JP2000344939A - Flame-retardant resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a flame-retardant resin composition not lowering a characteristic of a resin and adding high flame retardancy using a small amount of a flame retardant and the like by including a phosphorus-containing compound and a resin having a spiro ring on a principal chain in a thermoplastic resin. SOLUTION: This composition comprises including (B) a phosphorus- containing compound (e.g. red phosphorus, phosphoric acid ester or the like) as a flame retardant and (C) a resin having a spiro ring on a principal chain in (A) a thermoplastic resin preferably in 0.1-100 parts by weight of the sum of the components B and C based on 100 parts by weight of the component A. Preferably 1-100 parts by weight of the component B is used as a flame retardant based on 100 parts by weight of the component C. Preferably the component A is a polyester-based resin (e.g. polybutylene terephthalate or the like). Preferably the spiro ring of the component C is shown by the formula (X1 to X4 are each a 1-6C alkylene or the like; Y is P or the like; W is an alkylene or the like).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a flame-retardant resin composition containing a thermoplastic resin and useful for obtaining a molded article, a method for producing the same, and a molded article formed from the flame-retardant resin composition. About.

[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. Therefore, it is used for various purposes such as electric / electronic parts and automobile parts. On the other hand, as the field of use expands, flame retardancy is required to be improved.

[0003] Therefore, there has been proposed a method of making a thermoplastic resin flame-retardant by adding a flame retardant using a halogen compound or an antimony compound. For example, JP
Japanese Patent Application Laid-Open No. 3-150349 discloses a flame-retardant method in which a glass fiber, an organic halogen-based flame retardant, antimony trioxide, and an alkali metal or alkaline earth metal hydroxide are mixed with a mixed resin composed of a polyamide resin and nylon 66. A modified resin composition is disclosed. In addition, as a brominated polymer, brominated polycarbonate, brominated polystyrene,
Brominated poly p-vinylphenol and the like are commercially available as high molecular weight flame retardants. However, a halogen-based flame retardant may generate a dioxin-based compound when decomposed by combustion, which is not preferable in terms of environmental problems. 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.

JP-A-6-25506 discloses that a thermoplastic resin comprising a copolymer of an aromatic vinyl compound and a vinyl monomer, a graft copolymer of a rubbery polymer, and a novolak resin contains phosphorus. A flame retardant resin composition to which a system compound is added 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. JP-A-10-195283 discloses a flame-retardant polyester 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). A resin composition is disclosed.

[0005] However, although non-halogen flame retardants do not contain harmful halogens, they require a large amount of flame retardants because of their inferior flame retarding effect as compared with halogen flame retardants.
Addition of a large amount of a flame retardant causes bleed out and deterioration of the mechanical properties of the resin. Therefore, along with flame retardancy,
The mechanical properties cannot be improved. 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 high flame retardancy without deteriorating the properties of the resin. Further, although the above-mentioned flame retardant can make the specific resin flame-retardant, the flame-retardant effect is not sufficient for the whole thermoplastic resin.

[0007]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a non-halogen flame-retardant resin composition which is flame-retarded at a high level even with a small amount of a flame retardant, and a method for producing the same. It is in.

Another 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 molded article having improved flame retardancy.

[0010]

Means for Solving the Problems The present inventors have made intensive studies to achieve the above object, and as a result, by adding a specific non-halogen flame-retardant composition to a thermoplastic resin, a high level has been achieved. The inventors have found that flame retardancy can be achieved, and have completed the present invention.

That is, the flame-retardant resin composition of the present invention comprises:
A flame retardant resin composition containing a thermoplastic resin and a flame retardant, wherein the flame retardant is composed of a phosphorus-containing compound and a resin having a spiro ring in a main chain. This composition contains 0.1 to 100 flame retardants based on 100 parts by weight of the thermoplastic resin.
It may contain parts by weight. Further, the flame retardant may contain 1 to 100 parts by weight of the phosphorus-containing compound based on 100 parts by weight of the resin having a spiro ring in the main chain. The thermoplastic resin composition of the present invention is based on 100 parts by weight of the thermoplastic resin.
Red phosphorus may be contained in an amount of 1 to 15 parts by weight. The thermoplastic resin includes a polyester-based resin and the like. Phosphorus-containing compounds include red phosphorus, (poly) phosphates, phosphate esters, and the like. Furthermore, the flame-retardant resin composition of the present invention includes:
Additives such as a fluororesin, a hindered phenolic antioxidant, a phosphorus stabilizer and a filler may be used alone or in combination of two or more.

The resin having a spiro ring in the main chain may be a resin having a spiro ring unit represented by the following formula (1).

[0013]

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(Wherein X ₁ , X ₂ , X ₃ and X ₄ are each independently selected from an alkylene group, an oxyalkylene group, an iminoalkylene group and a thioalkylene group, and the carbon atom contained in each group is The number is 1 to 6. Y represents the following group,

[0015]

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W represents a bond, an alkylene group, an oxyalkylene group, an iminoalkylene group, a thioalkylene group, or a divalent organic group having a branched structure in which some or all of the hydrogen atoms have been substituted with an alkyl group. It is. ) The spiro ring unit may have, for example, at least a 2,4,8,10-tetraoxaspiro [5,5] -undecane structure. As the resin having a spiro ring in the main chain, an aromatic polyester resin having a spiro ring can be used.

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.

The present specification also discloses a flame retardant (or flame-retardant composition) composed of a combination of the phosphorus compound and a resin having a spiro ring in the main chain.

[0019]

DESCRIPTION OF THE PREFERRED EMBODIMENTS [Thermoplastic resin] As the thermoplastic resin, various resins used for molding, for example, olefin resin, acrylic resin, styrene resin, polyamide resin, polyester resin, Polycarbonate resins, polyphenylene oxide resins, vinyl resins and the like can be mentioned. (1) Olefin-based resin Examples of the olefin-based resin include α-olefins such as ethylene, propylene, 1-butene, 3-methyl-1-pentene, 4-methyl-1-butene, 1-hexene and 1-octene. (Particularly, α-C _2-10 olefin) homo- or copolymer. As a preferred olefin-based resin, an ethylene unit is a main component (for example, 75 to 10).
0% by weight) containing ethylene-based resin (for example, polyethylene, ethylene-propylene copolymer, ethylene- (meth) acrylic acid copolymer, etc.), and propylene unit as a main component (for example, 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 resins can be used alone or in combination of two or more.

