JP2001342357A - Flame-retardant resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a flame-retardant resin composition containing a non- halogen flame retardant. SOLUTION: The flame-retardant resin composition consists of a thermoplastic resin (a polyester resin, etc.), (A) and a flame retardant (B). The flame retardant (B) contains a polyphenylene oxide resin (B1), phosphoric esters (a fused phosphoric ester, etc.), (B2), an organophosphate of a nitrogen-containing cyclic compound (B3), etc. Here, the nitrogen-containing cyclic compound includes melamine, a melamine condensate, etc., and the organophosphoric acid includes a partial ester of a non-fused phosphoric acid, an organophosphonic acid, an organophosphinic acid, etc. The ratio of the flame retardant (B) to 100 pts.wt. polyester resin (A) is e.g. around from 10 to 300 pts.wt.

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 useful for flame-retarding a thermoplastic resin such as a polyester resin, a method for producing the same, and a resin composition formed from the flame-retardant resin composition. Molded articles.

[0002]

2. Description of the Related Art Thermoplastic resins such as polyester resins have excellent mechanical properties, electrical properties, weather resistance, water resistance, chemical resistance and solvent resistance. For this reason, they are used as engineering plastics in various applications such as electric / electronic parts, mechanical mechanism parts, and automobile parts. On the other hand, polyester-based resins are required to have improved mechanical properties and to be flame-retardant for safety as the field of use is expanded. Generally, a method is known in which a flame retardant is added to a polyester resin by adding a flame retardant using a halogen compound or an antimony compound. However, halogen-based flame retardants may generate a large amount of dioxin-based compounds during combustion decomposition,
Environmentally unfavorable. Therefore, a method has been proposed in which a polyester-based resin is made flame-retardant using a polycarbonate-based resin and a phosphorus-based compound as a non-halogen-based flame retardant.

[0003] JP-A-10-168297 discloses a flame-retardant resin composition comprising a thermoplastic polyester resin, a polycarbonate-based resin, an organic phosphorus-based flame retardant and stabilized red phosphorus. Also, JP-A-10-168
No. 295 discloses a flame-retardant resin composition composed of a polyester resin, a polycarbonate resin, and a masterbatch comprising stabilized red phosphorus and an olefin-based resin.

[0004] The above-mentioned non-halogen flame retardants do not contain harmful halogens, but are inferior in flame retardancy as compared with halogen flame retardants, and thus 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 difficult to improve the mechanical properties and the moldability together with the flame retardancy.

[0005] On the other hand, there is also known a method of using a polyphenylene oxide resin and a phosphorus compound to make a polyester resin flame-retardant. For example, JP-A-60-47056
Japanese Patent Application Publication No. JP-A-2003-115139 discloses a thermoplastic resin composition in which a thermoplastic linear polyester resin is mixed with a flame retardant comprising a polyphenylene oxide resin, an organic phosphate and a bromine compound. However, this method is not environmentally preferable because a halogen compound is used.

Therefore, it is conceivable to make the polyester resin flame-retardant without using a halogen compound.
For example, JP-A-6-504563 describes a resin composition comprising polybutylene terephthalate, polyphenylene oxide and resorcinol diphosphate. However, this resin composition has a UL-94 heat resistance test result of about V-2 and does not have sufficient flame retardancy.

[0007]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a resin composition having a high level of flame retardancy in a non-halogen flame retardant and a method for producing the same.

Another object of the present invention is to provide a flame-retardant resin composition without deteriorating the properties of a thermoplastic resin 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, added an organic phosphate of a nitrogen-containing cyclic compound to a polyphenylene oxide-based resin and a phosphoric ester to thereby provide a flame retardant. The present inventors have found that a thermoplastic resin can be made flame-retardant at a high level, thereby completing the present invention.

