JP2000178459A - Flame-retardant resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a flame-retardant resin composition made flame-retardant without using any halogen-based flame retardant. SOLUTION: This flame-retardant resin composition comprises a thermoplastic resin (e.g. a polyester resin) and a flame retardant; wherein the flame retardant is composed of a phosphorus-contg. compound (e.g. red phosphorus) and an aralkyl resin. This resin composition may comprise 100 pts.wt. of a thermoplastic resin and 0.1-100 pts.wt. of a flame retardant which, in turn, may composed of 100 pts.wt. of an aralkyl resin and 1-100 pts.wt. of a phosphorus-contg. compound; wherein the aralkyl resin is pref. such one as to have repeating group of the formula (Ar is an aromatic group; R1 and R2 are each an alkylene group; R3 is H or an alkyl; X is OH, amino or an N-substituted amino group).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a thermoplastic resin,
Flame-retardant resin composition containing a phosphorus-containing compound and a flame retardant composed of an aralkyl resin, and 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. Therefore, it is used for various applications such as electric / electronic parts, mechanical mechanism parts, and automobile parts. On the other hand, the thermoplastic resin is required to have improved mechanical properties and to be flame-retardant for safety as the field of application is expanded. Generally, a method is known in which a flame retardant is added to a thermoplastic resin by adding a flame retardant using a halogen compound or an antimony compound.

Japanese Patent Application Laid-Open No. 63-150349 discloses a mixed resin comprising a polyamide resin and nylon 66, glass fiber, an organic halogen-based flame retardant, antimony trioxide, and a hydroxide of an alkali metal or an alkaline earth metal. And a flame-retarded resin composition is disclosed. 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.

[0004] Japanese Patent Application Laid-Open No. 64-14277 discloses a flame retardancy obtained by adding a specific amount of a flame retardant comprising a silicone oil, a silicone resin, and a phosphorus-containing nitrogen compound (ammonium polyphosphate) to a thermoplastic resin (polypropylene). 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.

[0005] 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 to impart flame retardancy without deteriorating the properties of the resin by the conventional method. 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.

[0007]

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.

It is still another object of the present invention 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, 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 comprises a phosphorus-containing compound and an aralkyl resin. The flame retardant resin composition may contain about 0.1 to 100 parts by weight of a flame retardant based on 100 parts by weight of the thermoplastic resin. In addition, the flame retardant is the phosphorus-containing compound 1 to 100 with respect to 100 parts by weight of the aralkyl resin.
It may contain about parts by weight. The thermoplastic resin includes an olefin resin, an acrylic resin, a styrene resin, a polyamide resin, a polyester resin, a polycarbonate resin, a polyphenylene oxide resin, a vinyl resin, and the like. Phosphorus-containing compounds include red phosphorus, (poly)
Phosphates, phosphates and the like are included. Further, the aralkyl resin may have a repeating unit represented by the following formula (1).

[0012]

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(Wherein, Ar represents an aromatic group, R ¹ and R ² are the same or different and represent an alkylene group, R ³ represents a hydrogen atom or an alkyl group. X represents a hydroxyl group, an amino group or N -Represents a substituted amino group) Further, the flame-retardant resin composition of the present invention is a fluororesin,
It may contain at least one selected from a hindered phenolic antioxidant, a phosphorus-based stabilizer, a nitrogen-containing flame retardant, a filler and the like.

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.

[0015]

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) 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-based resins can be used alone or in combination of two or more.

(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) 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 (eg, 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. As the polystyrene-based graft copolymer, a copolymer in which at least a styrene-based monomer and a copolymerizable monomer are graft-polymerized on a rubber component (for example, A in which styrene and acrylonitrile are graft-polymerized on polybutadiene).
AAS resin in which styrene and acrylonitrile are graft-polymerized to BS resin and acrylic rubber, and A in which styrene and acrylonitrile are graft-polymerized to chlorinated polyethylene
CS resin, a polymer obtained by graft-polymerizing styrene and acrylonitrile to an ethylene-vinyl acetate copolymer, a polymer obtained by graft-polymerizing styrene and acrylonitrile to an 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. Examples of the block copolymer include copolymers 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 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).

