-5: Phenol aralkyl resin (Mirex XL-
D-6: Phosphoric acid-modified phenol aralkyl resin 100 parts by weight of phenol aralkyl resin (D-5) is heated and dissolved, and 5 parts by weight of phosphoric acid is added while maintaining at 140 ° C.
Over a period of time, and then further reacted at 150 ° C. for 2 hours. D-7: Polyvinylphenol (Marcalinker MS-)
1P, manufactured by Maruzen Petrochemical Co., Ltd.) D-8: Polyamide MXD6 (Renny 6002, manufactured by Mitsubishi Engineering Plastics Co., Ltd.) [Nitrogen-containing flame retardant E] E-1: Melamine cyanurate (MC610, Nissan Chemical Industries, Ltd.) [Antioxidant F] F-1: pentaerythrityl-tetrakis [3- (3,3)
5-Di-t-butyl-4-hydroxyphenyl) propionate] (Irganox 1010, manufactured by Ciba Geigy) [Phosphorus stabilizer G] G-1: Tetrakis (2,4-di-t-butylphenyl) -4,4'-biphenylenediphosphonite (Sandstub P-EPQ, manufactured by Sando Co., Ltd.) G-2: bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite (Adekastab PEP36, manufactured by Adeka Argus Co., Ltd.) [Drip-preventing agent H] H-1: Polytetrafluoroethylene [Filler I (glass fiber)] I-1: Chopped strand of 10 μm in diameter and 3 mm in length 1 to 29 and Comparative Examples 1 to 10 The above components were mixed with polybutylene terephthalate (A-1) in the proportions shown in Tables 1 to 7, and the mixture was extruded. Kneading, the resin composition was prepared and extruded. This resin composition was injection-molded to produce a molded article for testing, and the flammability and appearance of the heat-treated molded article were evaluated.

The results are shown in Tables 1 to 7.

[0225]

[Table 1]

[0226]

[Table 2]

[0227]

[Table 3]

[0228]

[Table 4]

[0229]

[Table 5]

[0230]

[Table 6]

[0231]

[Table 7]

Examples 30 to 40 and Comparative Examples 11 to 26 The above components were mixed with thermoplastic resin A at the ratios shown in Tables 8 to 12, kneaded with an extruder, and extruded to prepare a resin composition. This resin composition was injection-molded to prepare a test molded article, and the flammability and appearance of the heat-treated molded article were evaluated.

Tables 8 to 12 show the results.

[0234]

[Table 8]

[0235]

[Table 9]

[0236]

[Table 10]

[0237]

[Table 11]

[0238]

[Table 12]

Examples 41 to 45 and Comparative Examples 27 to 30 A kneaded mixture of thermoplastic resin blend A, resin C, antioxidant F, phosphorus-based stabilizer G, and anti-dripping agent H was mixed with a twin-screw extruder [ TEX30: manufactured by Japan Steel Works, Ltd.], phosphorus-containing compound B, flame-retardant aid D,
The resin composition was prepared by extruding at 280 ° C. while supplying a mixture of the nitrogen-containing compound E and the glass fiber I from a side feeder. In addition, each component was used in the ratio of Tables 13-14. This resin composition was dried and injection-molded to prepare a test molded article, and the flammability and appearance of the heat-treated molded article were evaluated.

Examples 46 to 50 and Comparative Examples 31 to 34 A mixed and stirred mixture of the thermoplastic resin master batch A and the components B to H was subjected to a twin-screw extruder [TEX30: manufactured by Nippon Steel Works Ltd.]
The resin composition was prepared by extruding at 280 ° C. while supplying the glass fiber I from the side feeder. In addition, each component was used in the ratio of Tables 13-14. This resin composition was dried and injection-molded to prepare a test molded article, and the flammability and appearance of the heat-treated molded article were evaluated.

The results are shown in Tables 13 and 14.