That is, the flame-retardant resin composition of the present invention comprises:
It is composed of a thermoplastic resin (A) and a flame retardant (B). The flame retardant (B) is a polyphenylene oxide resin (B1), a phosphate (such as a condensed phosphate) (B2), an organic phosphate of a nitrogen-containing compound (B3).
And so on. Examples of the thermoplastic resin (A) include polyester resins, polyamide resins, vinyl resins, olefin resins, and acrylic resins, particularly 1,4-cyclohexane dimethylene terephthalate, C _2-4 alkylene terephthalate, C _{2 -4} alkylene naphthalate and the like. Organic phosphates of nitrogen-containing compounds (B3)
May be a salt of melamine or a melamine condensate with a non-condensed phosphoric acid partial ester, an organic phosphonic acid or an organic phosphinic acid. The proportion of the flame retardant (B) is, for example, 10 to 100 parts by weight of the thermoplastic resin (A).
It may be about 300 parts by weight. The flame retardant (B) may contain 10 to 500 parts by weight of the polyphenylene oxide-based resin (B1) based on 100 parts by weight of the phosphoric acid ester (B2). B3) 5 to 1000 parts by weight may be contained. The flame-retardant resin composition may contain additives (resin-like flame retardant, nitrogen-containing flame retardant, inorganic flame retardant, styrene resin, etc.). The resinous flame retardant aid may be a resin having an aromatic ring having a hydroxyl group and / or an amino group in a main chain or a side chain, a polyarylate resin, an aromatic epoxy resin, a polycarbonate resin, or the like. Examples of the nitrogen-containing flame retardant aid include salts of a nitrogen-containing cyclic compound with sulfuric acid, boric acid, inorganic phosphoric acid, or a heterocyclic compound having a hydroxyl group, polyphosphoramide, cyclic urea compounds, and the like. The inorganic flame retardant aid may be, for example, a metal borate, a metal hydrogen phosphate, or red phosphorus. Further, the flame-retardant resin composition may contain a hindered phenol-based antioxidant, a phosphorus-based stabilizer, a fluorine-based resin, 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 the above-mentioned flame retardant, and a molded article formed from the above-mentioned flame-retardant resin composition. .

[0013]

DESCRIPTION OF THE PREFERRED EMBODIMENTS [Thermoplastic resin (A)] As the thermoplastic resin, various resins used for molding, for example, polyester resin, polyamide resin, vinyl resin, olefin resin, acrylic resin Base resin and the like.

(1) Polyester Resin Polyester resin is a homopolyester or copolyester obtained by polycondensation of a dicarboxylic acid component and a diol component, polycondensation of oxycarboxylic acid or lactone, or polycondensation of these components. It is. Preferred polyester resins are usually saturated polyester resins,
Particularly, an aromatic saturated polyester resin is included.

Examples of the dicarboxylic acid component include aromatic dicarboxylic acids (for example, naphthalene carboxylic acid such as phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, 2,6-naphthalenedicarboxylic acid, and 4,4'-diphenyl). Carboxylic acid, 4,4′-diphenoxy ether carboxylic acid, 4,4′-diphenylmethane dicarboxylic acid,
Dicarboxylic acids having about 8 to 16 carbon atoms, such as 4,4'-diphenylketone dicarboxylic acid). In addition, aliphatic dicarboxylic acids (e.g., succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedicarboxylic acid, dodecanedicarboxylic acid, hexadecanedicarboxylic acid, dimer acid, etc. About 40 dicarboxylic acids, preferably about 1 to 14 carbon atoms), alicyclic dicarboxylic acids (for example, 8 to 8 carbon atoms such as hexahydrophthalic acid, hexahydroisophthalic acid, hexahydroterephthalic acid, and hymic acid) About 12 dicarboxylic acids) or derivatives thereof (for example, derivatives capable of forming esters such as lower alkyl esters and acid anhydrides) may be used in combination. These dicarboxylic acid components may be used alone or in combination of two or more. In addition, if necessary,
A polycarboxylic acid such as trimellitic acid or pyromellitic acid may be used in combination.

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

The diol component includes, for example, 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.). Biphenol, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis- (4- (2-hydroxyethoxy)
An aromatic diol such as phenyl) propane and xylylene glycol may be used in combination. These diol components may be used alone or in combination of two or more. Further, if necessary, a polyol such as glycerin, trimethylolpropane, trimethylolethane or pentaerythritol may be used in combination.