[0023] 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 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. is there. Preferred polyester resins are usually saturated polyester resins,
Particularly, an aromatic saturated polyester resin is included.

Examples of the dicarboxylic acid component include aliphatic dicarboxylic acids (for example, those 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). These dicarboxylic acid components may be used alone or in combination of two or more. Further, if necessary, a polyvalent carboxylic acid such as trimetic 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-cyclohexane dimethylol, hydrogenated bisphenol A, etc.), aromatic diols [for example, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis- (4- (2-hydroxyethoxy) phenyl] ) Propane, xylylene glycol, etc.]. These diol components may be used alone or in combination of two or more. In addition, if necessary, glycerin,
A polyol such as 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 about 2 to 4 repetitions. Polyoxyalkylene glycols [glycols containing poly (oxy-C _2-4 alkylene) units such as diethylene glycol], 1,4-cyclohexane dimethylol and the like are included.

The oxycarboxylic acid includes, for example, 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 lactone such as ε-caprolactone).

Preferred polyester resins include homopolyesters and copolyesters containing alkylene acrylates such as alkylene terephthalate and alkylene naphthalate as main components (for example, about 50 to 100% by weight, preferably about 75 to 100% by weight), for example, , Polyalkylene terephthalate (for example, 1,4-cyclohexyl dimethylene terephthalate, polyethylene terephthalate (PET), polypropylene terephthalate (PP
T), homopolyesters such as poly C _2-4 alkylene terephthalate such as polybutylene terephthalate (PBT), polyalkylene naphthalate (eg, poly C _2-4 alkylene naphthalate such as polyethylene naphthalate and polybutylene naphthalate); A copolyester containing an alkylene terephthalate and / or alkylene naphthalate unit as a main component (for example, 50% by weight or more); a completely aromatic polyester in which both a dicarboxylic acid component and a diol component are aromatic compounds (for example, Polyarylate). 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 glycol (such as linear alkylene glycol such as ethylene glycol, propylene glycol and 1,4-butanediol), and the number of repetitions. 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.).

Incidentally, 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 is not impaired. Further, 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 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-based resin The polyphenylene oxide-based 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, etc.) Polysulfone (for example, thermoplastic polysulfone, poly (ether sulfone), poly (4,4'-bisphenol ether sulfone, etc.); polyether ketone; poly (ether ether ketone); polyether imide; thermoplastic polyurethane resin ( For example, a polymer obtained by reacting a diisocyanate compound such as tolylene diisocyanate with the glycol and / or the diamine,
Polyurethane elastomers which may have segments such as polytetramethylene glycol); thermoplastic polyimides; polyoxybenzylenes; thermoplastic elastomers 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 polyphenylene sulfide-based resins and vinyl-based resins, and more preferred examples include polyester-based resins, polycarbonate-based resins, polyamide-based resins, and styrene-based resins, and PBT-based resins are particularly preferred.

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 1.5 × 10
^Four~ 30 × 10^FourDegree.

[Flame Retardant] In the present invention, by constituting the flame retardant with a phosphorus-containing compound and an aralkyl resin, high flame retardancy can be imparted to a wide range of thermoplastic resins 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,
Aryl esters of alkyl phosphonic acids such as diphenyl methanephosphonate, alkyl esters of alkyl phosphonic acids such as diethyl methanephosphonate, and the like.

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 structural unit represented by the following formula (3).

[0054]

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(Wherein, R ^{4 to} R ⁷ represent an aryl group which may have a substituent, Z represents a divalent aromatic group, and n represents an integer of 1 to 5). In 3), examples of the aryl group represented by R ^{4 to} R ⁷ include a C _6-20 aryl group such as phenyl and naphthyl, and a substituent of the aryl group includes an alkyl group such as a methyl group and an ethyl group. Is mentioned. Examples of the divalent aromatic group include an arylene group (for example, a C _6-20 arylene group such as a phenylene and naphthylene group), a group having a plurality of the above-mentioned arylene groups [bisphenol residue (bisphenol A residue) , Bisphenol D residue,
A group in which a hydroxyl group has been removed from a bisphenol such as a bisphenol AD residue), a biphenylene group, etc.].