(2) Acrylic resin Examples of the acrylic resin include (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) and the like. Preferred acrylic resins include poly (methyl) methacrylate, alkyl acrylate-methyl methacrylate copolymer, (meth) acrylic acid-
Styrene copolymers, methyl (meth) acrylate-styrene copolymers and the like can be 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 styrene monomer (for example, styrene, vinyltoluene, α-methylstyrene, chlorostyrene, etc.) homopolymer or copolymer; styrene monomer And vinyl monomers (eg, unsaturated nitriles such as acrylonitrile, (meth) acrylates,
Copolymers with (meth) acrylic acid, α, β-monoolefinically unsaturated carboxylic acids such as maleic anhydride 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 on a rubber component (for example, AB obtained by graft-polymerizing styrene and acrylonitrile on polybutadiene).
S resin, AAS resin obtained by graft polymerization of styrene and acrylonitrile on acrylic rubber, AC obtained by graft polymerization of styrene and acrylonitrile on chlorinated polyethylene
S resin, a polymer obtained by graft-polymerizing styrene and acrylonitrile to ethylene-vinyl acetate copolymer, a polymer obtained by graft-polymerizing styrene and acrylonitrile to ethylene-propylene rubber, an MBS resin obtained by graft-polymerizing 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, a styrene-butadiene-styrene (SBS) block copolymer, a styrene-isoprene block copolymer,
Styrene-isoprene-styrene (SIS) block copolymer, hydrogenated styrene-butadiene-styrene (S
EBS) block copolymer, hydrogenated styrene-isoprene-styrene (SEPS) block copolymer) and the like.

(4) Polyamide Resin Polyamide includes polyamide derived from diamine and dicarboxylic acid; polyamide obtained by using aminocarboxylic acid and, if necessary, diamine and / or dicarboxylic acid; lactam; 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 ethylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, 2,2,4-trimethylhexamethylenediamine,
Aliphatic diamines such as 2,4,4-trimethylhexamethylenediamine and octamethylenediamine; aromatic diamines such as phenylenediamine and meta-xylylenediamine; bis (4-aminocyclohexyl) methane, bis (4-amino-3-) Alicyclic diamines such as methylcyclohexyl) methane; One or more of these diamines can be used.

Examples of the dicarboxylic acids include aromatic dicarboxylic acids such as phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, and naphthalene carboxylic acid; cyclohexane-1,4-dicarboxylic acid, cyclohexane-1,
3-dicarboxylic acid alicyclic dicarboxylic acids such as; glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, C _4-20 aliphatic dicarboxylic acids such as octadecanedioic acid; dimerized fatty acids ( Dimer acid).

[0026] As the amino acids, for example, amino heptanoic acid, aminononanoic acid, C _4-20 aminocarboxylic acids such as 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 the 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 The 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. Preferred polyester resins generally include saturated polyester resins, especially aromatic saturated polyester resins.

Examples of the dicarboxylic acid component include 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., naphthalenecarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, 2,6-naphthalenedicarboxylic acid, 4,4'-diphenylcarboxylic acid, 4,4
Dicarboxylic acids having about 8 to 16 carbon atoms, such as 4'-diphenoxyethercarboxylic acid, 4,4'-diphenylmethanedicarboxylic acid, and 4,4'-diphenylketonedicarboxylic acid, or derivatives thereof (for example, lower alkyl esters) , Acid anhydrides and other derivatives capable of forming an ester).

Further, if necessary, a polycarboxylic acid such as trimet acid and 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].

Further, if necessary, a polyol such as glycerin, trimethylolpropane, trimethylolethane or pentaerythritol may be used in combination.

Preferred diol components include C _2-4 alkylene glycols (linear alkylene glycols such as ethylene glycol, propylene glycol and 1,4-butanediol), and oxyalkylene units having about 2 to 4 repetitions. 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.

The lactone includes propiolactone, butyrolactone, valerolactone, caprolactone (for example,
_C3-12 lactone such as ε-caprolactone).

Preferred polyester resins include homopolyesters and copolyesters containing an alkylene arylate such as an alkylene terephthalate or an 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, poly 1,4-cyclohexane dimethylene terephthalate (PCT), polyethylene terephthalate (PET), polypropylene terephthalate (PPT), polybutylene terephthalate (PB)
Polyalkylene terephthalate such as T) and polyalkylene naphthalate (for example, poly C _2-4 such as polyethylene naphthalate and polybutylene naphthalate)
Homopolyesters such as alkylene naphthalate); copolyesters containing alkylene terephthalate and / or alkylene naphthalate units as main components (for example, 50% by weight or more); both dicarboxylic acid components and diol components are aromatic compounds Certain fully aromatic polyesters (eg, polyarylates, etc.) are 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 _2-4 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, for example, a transesterification reaction or a direct esterification method.

(6) Polycarbonate Resin Polycarbonate resin includes a dihydroxy compound,
Polymers obtained by reaction with phosgene or a carbonic acid diester [diaryl carbonate (such as diphenyl carbonate) or dialkyl carbonate (such as dimethyl carbonate and diethyl 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.

The terminal of the polycarbonate resin is
It may be blocked (bonded) with alcohols, mercaptans, phthalimides, etc. (particularly, monohydric alcohols). Examples of the monohydric alcohol that blocks the terminal of the polycarbonate resin include, for example, aryl alcohols (monohydric phenols which may be substituted with a C _1-10 alkyl group and / or a C _6-10 aryl group, For example, phenol, o, m or p-cresol, dimethylphenol, o, m or p-ethylphenol, o, m or p-
n-propylphenol, o, m or p-isopropylphenol, o, m or pn-butylphenol,
o, m or p-sec-butylphenol, o, m or pt-butylphenol, o, m or p-phenylphenol, o, m or p-benzylphenol, cumylphenol, etc., alkyl alcohols (methanol, C _1-20 alkyl alcohols such as ethanol, n-propanol, isopropanol, butanol, pentanol, hexanol, dodecyl alcohol, and stearyl alcohol; aralkyl alcohols (C _7-20 aralkyl alcohols such as benzyl alcohol and phenethyl alcohol) And so on.