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

The oxycarboxylic acids include, 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). , Polyalkylene terephthalate (for example, 1,4-cyclohexane dimethylene terephthalate (PCT), polyethylene terephthalate (PET), polypropylene terephthalate (PPT), polybutylene terephthalate (PBT)
Homopolyesters such as poly C _2-4 alkylene terephthalate) and polyalkylene naphthalate (eg, poly C _2-4 alkylene naphthalate such as polyethylene naphthalate and polybutylene naphthalate); alkylene terephthalate and / or alkylene naphthalate Copolyester containing a unit as a main component (for example, 50% by weight or more)]. 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.). In addition, as long as the polyester resin does not impair melt moldability, etc.,
It may have not only a straight chain but also a branched chain structure, and may be crosslinked. Further, it may be a liquid crystal polyester.

The polyester resin can be produced by a conventional method, for example, transesterification or direct esterification.

(2) 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 trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, 2,2,4-trimethylhexamethylenediamine, 2,4,4-trimethylhexamethylenediamine, octamethylenediamine Aliphatic diamines such as bis (4-aminocyclohexyl)
Alicyclic diamines such as methane and bis (4-amino-3-methylcyclohexyl) methane; Also,
Aromatic diamines such as phenylenediamine and metaxylylenediamine may be used in combination. These diamines are 1
One or more species can be used.

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

Examples of the aminocarboxylic acid include C _4-20 aminocarboxylic acids such as aminoheptanoic acid, aminononanoic acid and aminoundecanoic acid. One or more aminocarboxylic acids can be used.

Examples of the lactam include C _4-20 lactams such as butyrolactam, vivalolactam, caprolactam, caprylactam, enantholactam, undecanolactam and 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) And polyamides obtained from aromatic and aliphatic dicarboxylic acids (for example, terephthalic acid and adipic acid) and aliphatic diamines (for example, hexamethylene diamine). These polyamides can be used alone or in combination. Preferred polyamides include non-aromatic and aliphatic polyamides (nylon 6, nylon 66, nylon 610, nylon 612, nylon 11, nylon 12
Etc.), diamine component and dicarboxylic acid component,
A polyamide (nylon MXD6) in which at least a dicarboxylic acid component is an aliphatic compound is included.

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

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

(4) Olefin resin Examples of the olefin resin include α-olefins such as ethylene, propylene and 1-butene (especially α-C
_2-10 olefin) homo- or copolymer. Preferred olefin-based resins include polyethylene, polypropylene, ethylene-propylene copolymer and the like.

(5) Acrylic Resin The acrylic resin includes (meth) acrylic monomers such as (meth) acrylic acid, methyl (meth) acrylate, (meth) acrylamide, (meth) acrylonitrile and the like. Polymers and copolymers of (meth) acrylic monomers with other copolymerizable monomers are included.

The number average molecular weight of the above thermoplastic resin is
It is not limited to this, but can be selected as appropriate according to the type and application of the resin.
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.

The thermoplastic resins may be used alone or in combination of two or more.

Preferred thermoplastic resins include polyester resins, which may be liquid crystal polyesters, polyamide resins, vinyl resins, and the like, with polyester resins (PBT resins, etc.) being particularly preferred.

[Flame Retardant (B)] In the present invention, the flame retardant (B) is a polyphenylene oxide resin (B1)
By comprising a phosphate (B2) and an organic phosphate (B3) of a nitrogen-containing cyclic compound, high flame retardancy can be imparted without lowering the properties of the thermoplastic resin.

[Polyphenylene oxide resin (B
1)] When the flame retardant is constituted by using the polyphenylene oxide resin (B1), compared with the case where the flame retardant is constituted only by the phosphates (B2) and the organic phosphate (B3) of the nitrogen-containing cyclic compound, Flame retardancy can be significantly increased. Therefore, the amount of the flame retardant used can be reduced, and there is no possibility that the properties of the thermoplastic resin (eg, polyester-based resin) are deteriorated.

The polyphenylene oxide-based resin (polyphenylene ether-based resin) includes a homopolymer and a copolymer. Homopolymers include poly (2,6-dimethyl-1,4-phenylene) oxide and poly (2,5
-Dimethyl-1,4-phenylene) oxide, poly (2,5-diethyl-1,4-phenylene) oxide,
Poly (2-methyl-6-ethyl-1,4-phenylene)
Oxides, 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
Poly (mono or di C _1-6 ) such as -phenylene) oxide
Alkyl-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.

These polyphenylene oxide resins are:
You may use individually or in combination of 2 or more types.