As the condensate represented by the above formula (3),
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) and the like can be mentioned.

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 (4)
And a polymer having a structural unit represented by

[0058]

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(In the formula, R ⁸ and R ⁹ represent an aryl group which may have a substituent.) The aryl group is a C _6-20 aryl group, especially 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 a polyphosphonamide. Examples of the polyphosphonamide include a polymer having a structural unit represented by the following formula (5).

[0061]

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(Wherein, R ¹⁰ represents an alkyl group, a cycloalkyl group, an aryl group, or an aralkyl group, and R ¹¹ represents an alkylene group, an arylene group, or an aralkylene group.
¹² and R ¹³ are the same or different and represent a hydrogen atom, an alkyl group, or an aryl group. In addition, R ¹² and R ¹³ may form a ring together with the adjacent nitrogen atom and R ^11. ) 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 in the periodic table (such as an aluminum salt), and an ammonium salt. it can. 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 metal salt of an acid such as hypophosphorous acid, phosphonocarboxylic acid, or nitrogen-containing phosphoric acid which may be substituted with an alkyl group or an aryl group.

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

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

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 which have been subjected to a stabilization treatment (stabilized red phosphorus) can be usually used. In particular, the surface of red phosphorus is used alone or in combination with a resin (for example, a thermosetting resin or a thermoplastic resin), a metal, a metal compound (for example, a metal hydroxide, a metal oxide, or the like).
Red phosphorus coated in combination of more than one species is preferred.

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 coating of a metal component (a metal hydroxide or a metal oxide) and a coating of a resin are combined to form a coating with a plurality of layers, and in particular, a coating with a metal component and then a coating with a resin. Red phosphorus 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.

As red phosphorus, stabilized red phosphorus can usually 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.

(Aralkyl Resin) As the aralkyl resin used in the present invention, a compound having a repeating unit represented by the above formula (1) can be used.

The aromatic group represented by Ar is preferably an aromatic group having 6 to 20 carbon atoms, such as a phenylene group (eg, o-phenylene group, m-phenylene group, p-phenylene group) and a naphthylene group. Is a phenylene group (particularly, a p-phenylene group).

Examples of the alkylene group represented by R ¹ and R ² 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.

R^ThreeExamples 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.

Preferred aralkyl resins are phenol aralkyl resins wherein X is a hydroxyl group, especially
Examples of the resin include a resin in which R ¹ and R ² are a methylene group, Ar is a phenylene group, R ³ is a hydrogen atom, and a p-xylene-substituted phenol represented by the following formula as a repeating unit.

[0077]

Embedded image

The aralkyl resin is generally represented by the following formula (2)
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.

Y—R ¹ —Ar—R ² —Y (2) (in the formula, Y represents an alkoxy group, an acyloxy group, a hydroxyl group or a halogen atom; Ar, R ¹ and R ² are the same as described above) In (2), 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.

The compound represented by the above formula (2) includes
For example, xylylene glycol C _1-4 alkyl ethers (p- xylylene glycol dimethyl ether, p- xylylene, etc. glycol diethyl ether) aralkyl ethers such as, p- xylylene-.alpha., acyloxyalkyl aralkyl such as α'- diacetate Aralkyl diols such as, p-xylylene-α, α'-diol;
aralkyl halides such as p-xylylene-α, α′-dichloride and p-xylylene-α, α′-dibromide;

Examples of 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 (2) to phenols or anilines is, for example, the former / the 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 (2) with a phenol or aniline 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 (2), 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, about 50 to 250 ° C., preferably about 100 to 230 ° C. When aralkyl halides are used as a reactant, the reaction temperature may be lower than the above temperature, for example, 50 to 150.
C., about 70 to 130.degree.