(7) Polyphenylene oxide resin The polyphenylene oxide resin includes a homopolymer and a copolymer. As the homopolymer, poly (2,6)
-Dimethyl-1,4-phenylene) oxide, poly (2
-Methyl-6-ethyl-1,4-phenylene) oxide, poly (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 and the like.

Examples of the polyphenylene oxide copolymer include an alkylphenol-modified benzeneformaldehyde resin block obtained by reacting an alkylphenol such as cresol or p-tert-butylphenol with a benzeneformaldehyde resin or an alkylbenzeneformaldehyde resin, 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 Vinyl resins include 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.

Preferred vinyl resins include halogen-containing vinyl resins, for example, vinyl chloride resins such as polyvinyl chloride; polytetrafluoroethylene, polychlorotrifluoroethylene, polyvinylidene fluoride, polyvinyl fluoride, and tetrafluorocarbon. Examples thereof include fluorine-based resins such as an ethylene-hexafluoropropylene copolymer, a tetrafluoroethylene-perfluoroalkylvinyl ether copolymer, and a tetrafluoroethylene-ethylene copolymer.

(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 (for example, thermoplastic polysulfone, poly (ether sulfone), poly (4,4'-bisphenol ether sulfone, etc.); polyether imide; polyether ketone; poly (ether ether ketone); thermoplastic polyurethane resin (For example, a polymer obtained by reacting a diisocyanate compound such as tolylene diisocyanate with the glycol and / or the diamine, polytetramethylene glycol, etc. A thermoplastic elastomer; a polyoxybenzylene; a 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,
Examples thereof include a polyphenylene oxide resin, a polyphenylene sulfide resin, and a vinyl resin, and more preferably, a polyester resin, a polycarbonate resin, a polyamide resin, and a styrene resin, and particularly preferably a PBT resin.

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] The flame retardant of the present invention comprises a phosphorus-containing compound and a resin having a spiro ring in the main chain.
There is a feature that a thermoplastic resin can be highly flame-retarded by adding a small amount.

(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. These phosphorus-containing compounds can be used alone or in combination of two or more.

Among the above-mentioned organic phosphorus compounds, monomer-type organic phosphorus compounds include phosphate esters, phosphite esters, hypophosphite esters, phosphine oxides (such as triphenylphosphine oxide and tricresylphosphine oxide), phosphorus Acid amide, phosphite, hypophosphite and the like are included. As phosphate esters,
Aliphatic phosphates [tri-C _1-10 alkyl phosphates such as trimethyl phosphate, triethyl phosphate, tripropyl phosphate, triisopropyl phosphate, tributyl phosphate, triisobutyl phosphate; dimethyl phosphate, phosphoric acid Di C _1-10 alkyl phosphates such as diethyl, dipropyl phosphate, dibutyl phosphate, di (2-ethylhexyl) phosphate; mono C _1-10 alkyl phosphates, etc.], and aromatic phosphates [phosphoric acid] Triphenyl, tricresyl phosphate, trixylyl phosphate, diphenylcresyl phosphate, tri (isopropylphenyl) phosphate,
Tri-C phosphate such as diphenylethylcresyl phosphate
_6-20 aryl esters], aliphatic-aromatic phosphates (eg, methyldiphenyl phosphate, phenyldiethyl phosphate, etc.).

As the phosphite, there may be mentioned, for example, aromatic phosphites (triphenyl phosphite, tricresyl phosphite, trixylyl phosphite, diphenylcresyl phosphite) corresponding to the above-mentioned phosphoric esters. _Phosphites such as tri-C _6-20 aryl esters), aliphatic phosphites (trimethyl phosphite, triethyl phosphite, tripropyl phosphite, triisopropyl phosphite, tributyl phosphite, C _1-10 alkyl phosphites such as triisobutyl phosphate; di C _1-10 alkyl phosphites such as dimethyl phosphite, diethyl phosphite, dipropyl phosphite and dibutyl phosphite; phosphorous phosphite acid mono-C _1-10 alkyl ester, etc.), aliphatic - alkylphosphonic acids such as an aromatic phosphorous ester (methanephosphonic acid diphenyl Such as reel ester), and the like.

The monomer-type organic phosphorus compounds include hypophosphites, phosphonocarboxylates, phosphinicocarboxylates, and nitrogen-containing phosphates which may be substituted with an alkyl group or an aryl group. Is also included.

As the polymer type organic phosphorus compound,
A condensate of the monomer type organic phosphorus compound can be used. The condensate may have a structural unit represented by the following formula (2).

[0060]

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(Wherein, R ^{3 to} R ⁶ represent an aryl group which may have a substituent, Z represents an arylene group, and n represents 1 to
In the formula (2), examples of the aryl group represented by R ^{3 to} R ⁶ 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. _{Examples of the} arylene group include C _6-20 arylene groups such as phenylene, naphthylene and biphenylene.

The condensate represented by the above formula (2) includes
For example, resorcinol bis (diphenyl phosphate), resorcinol bis (dicresyl phosphate), resorcinol bis (dicylenyl phosphate), hydroquinone bis (diphenyl phosphate), hydroquinone bis (dicresyl phosphate), hydroquinone bis (dicylenyl phosphate), Bisphenol-A bis (diphenyl phosphate, bisphenol-A bis (dicresyl phosphate), bisphenol-A bis (dicylenyl 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). Examples of the phosphoric acid ester of such a polymer include the following formula (3)
And a polymer having a structural unit represented by

[0064]

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(In the formula, R ⁷ and R ⁸ represent an aryl group which may have a substituent.) The aryl group may be 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 compounds include polyphosphinicocarboxylic acid esters and polyphosphonamides. Examples of the polyphosphonamide include a polymer having a structural unit represented by the following formula (4).

[0067]

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(Wherein, R ⁹ represents an alkyl group, a cycloalkyl group, an aryl group, or an aralkyl group, and R ¹⁰ represents an alkylene group, an arylene group, or an aralkylene group.
¹¹ and R ¹² are the same or different and each represent a hydrogen atom, an alkyl group, or an aryl group. In addition, R ¹¹ and R ¹² 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-phenylphosphiniphosphinicopropionic acid) and nitrogen-containing phosphoric acid.