[Phosphates (B2)] The phosphates include monomeric phosphates (phosphates, phosphites, hypophosphites), polymer phosphates and the like. .

As the phosphate ester, aliphatic phosphate ester
Stele [trimethyl phosphate, triethyl phosphate, phosphoric acid
Tripropyl, Triisopropyl phosphate, Trib phosphate
Tri-C phosphate such as chill and triisobutyl phosphate_1-10A
Alkyl ester; a resin corresponding to the phosphoric acid triester
Diacid C_1-10Alkyl ester and phosphoric acid mono-C_1-10A
Alkyl ester], aromatic phosphate [phosphoric acid]
Triphenyl, tricresyl phosphate, trixylyl phosphate
, Diphenylcresyl phosphate, triphosphate (isopro
Pyrphenyl), diphenylethylcresyl phosphate, etc.
Triphosphate C _6-20Aryl esters, etc.), aliphatic-
Aromatic phosphate esters (methyldiphenyl phosphate, phosphorus
Phenyldiethyl acid).

Phosphite (phosphonate)
Include, for example, aromatic phosphites (tri-C phosphite wherein aryl is phenyl, cresyl, xylyl, etc.)
_6-20 aryl ester, etc., aliphatic phosphite (alkyl is methyl, ethyl, propyl, isopropyl, butyl, isobutyl, etc., tri-C _1-10 alkyl phosphite; corresponding to the above-mentioned trialkyl phosphite) Di- or mono-C _1-10 alkyl phosphites), organic phosphites [eg, C _1-6 alkyl phosphonic acids wherein alkyl is alkyl as exemplified above and aryl is phenyl, cresyl, xylyl, etc. Di C
The alkyl phosphonic acid diester; _1-6 alkyl, C _1-6 alkylphosphonic di C _{6-1 0} aryl, alkyl phosphonic acid diester of a C _1-6 alkyl phosphonic acid C _1-6 alkyl C _6-10 aryl corresponding C _{6- 10} aryl - phosphonic diesters; phosphonocarboxylic acid ester (C _1-4 alkoxycarbonyloxy C _1-4 alkyl phosphonic acid diester corresponding to the alkyl phosphonic acid diester, such as dimethyl methoxycarbonylmethyl acid) etc. Phosphonocarboxylic acid triesters]. Further, a metal salt of a phosphonocarboxylic acid which may be substituted with an alkyl or aryl group is also included.

The hypophosphite (phosphinic acid ester) is substituted (monosubstituted or disubstituted) with an alkyl group (such as a C _1-4 alkyl group) or an aryl group (such as a C _6-10 aryl group). Phosphinates (eg, C _1-6 alkyl phosphinates such as methyl phosphinate, C _6-10 aryl phosphinates such as phenyl phosphinate) and the like. Further, a metal salt of a phosphinicocarboxylic acid (for example, 3-methylphosphinicopropionic acid, 3-phenylphosphinicopropionic acid, etc.) which may be substituted by an alkyl group or an aryl group is also included.

The monomer type phosphoric acid esters also include nitrogen-containing phosphoric acid esters (nitrogen-containing phosphoric acid esters corresponding to the above-mentioned phosphoric acid esters, phosphonic acid esters, phosphinic acid esters, etc.).

As the polymer type phosphoric acid ester,
Condensed phosphate esters can be used. Examples of the condensed phosphoric ester include a condensed phosphoric ester having an aromatic ring, and may have, for example, a structural unit represented by the following formula (1).

[0048]

Embedded image

(Wherein, R ^{1 to} R ⁴ represent an aryl group which may have a substituent, and Z ¹ represents a divalent aromatic group.
Represents an integer of 1 to 5) In the formula (1), examples of the aryl group represented by R ^{1 to} R ⁴ include a C _6-20 aryl group such as phenyl and naphthyl, and a substituent of the aryl group. Is an alkyl group such as a methyl group and an ethyl group. 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 biphenylene group, and a bisphenol residue (bisphenol A).
Residue, bisphenol D residue, bisphenol AD residue).