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.

In 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 aralkyl resin thus obtained has a softening point of, 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).

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

(Ratio of phosphorus-containing compound to aralkyl resin) The amount of the phosphorus-containing compound used in the flame retardant is selected within a range capable of imparting flame retardancy, and 100 parts by weight of the phenol aralkyl resin is used. 1 to 100 parts by weight, preferably 5 to 80 parts by weight, more preferably 1 to 100 parts by weight
It is about 0 to 60 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 to 100 parts by weight
It is about 50 parts by weight, more preferably about 5 to 30 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. When 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 contains various additives (for example, other flame-retardants, fluorine-based resins, antioxidants or stabilizers) as necessary. The total content of these additives may be, for example, 0.01 to 5 parts by weight based on 100 parts by weight of the thermoplastic resin.
It is about 0 parts by weight, preferably about 0.1 to 30 parts by weight, and more preferably about 0.5 to 20 parts by weight.

(Other Flame Retardants) The flame retardant resin composition of the present invention further imparts flame retardancy to the composition so that other flame retardants such as nitrogen-containing flame retardants, sulfur-containing flame retardants, and silicon-containing flame retardants are used. , Alcohol-based flame retardants, inorganic-based flame retardants (metal oxides,
Metal hydroxide).

Examples of the nitrogen-containing flame retardant include amines such as ureas, guanidines, and triazine compounds (eg, 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 organic sulfonic acid, sulfamic acid, organic sulfamic acid, and salts, esters, and amides thereof, in addition to the sulfate ester.

The silicon-containing flame retardants include (poly) organosiloxanes. Examples of the (poly) organosiloxane include monoorganosiloxanes such as dialkylsiloxanes (eg, dimethylsiloxane), alkylarylsiloxanes (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, as a metal oxide
Is, for example, molybdenum oxide, tungsten oxide, oxide
Titanium, zirconium oxide, tin oxide, copper oxide (Cu
O, Cu _TwoO), zinc oxide, aluminum oxide,
Nickel, iron oxide (FeO, Fe_TwoO _Three, Fe_ThreeO_FourSuch),
Manganese oxide, antimony trioxide, antimony tetroxide,
And antimony pentoxide. Metal hydroxide
For example, aluminum hydroxide, magnesium hydroxide
, Tin hydroxide, and zirconium hydroxide.

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

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 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.

(Fluorine Resin) The flame-retardant resin composition of the present invention may further contain an anti-drip agent such as a fluorine resin. The drip preventing agent can suppress the drip (drip) of the fire and the melt during combustion. The fluororesin includes homo- or copolymers of fluorine-containing monomers such as tetrafluoroethylene, chlorotrifluoroethylene, vinylidene fluoride, hexafluoropropylene, and perfluoroalkylvinyl ether; the fluorine-containing monomers, ethylene, propylene, and acrylate. And other copolymerizable monomers. 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,
One type or a mixture of two or more types can be used.

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 100 to 700 μm.

The content of the fluororesin is, for example, about 0.01 to 10 parts by weight, preferably about 0.1 to 5 parts by weight, and more preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the thermoplastic resin. It is about 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. 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 (or stabilizers). included.

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 the 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 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].

[0112] 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-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 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 flame retardant resin composition of the present invention may contain other additives according to the purpose. Other additives include stabilizers (such as ultraviolet absorbers, heat stabilizers, and weather stabilizers), lubricants, release agents, and colorants. (Filler) 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 (for example, milled glass fiber),
Silicates such as calcium silicate, aluminum silicate, kaolin, talc, clay, diatomaceous earth and wollastonite; metal oxides such as iron oxide, titanium oxide, zinc oxide and alumina; calcium carbonate and magnesium carbonate Metal carbonates include metal sulfates such as 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 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. Such sizing agents or surface treatment agents include functional compounds. Examples of the functional compound include an epoxy-based compound, a silane-based compound, a titanate-based compound, preferably an epoxy-based compound, particularly a bisphenol A-type epoxy resin and a novolak-type epoxy resin.