[0242]

[Table 13]

[0243]

[Table 14]

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI theme coat ゛ (Reference) C08K 5/521 C08K 5/521 C08L 63/02 C08L 63/02 67/02 67/02

Claims (23)

[Claims] 1. A flame-retardant resin composition containing a thermoplastic resin and a flame retardant, wherein the flame retardant is at least one selected from a phosphorus-containing compound, a polyarylate resin and an aromatic epoxy resin. And a flame-retardant resin composition. 2. The flame-retardant resin composition according to claim 1, which contains 0.1 to 100 parts by weight of a flame retardant based on 100 parts by weight of the thermoplastic resin. 3. The flame-retardant resin composition according to claim 1, wherein the flame retardant contains 1 to 1000 parts by weight of the phosphorus-containing compound based on 100 parts by weight of the total of the polyarylate resin and the aromatic epoxy resin. 4. The thermoplastic resin is at least one selected from an olefin resin, an acrylic resin, a styrene resin, a polyamide resin, a polyester resin, a polycarbonate resin, a polyphenylene oxide resin, and a vinyl resin. The flame-retardant resin composition according to claim 1, which is a thermoplastic resin. 5. The flame-retardant resin composition according to claim 1, wherein the thermoplastic resin is a polyalkylene arylate or a copolyester containing alkylene arylate as a main component. 6. A homo- or copolyester wherein the thermoplastic resin has at least one unit selected from 1,4-cyclohexane dimethylene terephthalate, ethylene terephthalate, butylene terephthalate, propylene terephthalate, ethylene naphthalate and butylene naphthalate. The flame-retardant resin composition according to claim 1, wherein 7. The flame-retardant resin composition according to claim 1, wherein the thermoplastic resin is polybutylene terephthalate or a copolyester containing butylene terephthalate as a main component. 8. The flame-retardant resin composition according to claim 1, wherein the phosphorus-containing compound is at least one selected from red phosphorus, a (poly) phosphate, and a phosphate ester. 9. The flame-retardant resin composition according to claim 1, wherein the phosphorus-containing compound is stabilized red phosphorus. 10. The aromatic polyol component constituting the polyarylate resin is a bisphenol.
The flame-retardant resin composition according to the above. 11. The flame-retardant resin composition according to claim 1, wherein the epoxy resin is at least one selected from an ether-based epoxy resin and an amine-based epoxy resin. 12. The flame-retardant resin composition according to claim 1, wherein the epoxy resin is a bisphenol-type or novolak-type epoxy resin. 13. The flame retardant according to claim 1, further comprising, as the flame retardant auxiliary, at least one selected from a resin having an aromatic ring having a hydroxyl group or an amino group in a main chain or a side chain, and an aromatic nylon. Flammable resin composition. 14. The flame-retardant resin composition according to claim 13, wherein the resin having an aromatic ring in the main chain is a novolak resin or an aralkyl resin. 15. The flame-retardant resin composition according to claim 13, wherein the resin having an aromatic ring in the side chain is an aromatic vinyl resin. 16. The method according to claim 1, further comprising a nitrogen-containing flame retardant.
The flame-retardant resin composition according to the above. 17. The flame-retardant resin composition according to claim 1, further comprising a fluorine-based resin. 18. The flame-retardant resin composition according to claim 1, further comprising at least one of a hindered phenol antioxidant and a phosphorus stabilizer. 19. The flame-retardant resin composition according to claim 1, further comprising a filler. 20. A method for producing a flame-retardant resin composition by mixing a thermoplastic resin with the flame retardant according to claim 1. 21. A master batch composed of at least two components selected from a thermoplastic resin, a resin component constituting a flame retardant, and a phosphorus-containing compound, and a thermoplastic resin, which is melt-mixed. For producing a flame-retardant resin composition of the invention. 22. A molded article formed from the flame-retardant resin composition according to claim 1. 23. The molded article according to claim 22, wherein the molded article is an electric / electronic part, a mechanical mechanism part, or an automobile part.