The condensate represented by the above formula (1) includes
For example, resorcinol phosphates (resorcinol bis (diphenyl phosphate), resorcinol bis (dicresyl phosphate), resorcinol bis (dicylenyl phosphate), hydroquinone bis (diphenyl phosphate)), hydroquinone phosphates (hydroquinone bis (dicresyl phosphate), Hydroquinone bis (dixylenyl phosphate)), biphenol phosphates (biphenol bis (diphenyl phosphate), biphenol bis (dicresyl phosphate), biphenol bis (dixylenyl phosphate)), bisphenol phosphates (bisphenol-A bis (diphenyl phosphate) ), Bisphenol-A bis (dicresyl phosphate), bisphenol-A (Magnetic Sile nil phosphate)), and the like. Preferred condensates include resorcinol phosphates.

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

[0052]

Embedded image

(Wherein R ⁵ and R ⁶ represent an aryl group) As the aryl group, an aryl group (C
_6-20 aryl groups, especially phenyl) and substituted aryl groups (alkyl-substituted aryl groups).

Preferred phosphates include aromatic phosphates, condensed phosphates and the like, particularly condensed phosphates.

[Organic phosphate of nitrogen-containing cyclic compound (B
3)] The nitrogen-containing cyclic compound includes a compound having at least one amino group and a hetero ring containing at least one nitrogen atom in the ring. May have a hetero atom. Such nitrogen-containing heterocycles include imidazole,
Examples include 5- or 6-membered unsaturated nitrogen-containing heterocycles having a plurality of nitrogen atoms as ring constituent atoms, such as thiadiazole, thiadiazoline, furazane, triazole, thiadiazine, pyrazine, pyrimidine, pyridazine, triazine, and purine. Among such hetero rings, a 5- or 6-membered unsaturated nitrogen-containing ring having a plurality of nitrogen atoms as ring constituent atoms is preferable, and triazole and triazine are particularly preferable.

As the triazole compound, 1,2,3
-Triazole (1H-1,2,3-triazoles;
2H-1,2,3-triazoles), 1,2,4
-Triazole (1H-1,2,4 such as guanazole)
-Triazoles; 4H-1,2,4 such as guanazine
-Triazoles, etc.). The amino group may be substituted on a suitable site (nitrogen atom and carbon atom, particularly carbon atom) constituting the triazole ring. The number of amino groups is not particularly limited, and is about 1 to 3, preferably about 1 to 2.

As the triazine compound, 1,3,5-
Triazines [melamine, substituted melamine (alkyl melamine such as 2-methyl melamine, guanyl melamine, etc.), melamine condensate (melam, melem, melon, etc.), co-condensation resin of melamine (melamine-formaldehyde resin, phenol-melamine resin, Melamine or a derivative thereof such as benzoguanamine-melamine resin, aromatic polyamine-melamine resin); cyanuric amides such as ammeline and ammelide; guanamine, methylguanamine, acetoguanamine, benzoguanamine;
Guanamines such as succinoguanamine and CTU-guanamine or derivatives thereof], 1,2,3-triazines (1,2,3-triazine, benzo-1,2,3-triazine and the like), 1,2,4 -Various aminotriazines such as triazines. The amino group may be substituted on a suitable site (nitrogen atom and carbon atom, particularly carbon atom) constituting the triazine ring. The number of amino groups is not particularly limited, and is, for example, about 1 to 4, preferably about 1 to 3, and more preferably about 2 to 3.

The nitrogen-containing cyclic compound having an amino group may be used alone or in combination of two or more.
Preferred nitrogen-containing cyclic compounds include amino group-containing triazine compounds, particularly amino group-containing 1,3,5-triazines (melamine, melamine condensate, etc., particularly melam, melem).

The nitrogen-containing cyclic compound may form a salt with an organic phosphoric acid at the nitrogen atom site (imino group) constituting the ring, but usually, at least one amino group substituted on the ring and the organic phosphoric acid. It is preferred to form a salt with When it has a plurality of amino groups, all of the amino groups may form a salt with the organic phosphoric acid.

As the organic phosphoric acid, non-condensed phosphoric acid (peroxophosphoric acid, orthophosphoric acid, phosphorous acid (phosphonic acid))
Examples thereof include partial esters of orthophosphoric acid and phosphonic acid, and phosphorous acid (phosphonic acid) or hypophosphorous acid (phosphinic acid) substituted with an organic group. The partial ester has at least one site capable of forming a salt with the amino group of the nitrogen-containing cyclic compound.