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 flame retardant of the present invention can make the resin highly flame retardant, probably because it promotes carbonization of the resin surface during combustion. By combining a phosphorus-containing compound and an aralkyl resin, even a small amount can effectively render the thermoplastic resin flame-retardant, and does not reduce bleed-out or heat resistance.

[Production Method of Flame-Retardant Resin Composition] The flame-retardant resin composition of the present invention may be a mixture of powder and granules or a molten mixture. The thermoplastic resin, the flame retardant, and the drip if necessary It can be prepared by mixing an antioxidant, an antioxidant, a filler or other additives in a conventional manner. For example, a method of mixing the components, kneading and extruding with a single-screw or twin-screw extruder to prepare pellets, and then molding.
Once a pellet (masterbatch) having a different composition is prepared, the pellet is mixed (diluted) in a predetermined amount and subjected to molding, and a method of obtaining a molded product having a predetermined composition is performed. A direct charging method 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, it is convenient to prepare a master batch by temporarily melting and mixing at least two components selected from a thermoplastic resin, an aralkyl 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.

The masterbatch includes, for example, (1) a masterbatch composed of a part of a thermoplastic resin and a phosphorus-containing compound, (2) a masterbatch composed of an aralkyl resin and a phosphorus-containing compound, (3) A) A masterbatch composed of a part of a thermoplastic resin, an aralkyl resin, and a phosphorus-containing compound.

The masterbatch may contain various additives, for example, a fluorine resin, 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.

Further, 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.

[0134]

According to the present invention, since a flame retardant composed of a phosphorus-containing compound and an aralkyl resin is used, the thermoplastic resin can be made flame-retardant without using a halogen-based flame retardant. Furthermore, the flame-retardant resin composition of the present invention can suppress bleed-out and discoloration, and can maintain mechanical properties at a high level without using a special compound.

[0135]

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 and the like of the resin composition were evaluated by the following tests.

(Flammability Test) Flammability was evaluated based on UL 94 at a test piece thickness of 0.8 mm.

(Tensile test and bending test) ASTM D
The tensile properties and bending properties were evaluated according to -638 and D-790.

(Forming Appearance and Discoloration) The combustion test piece was treated in a gear oven at 120 ° C. for 24 hours, and the appearance and discoloration were evaluated. The evaluation criteria are shown below.

Appearance: ＝= No bleed-out observed Δ = Slight bleed-out observed X = Severe bleed-out observed Discoloration: ＝= Nearly discoloration observed X = Appreciable discoloration observed In Examples and Comparative Examples, the following thermoplastic resins and flame retardants were used.

[Thermoplastic Resin A] A-1: Polybutylene terephthalate (Duranex, intrinsic viscosity = 1.0, manufactured by Polyplastics Co., Ltd.) A-2: Polybutylene phthalate modified with 12.5 mol% isophthalic acid A-3: Polyethylene terephthalate (Bellpet E
FG10, manufactured by Kanebo Co., Ltd.) A-4: Polycarbonate (Panlite L1225, manufactured by Teijin Chemicals Ltd.) A-5: Nylon-6,6 (polyplastic nylon 66, manufactured by Polyplastics Co., Ltd.) A-6 : ABS resin (styrene 41% by weight, acrylonitrile 14% by weight, butadiene 45% by weight) A-7: ABS resin (Sebian JD, manufactured by Daicel Chemical Industries, Ltd.) A-8: PBT elastomer (PBT segment 60% by weight, Poly (tetramethylene oxide glycol) terephthalate segment 40% by weight) A-9: PET-based liquid crystal elastomer Melting and mixing PET and p-acetoxybenzoic acid to form a polyester fragment by an acidolysis reaction, and polycondensing the fragment. Liquid crystal polyester obtained by It has the following structural units.

[0142]

Embedded image

The ratio of k, l and m is k / l / m
= 80/20/20 (molar ratio).