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

Preferred phosphorus-containing compounds include phosphate esters (aliphatic phosphate esters, aromatic phosphate esters, etc.), inorganic phosphorus compounds [(poly) phosphates such as ammonium polyphosphate and melamine polyphosphate, red And red phosphorus.

Red phosphorus has a high flame retardant effect, and can impart flame retardancy to a resin even in a small amount. Further, since the effect can be obtained with a small amount, flame retardancy can be achieved without impairing the characteristics (for example, mechanical characteristics and electrical characteristics) of the resin. As the red phosphorus, those subjected to a stabilization treatment (stabilized red phosphorus) are particularly preferably used. In particular, a method of pulverizing red phosphorus without pulverizing the red phosphorus and forming a crushed surface having high reactivity with water or oxygen on the surface of the red phosphorus, and furthermore, the surface of the red phosphorus is a resin (for example, , A thermosetting resin, a thermoplastic resin), a metal, a metal compound (for example, a metal hydroxide, a metal oxide, or the like) alone or in combination of two or more thereof is preferably red phosphorus.

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 of pulverizing red phosphorus into fine particles without forming a crushed surface on the surface of red phosphorus, and combining a metal component (metal hydroxide or metal oxide) film and a resin film to form a plurality of layers. In particular, red phosphorus which is coated with a metal component film and coated with a resin coating multiple times 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. Further, use is preferred from the viewpoints of safety when manufacturing a molded article and quality of a molded article.

The preparation of these stabilized red phosphorus is described in JP-A-9-67467, JP-A-6-115914, JP-A-5-229806, and JP-A-3-259.
No. 956, Japanese Unexamined Patent Publication No. Hei 2-2099991, Japanese Unexamined Patent Publication No. Hei 1-150309, Japanese Unexamined Patent Publication No. 62-21704, Japanese Unexamined Patent Publication No. 52-125489, EP29650
1A1 and EP249723A2 can be referred to.

As the red phosphorus, generally, stabilized red phosphorus can be used in the form of powder. The particle size of the stabilized red phosphorus is, for example, 0.01 to 100 μm, and preferably 0.1 to 70 μm.
μm, and more preferably about 0.1 to 50 μm.

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, those having different coating treatments and those having different particle sizes can be arbitrarily combined.

(Resin having a Spiro Ring in the Main Chain) A resin having a spiro ring in the main chain (hereinafter sometimes simply referred to as a spiro ring-containing resin) contains a spiro ring unit represented by the following formula (1). .

[0081]

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(Wherein X ₁ , X ₂ , X ₃ and X ₄ are independently selected from an alkylene group, an oxyalkylene group, an iminoalkylene group and a thioalkylene group, and the carbon atom contained in each group is The number is 1 to 6. Y represents the following group,

[0083]

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W represents a bond, an alkylene group, an oxyalkylene group, an iminoalkylene group, a thioalkylene group, or a divalent organic group having a branched structure in which some or all of the hydrogen atoms have been substituted with an alkyl group. It is. Examples of the alkylene groups represented by the groups X ₁ , X ₂ , X ₃ and X ₄ include C _1-6 alkylene groups such as methylene, ethylene, trimethylene, tetramethylene, pentamethylene, and hexamethylene groups. . As the oxyalkylene group, for example, oxymethylene, oxyethylene,
And C _1-6 oxyalkylene groups such as oxytrimethylene, oxytetramethylene, oxypentamethylene, and oxyhexamethylene groups. Examples of the iminoalkylene group include C _1-6 iminoalkylene groups such as iminomethylene, iminoethylene, iminotrimethylene, iminotetramethylene, iminopentamethylene, and iminohexamethylene. Examples of the thioalkylene group include C _1-6 thioalkylene groups such as thiomethylene, thioethylene, thiotrimethylene, thiotetramethylene, thiopentamethylene, and thiohexamethylene.

Examples of the alkylene group, oxyalkylene group, iminoalkylene group or thioalkylene group represented by the group W include the same groups as those exemplified for the group Y.

The above alkylene group, oxyalkylene group,
Examples of the alkyl group capable of partially or entirely substituting an iminoalkylene group or a thioalkylene group include methyl, ethyl,
C _1-4 alkyl groups such as propyl and butyl.

Specific examples of the group W include, for example, methylene, ethylene, propylene, tetramethylene, 2,2-
And a dimethyltrimethylene group.

The structure corresponding to the spiro ring unit obtained by removing the group W from the above formula (1) includes, for example, tetraoxaspiro [5,5] -undecane (for example, 2,4,8,10
-Tetraoxaspiro [5,5] -undecane, 1,
5,7,11-tetraoxaspiro [5,5] -undecane and the like.

The resin having a spiro ring in the main chain is, for example,
It can be formed by using a diol or a diamine shown below as a constituent monomer.

As the diol having a spiro ring, for example, 2,4,8,10-tetraoxaspiro [5,5]
Diols having undecane units, for example β, β,
β ′, β ′,-tetramethyl-2,4,8,10-tetraoxaspiro [5,5] undecane-3,9-diethanol and the like. As the diamine having a spiro ring, for example, a diamine having a 2,4,8,10-tetraoxaspiro [5,5] -undecane unit, for example, 3,9-bis (1,1-bismethyl-2-amino) Ethyl) -2,4,8,10-tetraoxaspiro [5
5] -undecane, 3,9-bis (3-aminopropyl) -2,4,8,10-tetraoxaspiro [5,
3,9-bis (aminoalkyl) -2,4,8,10-tetraoxaspiro [5, such as 5] -undecane
5] -undecane, particularly 3,9-bis (amino C _2-6 alkyl) -2,4,8,10-tetraoxaspiro [5,5] -undecane.

As the resin having a spiro ring in the main chain, a resin obtained from a diol or a diamine having a spiro ring unit represented by the formula (1) (for example, a polyester resin, a polycarbonate resin, a polyurethane resin, a polyamide resin) Resin, epoxy resin, etc.). These resins can be used alone or in combination of two or more.