The phosphoric acid ester (organic orthophosphoric acid) includes phosphoric acid mono- or diesters of alcohols (monohydric or polyhydric alcohol, monohydric or polyhydric phenols). The alcohols include C, such as methanol, ethanol, propanol, butanol, and hexanol.
_1-10 aliphatic monol; C _1-10 such as ethylene glycol, propylene glycol, butanediol, neopentyl glycol, glycerol, and pentaerythritol
C _2-10 aliphatic polyol having a hetero atom such as nitrilotriacetic methanol; aliphatic polyols cyclopentanol, C _5-8 alicyclic monool such as cyclohexanol (preferably C _5-6 cycloalkanol); cyclohexanediol _C5-8 alicyclic diols (preferably _C5-6 cycloalkanediols); monovalent _C7-20 aralkyl alcohols such as benzyl alcohol and phenethyl alcohol; phenol, cresol, xylenol, trimethylphenol, naphthol, Monohydric phenols such as hydroxybiphenyl; benzenediol,
Polyphenols such as naphthalene diol and bisphenol are included.

Examples of the phosphate include mono- or di-C _1-10 alkyl phosphates such as methyl phosphate and dibutyl phosphate; and C _2-10 aliphatic polyhydric alcohols such as ethylene glycol monophosphate and pentaerythritol bisphosphate. mono- to tetraphosphate; monophenyl phosphate, mono cresyl phosphate, mono carboxymethyl Les sulfonyl phosphate, mono-trimethylphenyl phosphate, diphenyl phosphate, dicresyl phosphate, magnetic Sile alkenyl phosphates, di-substituted group such as methyl phenyl phosphate (C _1-4 phosphoric acid esters of good monohydric phenols have a such as an alkyl group) (e.g., C _1-4 alkyl group which may have a mono- or di-C _6-14 aryl phosphate); phenylene bis Substituents such as Sufeto (C
_1-4 mono- or diphosphates alkyl group) which may have a polyhydric phenol (e.g., C _1-4 which may have an alkyl group C _6-14 Arirenmono or diphosphate), etc. And alkyl-aryl phosphates [eg, C _1-10 alkyl C _6-14 aryl phosphates such as methyl phenyl phosphate (preferably C _1-6 alkyl C _6-10 aryl phosphates) and the like].

In the organic phosphonic acid, a phosphonic acid monoester corresponding to the above-mentioned phosphoric acid ester or a hydrogen atom directly bonded to a phosphorus atom of the phosphonic acid has an organic group (aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic group). Organic phosphonic acid substituted with an organic group such as an aromatic hydrocarbon group), and organic phosphonic acid monoesters of the alcohols.

The organic phosphonic acids include aliphatic phosphones
Acids [methylphosphonic acid, ethylphosphonic acid,
Alkyl phosphones such as sulfonic acid and butyl phosphonic acid
Acid; 1-hydroxyethylidene-1-phosphonic acid, 1-
Fatty acids such as hydroxyethylidene-1,1-diphosphonic acid
Mono- or diphosphonic esters of aliphatic polyols;
Phosphono C such as phonoacetic acid and 3-phosphonopropionic acid
_1-10Aliphatic carboxylic acid, its carboxylic acid ester (phospho
Ethyl honoacetate, ethyl 3-phosphonopropionate, etc.
Carboxylic acid esters of phosphonocarboxylic acids)
Which phosphonocarboxylic acids, such as ethylenebisphosphonic acid
Which C_1-10Alkylenediphosphonic acid; nitrilotris
Fats containing hetero atoms such as (methylene phosphonic acid)
Phosphonic acids substituted with aromatic polyvalent groups], aromatic phosphonic acids
Acid [C such as phenylphosphonic acid and tolylphosphonic acid
_6-10Arylphosphonic acid; phos such as phosphonobenzoic acid
Hono C _7-15Aromatic carboxylic acid or carboxylic acid ester thereof
(E.g., phosphonoaromatic compounds such as ethyl phosphonobenzoate)
Carboxylic acid esters of boric acid, etc.); phenylene bis
Substituents such as phosphonic acid (C_1-4Alkyl group, etc.)
A phosphonic acid substituted with an aromatic polyvalent group which may be
Etc.] are included. Further, the organic phosphonic acid is
Phosphonic acid (polyvinyl phosphonic acid,
Polyvinylidenephosphonic acid).