A-10: Polybutylene terephthalate (Duranex, intrinsic viscosity = 0.75, manufactured by Polyplastics Co., Ltd.) [Flame retardant] (phosphorus-containing compound B) B-1: Red phosphorus (Nova Excel 140, 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, red phosphorus (B- 1) and (B-1) prepared from 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 phosphate ester (PX-201, manufactured by Daihachi Chemical Industry Co., Ltd.) B-8: Condensed phosphate ester (Phirol Flex RDP, manufactured by Akzo Nobel Co., Ltd.) B -9: Condensed phosphate ester (Phirol Flex BDP, manufactured by Akzo Nobel Co., Ltd.) B-10: Bisphenol A bis (dicresyl phosphate) B-11: Melamine polyphosphate (MPP-A, Sanwa Chemical Co., Ltd.) (Aralkyl resin and phenol novolak resin C) C-1: Phenol aralkyl resin (Mirex XL-
225, manufactured by Mitsui Chemicals, Inc.) C-2: Phenol aralkyl resin (Mirex XL-
325, manufactured by Mitsui Chemicals, Inc.) C-3: Phenol aralkyl resin (Mirex XLC
-LL, manufactured by Mitsui Chemicals, Inc.) C-4: Boric acid-modified phenol aralkyl resin 100 parts by weight of phenol aralkyl resin (C-1) is heated and melted, and 5 parts by weight of boric acid is added while maintaining at 140 ° C.
A boric acid-modified aralkyl resin obtained by adding over time and then reacting at 150 ° C. for 2 hours.

C-5: Phosphoric acid-modified phenol aralkyl resin 100 parts by weight of phenol aralkyl resin (C-1) are heated and melted, and 5 parts by weight of phosphoric acid is added while maintaining the temperature at 140 ° C.
A phosphoric acid-modified aralkyl resin obtained by adding over time and then reacting at 150 ° C. for 2 hours.

C-6: Aniline aralkyl resin An aralkyl resin obtained by heating and melting aniline and p-xylylene-α, α'-dichloride.

C-7: Phenol aralkyl resin (Sumilite Resin PR-54443, Sumitomo Durez Co., Ltd.)
C'-1: Phenol novolak resin (Sumilite Resin PR-53195, manufactured by Sumitomo Durez Co., Ltd.) [Nitrogen-containing flame retardant D] D-1: Melamine cyanurate (MC610, manufactured by Nissan Chemical Industries, Ltd.) [Antioxidant E] E-1: pentaerythritol-tetrakis [3-
(3,5-di-t-butyl-4-hydroxyphenyl)
Propionate] (Irganox 1010, manufactured by Ciba Geigy) [Phosphorus stabilizer F] F-1: Tetrakis (2,4-di-t-butylphenyl) -4,4′-biphenylenediphosphonite (Sand F-2: Calcium monophosphate F-3: Bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite (ADEKA STAB PEP36, ADEKA CORPORATION) Gas Co., Ltd.) [Fluorine-based resin G] G-1: Polytetrafluoroethylene [Filler H (glass fiber)] H-1: Chopped strand having a diameter of 10 μm and a length of 3 mm Examples 1 to 15 and Comparative Examples 1-5 polybutylene terephthalate (A-1 or A-10)
The above components were mixed at a ratio (weight ratio) shown in Tables 1 to 4, kneaded by 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, bending strength, and appearance were evaluated.

Tables 1 to 4 show the results.

[0151]

[Table 1]

[0152]

[Table 2]

[0153]

[Table 3]

[0154]

[Table 4]

Examples 16 to 24 and Comparative Examples 6 to 19 The above components were mixed with thermoplastic resin A at the ratios (weight ratios) shown in Tables 5 to 9, kneaded by an extruder, and extruded to prepare a resin composition. did. This resin composition was injection-molded to produce a test molded article, and the flammability and appearance were evaluated.

Tables 5 to 9 show the results.