Polyester resin having a spiro ring in the main chain The polyester resin having a spiro ring in the main chain includes a diol component containing at least a diol having a spiro ring, a dicarboxylic acid component, and if necessary, a lactone. Homopolyesters or copolyesters obtained by the reaction are included. Preferred polyester resins are usually
Saturated polyester resins, particularly aromatic saturated polyester resins, are included.

The diol component only needs to contain at least a diol having a spiro ring, and a diol having a spiro ring and a non-spiro ring diol may be used in combination. As the non-spirocyclic diol, diols exemplified in (5) Polyester resin in the section of [Thermoplastic resin], for example, aliphatic alkylene diols (for example, C _2-12 alkylene glycol, preferably
_2-10 alkylene glycol), polyoxy C _2-4 alkylene glycol, alicyclic diol, aromatic diol and the like. Preferred non-spirocyclic diol, alkylene glycols (e.g., ethylene glycol, propylene glycol, etc. C _2-4 alkylene glycols such as 1,4-butanediol), a polyoxyalkylene glycol [number of repetitions is about 2 to 4 of Oxy C
Glycols having _2-4 alkylene units (eg, poly (oxy-C _2-4 alkylene) glycols such as diethylene glycol, dipropylene glycol, ditetramethylene glycol, triethylene glycol, tripropylene glycol, and polytetramethylene glycol). . These non-spirocyclic diols can be used alone or in combination of two or more.

The ratio of the diol having a spiro ring to the non-spiro ring diol is 0.2 / 99.8 to the former / the latter.
100/0 (molar ratio), preferably 0.5 / 99.5 to
70/30 (molar ratio), more preferably 1/99 to 50
/ 50 (molar ratio), usually 1/99 to 30 /
It is about 70 (molar ratio).

As the dicarboxylic acid component, the dicarboxylic acids (aliphatic dicarboxylic acids, alicyclic dicarboxylic acids, and aromatic dicarboxylic acids) listed in (5) Polyester resin in the section of [Thermoplastic resin] or esters thereof can be used. Possible derivative components are included. These dicarboxylic acid components can be used alone or in combination of two or more. The preferred dicarboxylic acid component usually contains at least an aromatic dicarboxylic acid (such as benzenedicarboxylic acid and naphthalenedicarboxylic acid), and an aromatic dicarboxylic acid and an aliphatic dicarboxylic acid may be used in combination. The ratio of the aromatic dicarboxylic acid to the aliphatic dicarboxylic acid is usually the former / the latter =
100/0 to 30/70 (molar ratio), preferably 100
/ 0 to 50/50 (molar ratio), more preferably 100
/ 0 to 70/30 (molar ratio).

Lactones include propiolactone, butyrolactone, valerolactone, caprolactone (for example,
_C3-12 lactone such as ε-caprolactone). These lactones can be used alone or in combination of two or more.

If necessary, polyol (glycerin, trimethylolpropane, trimethylolethane,
Pentaerythritol and the like, and polyvalent carboxylic acids (such as trimellitic acid and pyromellitic acid) may be used in combination.

Specific examples of the aromatic polyester resin having a spiro ring in the main chain include a diol having at least a spiro ring (particularly, a diol having a 2,4,8,10-tetraoxaspiro [5,5] -undecane unit). Diol) containing a diol component and a dicarboxylic acid component containing at least an aromatic dicarboxylic acid (such as naphthalenedicarboxylic acid), such as a diol having a spiro ring and a C _2-4 alkylene glycol ( Examples include a copolyester resin composed of a diol component composed of ethylene glycol or the like or polyoxy _C2-4 alkylene glycol and an aromatic dicarboxylic acid component (naphthalenedicarboxylic acid or the like). These polyester resins can be used alone or in combination of two or more. Polyester resin having a spiro ring in the main chain, a conventional method, for example, transesterification,
It can be produced by a direct esterification method or the like.

Polycarbonate resin having a spiro ring in the main chain Polycarbonate resin having a spiro ring in the main chain includes:
A polymer obtained by a reaction between a diol having a spiro ring and phosgene or a carbonic acid diester [diaryl carbonate (eg, diphenyl carbonate) or dialkyl carbonate (eg, dimethyl carbonate, diethyl carbonate)] is included. The diol having a spiro ring may be used in combination with the bisphenol compound (such as bisphenol A) exemplified in (6) Polycarbonate resin in [Thermoplastic resin]. These polycarbonate resins can be used alone or in combination of two or more.

Polyurethane resin having a spiro ring in the main chain In the present specification, the polyurethane resin having a spiro ring in the main chain includes at least one component selected from a diol having a spiro ring and a diamine having a spiro ring. And a polymer obtained by a reaction with a diisocyanate component. That is, the polyurethane resin is a polyurethane resin obtained by reacting a diol having a spiro ring with a diisocyanate component, a polyurea urethane resin obtained by reacting a diamine having a spiro ring with a diisocyanate component, and a diol having a spiro ring. And a polyurethane urea resin obtained by reacting a diamine having a spiro ring with a diisocyanate component.

The diol component and / or diamine component is
The diol and / or the diamine having a spiro ring may be contained at least, and the diol and / or the non-spiro ring diamine may be contained. Examples of the non-spirocyclic diol include the diol components exemplified in the section of the polyester, and examples of the non-spirocyclic diamine include the diamine components exemplified in the section of the polyamide resin.

Examples of the diisocyanate component include aromatic diisocyanates (for example, phenylene diisocyanate, tolylene diisocyanate, diphenylmethane
4,4′-diisocyanate, etc.), araliphatic diisocyanate (eg, xylylene diisocyanate), alicyclic diisocyanate (eg, isophorone diisocyanate), aliphatic diisocyanate (eg, 1,6-hexamethylene diisocyanate, lysine diisocyanate) Etc.) are included. The diisocyanate component can be used alone or in combination of two or more. The diisocyanate component may be an adduct, and if necessary, may be used in combination with a polyisocyanate component such as triphenylmethane triisocyanate. Preferred diisocyanate components include aromatic and araliphatic diisocyanates.

The polyurethane-based resin is prepared by converting at least one active hydrogen atom selected from the diols and diamines having a spiro ring and the isocyanate group of the polyisocyanate component into the former / the latter = 0.8 / 1 to 1.2. / 1
(Molar ratio) by reacting at a ratio of about (molar ratio). These polyurethane resins can be used alone or in combination of two or more.