[0157]

[Table 5]

[0158]

[Table 6]

[0159]

[Table 7]

[0160]

[Table 8]

[0161]

[Table 9]

Examples 25 to 34 and Comparative Examples 20 to 28 The above components were mixed with thermoplastic resin A at the ratios (weight ratios) shown in Tables 10 to 13, kneaded by an extruder, and extruded to prepare a resin composition. did. This resin composition was injection molded to prepare a test molded article, and the flammability, appearance and discoloration were evaluated.

Tables 10 to 13 show the results.

[0164]

[Table 10]

[0165]

[Table 11]

[0166]

[Table 12]

[0167]

[Table 13]

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[Procedure amendment]

[Submission date] October 12, 1999 (1999.10.
12)

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0055

[Correction method] Change

[Correction contents]

(Wherein, R ^{4 to} R ⁷ represent an aryl group which may have a substituent, Z represents a divalent aromatic group, and n represents an integer of 1 to 5). In 3), examples of the aryl group represented by R ^{4 to} R ⁷ include a C _6-20 aryl group such as phenyl and naphthyl, and a substituent of the aryl group includes an alkyl group such as a methyl group and an ethyl group. Is mentioned. As the divalent aromatic group, an arylene group (e.g., phenylene, etc. C _6-20 arylene group such as a naphthylene group), a group have a plurality of the arylene group [bisphenol residue (bisphenol A residues , A bisphenol D residue, a bisphenol AD residue), a group in which a hydroxyl group has been removed from a bisphenol, a biphenylene group, etc.].

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08L 71/10 C08L 71/10 77/00 77/00

Claims (21)

[Claims] 1. 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 an aralkyl resin. 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 100 parts by weight of the phosphorus-containing compound based on 100 parts by weight of the aralkyl resin. 4. The thermoplastic resin is at least one selected from olefin resins, acrylic resins, styrene resins, polyamide resins, polyester resins, polycarbonate resins, polyphenylene oxide resins, and vinyl resins. 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 polyester resin. 6. The thermoplastic resin according to claim 1, wherein the thermoplastic resin has at least one unit selected from 1,4-cyclohexyldimethylene terephthalate, ethylene terephthalate, butylene terephthalate, propylene terephthalate, ethylene naphthalate, and butylene naphthalate. The flame-retardant resin composition according to claim 1, which is a polyester. 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 flame-retardant resin composition according to claim 1, wherein the aralkyl resin has a repeating unit represented by the following formula (1). Embedded image (Wherein, Ar represents an aromatic group, R ¹ and R ² are the same or different and represent an alkylene group, R ³ represents a hydrogen atom or an alkyl group, X represents a hydroxyl group, an amino group or N-
Represents a substituted amino group) 11. The flame-retardant resin composition according to claim 1, wherein the aralkyl resin is obtained by reacting a compound represented by the following formula (2) with a phenol or aniline. Y—R ¹ —Ar—R ² —Y (2) (in the formula, Y represents an alkoxy group, an acyloxy group, a hydroxyl group or a halogen atom; Ar, R ¹ and R ² are the same as described above) 12. The flame-retardant resin composition according to claim 1, wherein the aralkyl resin is modified with a boron compound or a phosphorus compound. 13. The flame-retardant resin composition according to claim 1, further comprising a fluorine-based resin. 14. The flame-retardant resin composition according to claim 1, further comprising a hindered phenolic antioxidant. 15. The flame-retardant resin composition according to claim 1, further comprising a phosphorus-based stabilizer. 16. The flame-retardant resin composition according to claim 1, further comprising a nitrogen-containing flame retardant. 17. The flame-retardant resin composition according to claim 1, further comprising a filler. 18. A method for producing a flame-retardant resin composition according to claim 1, wherein a thermoplastic resin and a flame retardant are mixed. 19. The flame-retardant resin according to claim 18, wherein a master batch composed of at least two components selected from a thermoplastic resin, an aralkyl resin, and a phosphorus-containing compound is melt-mixed with the thermoplastic resin. A method for producing a composition. 20. A molded article formed from the flame-retardant resin composition according to claim 1. 21. The molded article according to claim 20, wherein the molded article is an electric / electronic part, a mechanical mechanism part, or an automobile part.