Epoxy resins having a spiro ring in the main chain Epoxy resins having a spiro ring in the main chain include ether epoxy resins obtained by the reaction of a diol having a spiro ring with epichlorohydrin, and spiro rings. And an amine-based epoxy resin obtained by the reaction of a diamine having the above formula with epichlorohydrin. These epoxy resins can be used alone or in combination of two or more.

In the resin composition, the epoxy resin comprises:
If necessary, amine-based curing agents (eg, aliphatic amines such as ethylenediamine, aromatic amines such as metaphenylenediamine, xylylenediamine, etc.), polyaminoamide-based curing agents, and acid and acid anhydride-based curing agents It may be used after being cured by a curing agent.

Polyamide resin having a spiro ring in the main chain The polyamide resin having a spiro ring in the main chain includes a diamine component containing at least a diamine having a spiro ring;
A homopolyamide or copolyamide obtained from a dicarboxylic acid component and, if necessary, a lactam is included.

The diamine component only needs to contain at least a diamine having a spiro ring, and may be used in combination with a non-spiro ring type diamine. As a non-spirocyclic diamine,
Examples of the diamine component (aliphatic diamine, alicyclic diamine, aromatic diamine) exemplified in the section of the polyamide resin can be given. Examples of the dicarboxylic acid component include the dicarboxylic acids (aliphatic dicarboxylic acids, alicyclic dicarboxylic acids, and aromatic dicarboxylic acids) listed in (4) Polyamide resin. These dicarboxylic acid components can be used alone or in combination of two or more. Examples of the lactam include the lactams exemplified in the section of the polyamide-based resin.

The polyamide resin having a spiro ring in the main chain can be produced by a conventional method, for example, a melt polycondensation method. These polyamide resins can be used alone or in combination of two or more.

The number average molecular weight of the spiro ring-containing resin is as follows:
There is no particular limitation, for example, 800 to 50 × 10 ⁴ , preferably 1000 to 30 × 10 ⁴ , more preferably 15 to 10 × 10 ⁴ .
00-1010 can choose from ⁴ about the range, usually, 80
It may be about 0-5 × 10 ⁴ .

(Ratio of Phosphorus-Containing Compound to Spiro Ring-Containing Resin) The amount of the phosphorus-containing compound used in the flame retardant is selected within a range capable of imparting flame retardancy.
1 to 200 parts by weight, preferably 10 to 100 parts by weight,
It is about 150 parts by weight, more preferably about 15 to 130 parts by weight. Usually, it is about 20 to 120 parts by weight.

(Use rate of flame retardant) The flame retardant of the present invention
By combining a phosphorus-containing compound and a spiro ring-containing resin, a high flame retardancy can be imparted to a thermoplastic resin even with a small amount of addition. 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, and the flame retardant is 0.1 to 100 parts by weight, preferably 100 parts by weight of the thermoplastic resin, preferably 1 to 80 parts by weight,
More preferably, it is about 5 to 60 parts by weight (particularly 5 to 40 parts by weight). When the amount of the flame retardant is less than 0.1 part by weight, it is difficult to make the flame retardant.

[0112] The amount of red phosphorus used is expressed in terms of red phosphorus.
The amount is about 0.1 to 30 parts by weight, preferably 1 to 25 parts by weight (for example, 1 to 15 parts by weight), and more preferably about 2 to 20 parts by weight, based on 100 parts by weight of the thermoplastic resin.

[Additives] The flame-retardant resin composition of the present invention contains various additives (for example, other flame retardants, anti-drip agents, antioxidants or stabilizers) as necessary. The total content of these additives may be 0.01 to 50 parts by weight, preferably 0.1 to 30 parts by weight, and more preferably 0.5 to 50 parts by weight, based on 100 parts by weight of the thermoplastic resin. About 20 parts by weight.

[Other Flame Retardants] The flame-retardant resin composition of the present invention provides other flame retardants, for example, nitrogen-containing flame retardants, sulfur-containing flame retardants, and silicon-containing flame retardants. It may contain a flame retardant, an alcohol flame retardant, an inorganic flame retardant (metal oxide, metal hydroxide, etc.).

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

Examples of the sulfur-containing flame retardant include, in addition to the sulfate ester, organic sulfonic acid, 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.). In particular, since the metal oxide also functions as a stabilizer for red phosphorus, even a small amount of the metal oxide is effective.

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 iron trioxide. Antimony, antimony tetroxide, antimony pentoxide and the like can be mentioned. Further, as the metal hydroxide, for example,
Examples include aluminum hydroxide, magnesium hydroxide, tin hydroxide, and zirconium hydroxide. In particular, since the metal oxide also functions as a stabilizer for red phosphorus, even a small amount of the metal oxide is effective.

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

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, especially about 0.1 to 100 parts by weight of the thermoplastic resin.
It can be selected from a range of about 20 parts by weight.

[Anti-Drip Agent] The flame-retardant resin composition of the present invention may further contain an anti-drip agent such as a fluororesin. The drip prevention agent can suppress the dripping of the fire and the melt during combustion. The fluorine-based resin includes a homo- or copolymer of a fluorine-containing monomer such as tetrafluoroethylene, chlorotrifluoroethylene, vinylidene fluoride, hexafluoropropylene, or perfluoroalkylvinyl ether; the fluorine-containing monomer, ethylene, propylene, ( A copolymer with a copolymerizable monomer such as (meth) acrylate is included. Examples of such a fluorine-based resin include homopolymers such as polytetrafluoroethylene, polychlorotrifluoroethylene, and polyvinylidene fluoride; tetrafluoroethylene-hexafluoropropylene copolymer, and tetrafluoroethylene-perfluoroalkyl Copolymers such as vinyl ether copolymer, ethylene-tetrafluoroethylene copolymer and 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 size 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 fluororesins can be used alone or in combination of two or more. The content of the fluorine-based resin is, for example, about 0.01 to 10 parts by weight, based on 100 parts by weight of the thermoplastic resin,
Preferably it is about 0.1 to 5 parts by weight, more preferably about 0.1 to 3 parts by weight.

[Antioxidant or Stabilizer] The flame-retardant resin composition of the present invention may contain an antioxidant or a stabilizer for maintaining heat resistance stably for a long period of time. Antioxidants or stabilizers include, for example, phenol-based (such as hindered phenols), amine-based (such as hindered amines), phosphorus-based, sulfur-based, hydroquinone-based, and quinoline-based antioxidants. Hindered phenolic antioxidants and / or phosphorus stabilizers are commonly used.

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.

Among hindered phenols, in particular,
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 alkanetriol-bis [3- (3,5-di-branched C3-6alkyl-4
-Hydroxyphenyl) propionate]; for example, pentaerythritol tetrakis [3- (3,5-di-t
-Butyl-4-hydroxyphenyl) propionate]
C _4-8 alkanetetraol tetrakis [3-
(3,5-di-branched C _3-6 alkyl-4-hydroxyphenyl) propionate] and the like.

[0129] 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], 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-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2 , 6-Di-t-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (nonylphenyl) pentaerythritol diphosphite, bis (nonylphenyl) pentaerythritol diphosphite, etc.], triphenyl phosphate stabilizer (For example, 4
-Phenoxy-9-α- (4-hydroxyphenyl)-
p-cumenyloxy-3,5,8,10-tetraoxa-4,9-diphosphapyro [5,5] undecane, tris (2,4-di-t-butylphenyl) phosphate, etc.), diphosphonite stabilizers (for example, Tetrakis (2,4-di-t-butyl) -4,4′-biphenylenediphosphonite and the like. Phosphorus stabilizers are usually branched C _3-6 alkylphenyl groups (particularly t-
Butylphenyl group).

The hydroquinone 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, about 0.01 to 5 parts by weight, preferably about 0.05 to 2.5 parts by weight, particularly about 0.1 to 1 part by weight based on 100 parts by weight of the thermoplastic resin. You can choose from a range.

When an inorganic phosphorus compound is added, the thermal stability is further improved. Examples of the inorganic phosphorus compound include inorganic phosphoric acid (phosphoric acid, phosphorous acid, phosphonic acid, phosphinic acid, polyphosphoric acid, polyphosphorous acid, phosphonocarboxylic acid, nitrogen-containing phosphoric acid, and the like) and acidic metal salts thereof. And the like.

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 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 the resin highly flame retardant, probably because it promotes carbonization of the resin surface during combustion. Further, by combining the phosphorus-containing compound and the spiro ring-containing resin, even a small amount of the thermoplastic resin can be effectively made flame-retardant, and bleed-out and heat resistance are not reduced.

[Filler] The flame-retardant 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 (plate-like filler, granular 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 (such as milled glass fiber), calcium silicate, aluminum silicate, kaolin, talc, clay, and silica. Silicates such as algae 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; carbonates of metals such as calcium sulfate and barium sulfate Salts; metal sulfates such as calcium sulfate and barium sulfate, and metal powders such as silicon carbide. Examples of the plate-like filler include glass flake, mica, graphite, and various metal foils.

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

Further, particularly preferred 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. As such a sizing agent or surface treatment agent,
For example, a functional compound such as an epoxy compound, a silane compound, or a titanate compound is used. Preferably, an epoxy compound, in particular, a bisphenol A type or novolak type epoxy resin is used.

The filler may have been subjected to surface treatment or convergence 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.

When performing the surface treatment, the amount of the functional surface treating agent used is, for example, 5% by weight or less, preferably about 0.05 to 2% by weight, based on the filler.

[Production Method of Flame-Retardant Resin Composition] The flame-retardant resin composition of the present invention may be a powder mixture or a melt mixture, and may contain a thermoplastic resin, a flame retardant, and if necessary, a drip. It can be prepared by mixing an inhibitor and other additives in a conventional manner. 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 the preparation of a composition used for a molded article, a granular material of a thermoplastic resin (for example, a granular material obtained by crushing a part or all of a polyester resin)
And mixing with other components (such as a flame retardant) and melt-kneading is advantageous in improving the dispersion of the other components.

From the viewpoint of handling, it is convenient to prepare a master batch by temporarily melting and mixing at least two components selected from a thermoplastic resin, a spiro ring-containing resin 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 composed of resin components,
A part of the thermoplastic resin is often used for a master batch.

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 spiro ring-containing resin and a phosphorus-containing compound, and (3) a part of a thermoplastic resin. And a master batch composed of a spiro ring-containing resin and a phosphorus compound.

The masterbatch may contain various additives, for example, a fluororesin, an antioxidant, a phosphorus-based stabilizer, a filler, and the like, if necessary.

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

[0150] Molded articles formed by conventional methods such as extrusion molding, injection molding, and compression molding after melt-kneading the flame-retardant resin composition of the present invention have excellent flame retardancy and moldability. Therefore, it can be used for various purposes. For example, it can be suitably used for mechanical mechanism parts, electric / electronic parts, automobile parts, packaging materials and cases, and the like.

[0151]

According to the present invention, since a thermoplastic resin is combined with a flame retardant composed of a phosphorus-containing compound and a resin having a spiro ring in the main chain, it is possible to use a small amount without using a halogen-based flame retardant. Even flame retardant. Furthermore, the flame-retardant resin composition of the present invention can suppress bleed-out and can maintain mechanical properties at a high level without using a special compound.

[0152]

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 resin composition was evaluated for flame retardancy and physical properties 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 was observed Δ: Slight bleed-out was observed ×: Bleed-out was observed in a large amount 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.)
[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 master batch Using a vented twin screw extruder, red phosphorus (B-2) and polybutylene terephthalate (A-1) were used to prepare (B-1)
-2) / (A-1) = 30/70 (weight ratio) red phosphorus masterbatch. [Spiro Ring-Containing Resin C] Production Example 1 (Synthesis of Spiro Ring-Containing Resin (C-1)) Titanium tetrabutoxide (hereinafter abbreviated as TBT) 0.5 as a catalyst
In the presence of 5 parts by weight (550 ppm), β, β, β ′,
β ',-tetramethyl-2,4,8,10-tetraoxaspiro [5,5] undecane-3,9-diethanol (hereinafter abbreviated as SPG) 20.9 parts by weight and 2,6-naphthalenedicarboxylic acid Acid dimethyl ester (hereinafter referred to as NDA
8-1 part by weight) and ethylene glycol 2
7.8 parts by weight were subjected to a transesterification reaction according to a conventional method.
Next, the temperature of the reaction system was gradually increased and reduced, and finally 260
An amorphous copolyester (C-1) was obtained by performing a polycondensation reaction under a reduced pressure of 1 mmHg or less at a temperature of 1 ° C. Glass transition temperature was 122 ° C. (Synthesis of Spiro Ring-Containing Resin (C-2)) Production Example 2 Instead of NDA-1, a mixture of 2,6-naphthalenedicarboxylic acid dimethyl ester and 2,7-naphthalenedicarboxylic acid dimethyl ester (mixing ratio 2,6 Body / 2
A copolyester (C-2) was obtained in the same manner as in Production Example 1, except that 7 units = 9/1 (weight ratio, hereinafter abbreviated as NDA-2). Glass transition temperature was 122 ° C. Production Example 3 (Synthesis of Spiro Ring-Free Resin (C-3)) NDA-1
Production Example 1 except that 84.0 parts by weight and 157 parts by weight of ethylene glycol were used and the final polycondensation temperature was 290 ° C.
Polycondensation was performed in the same manner as in Example 1 to obtain a crystalline polyester (C-3) having a glass transition temperature of 121 ° C and a melting point of 268 ° C.

[Antioxidant D] D-1: Pentaerythritol-tetrakis [3-]
(3,5-di-t-butyl-4-hydroxyphenyl)
Propionate] (Irganox 1010, manufactured by Ciba Geigy) [Phosphorus stabilizer E] E-1: Tetrakis (2,4-di-t-butylphenyl) -4,4′-biphenylenediphosphonite (sandwich) Stub P-EPQ, manufactured by Sando Co., Ltd.) [Drip preventing agent F] F-1: Polytetrafluoroethylene [Filler G (glass fiber)] G-1: Chopped strand having a diameter of 10 μm and a length of 3 mm Example 1 -4 and Comparative Examples 1 and 2 The above components were mixed with polybutylene terephthalate (A-1) at the ratio shown in Table 1, kneaded with an extruder, and extruded to prepare a resin composition. This resin composition was injection-molded to produce a test molded article, and the flammability, tensile properties and molded appearance (bleed-out) were evaluated.

Table 1 shows the results.

[0157]

[Table 1]

 ──────────────────────────────────────────────────の Continuing on the front page (72) Inventor Shinya Yamada 973 Miyajima, Fuji-shi, Shizuoka Prefecture F-term inside Polyplastics Co., Ltd. EJ017 EU186 EW046 EW066 EW068 FD019 FD038 FD077 FD078 FD13X FD136

Claims (22)

[Claims] 1. A resin composition comprising a thermoplastic resin and a flame retardant, wherein the flame retardant comprises a phosphorus-containing compound and a resin having a spiro ring in the main chain. . 2. The flame-retardant resin composition according to claim 1, wherein the thermoplastic resin is a polyester resin. 3. The flame-retardant resin composition according to claim 1, wherein the thermoplastic resin is a homo- or copolyester having at least one unit selected from alkylene terephthalate and alkylene naphthalate. 4. A homo- or copolyester in which 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 5. 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. 6. The method of claim 1, wherein the phosphorus-containing compound is at least one selected from red phosphorus, a (poly) phosphate and a phosphate.
The flame-retardant resin composition according to claim 1, which is a seed. 7. The flame-retardant resin composition according to claim 1, wherein the phosphorus-containing compound is stabilized red phosphorus. 8. The flame-retardant resin composition according to claim 1, wherein the resin having a spiro ring in the main chain contains at least a spiro ring unit represented by the following formula (1). Embedded image (In the formula, X ₁ , X ₂ , X ₃ , and X ₄ are independently selected from an alkylene group, an oxyalkylene group, an iminoalkylene group, and a thioalkylene group, and each group has 1 carbon atom. And Y is the following group: W is a bond, an alkylene group, an oxyalkylene group, an iminoalkylene group, a thioalkylene group, or a divalent organic group containing a branched structure in which some or all of the hydrogen atoms have been substituted with an alkyl group. ) 9. The flame-retardant resin composition according to claim 8, wherein the spiro ring unit has at least a 2,4,8,10-tetraoxaspiro [5,5] -undecane structure. 10. The flame-retardant resin composition according to claim 1, wherein the resin having a spiro ring in the main chain is an aromatic polyester having a spiro ring. 11. A resin having a spiro ring in the main chain, wherein the resin comprises at least a diol component containing a diol having a tetraoxaspiro [5,5] -undecane unit, and a dicarboxylic acid containing at least an aromatic dicarboxylic acid or an ester-forming derivative thereof. The flame-retardant resin composition according to claim 1, which is a polyester comprising an acid component. 12. With respect to 100 parts by weight of the thermoplastic resin,
The flame-retardant resin composition according to claim 1, comprising 0.1 to 50 parts by weight of a flame retardant. 13. The flame-retardant resin composition according to claim 1, wherein the flame retardant contains 1 to 200 parts by weight of the phosphorus-containing compound based on 100 parts by weight of the resin having a spiro ring in the main chain. 14. With respect to 100 parts by weight of the thermoplastic resin,
The flame-retardant resin composition according to claim 1, comprising 1 to 15 parts by weight of red phosphorus. 15. The flame-retardant resin composition according to claim 1, further comprising a fluorine-based resin. 16. The flame-retardant resin composition according to claim 1, further comprising a hindered phenolic antioxidant. 17. The flame-retardant resin composition according to claim 1, further comprising a phosphorus-based stabilizer. 18. The flame-retardant resin composition according to claim 1, further comprising a filler. 19. A method for producing a flame-retardant resin composition by mixing a thermoplastic resin with the flame retardant according to claim 1. 20. A masterbatch comprising at least two components selected from the group consisting of a resin having a spiro ring in the main chain, a phosphorus-containing compound and a thermoplastic resin according to claim 1,
The method for producing a flame-retardant resin composition according to claim 19, wherein the thermoplastic resin is melt-mixed. 21. A molded article formed from the flame-retardant resin composition according to claim 1. 22. The molded article according to claim 21, wherein the molded article is a mechanical mechanism part, an electric / electronic part, or an automobile part.