Examples of the organic phosphonic acid monoester include monoesters of the organic phosphonic acid and the alcohols exemplified in the section of the phosphoric acid ester, for example, C _1-6 alkylphosphonic acid mono-C ₁ such as methylphosphonic acid monomethyl ester. (such as ethoxycarbonylmethyl phosphonic acid monoethyl, C _2-6 alkoxycarbonyl C _1-6 alkyl phosphonic acid mono C _1-6 alkyl ester such as monoethyl ethoxycarbonylethyl acid) diesters of phosphonocarboxylic acid; _-6 alkyl esters methylphosphonic C _1-6 alkyl phosphonic acid mono C _6-10 aryl ester such as acid monophenyl ester; C _6-10 aryl phosphonic acid C such as phenyl phosphonic acid monomethyl ester
_1-6 alkyl ester; C _6-10 arylphosphonic acid mono C _6-10 such as phenylphosphonic acid monophenyl ester
Aryl esters and the like.

The organic phosphinic acid includes an organic phosphinic acid in which an organic group (a hydrocarbon group such as an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, or an aromatic hydrocarbon group) is bonded to a phosphorus atom of the phosphinic acid. It is. Examples of such organic phosphinic acids include substituted phosphinic acids corresponding to the above-mentioned substituted phosphonic acids, for example, mono- or di-C _1-6 alkylphosphinic acids such as methylethylphosphinic acid and diethylphosphinic acid; Hosufinikoji C _1-6 aliphatic carboxylic acids, such as phosphinyl co carboxylic acid [Hosufinikoji acetate; _1-6 alkyl C _6-10 aryl phosphinic acid 3- C _1-6 Arukiruhosu such (methyl phosphinyl co) propionic acid Finiko - mono C _1-6 aliphatic carboxylic acid, 3- (phenyl-phosphinyl co) C _6-10 aryl phosphinyl U-propionic acid - mono C _1-6 aliphatic carboxylic acids, these phosphinyl co carboxylic Carboxylic acid esters of acids; C such as phenylphosphinic acid
_6-10 aryl phosphinic acid; phosphinothricin Nikomono or di-C
_6-10 aryl carboxylic acids or carboxylic acid esters thereof;
Hydroxyphosphine oxide (such as 1-hydroxydihydrophosphonyl oxide and 1-hydroxyphosphorane oxide);

The organic phosphoric acid may be a cyclic organic phosphoric acid (eg, 9,10-dihydro-10-hydroxy-1).
0-oxo-9-oxa-10-phosphaphenanthrene).

The above-mentioned organic phosphate can form a salt with a nitrogen-containing cyclic compound at a part or the whole of a site where a salt can be formed, and any salt can be used. Examples of such organic phosphates include salts of amino group-containing triazine compounds, such as melamine salts of organophosphates (pentaerythritol bisphosphate melamine, pentaerythritol bisphosphate dimeramine, etc.), C _1-6 alkyl-substituted Melamine salts of phosphonic acids, melamine salts of mono- or diphosphonic esters of C _1-6 aliphatic diols (1-hydroxyethylidene-1,1-diphosphonic acid / dimeramine,
-Hydroxyethylidene-1,1-diphosphonic acid / tetramelamine), a melamine salt of a phosphonic acid substituted with an aliphatic polyvalent group having a hetero atom [nitrilotris (methylenephosphonic acid) / tetramelamine salt, nitrilotris ( Methylenephosphonic acid) / hexamelamine salt, and C _6-10 arylphosphonic acid / melamine (phenylphosphonic acid / melamine, phenylphosphonic acid / dimeramine, etc.), phosphinicocarboxylic acid / melamine salt (3- (phenylphosphonic acid) (Finico) propionic acid / melamine, aryl (phosphinicocarboxylic acid / melamine salt such as 3- (phenylphosphinico) propionic acid / dimeramine); melem salt, melam salt, melon salt, guanamine salt corresponding to the melamine salt ; And pentaerythritol bisphosphate Such double salt corresponding to the melamine salt, such as Ming melem and the like. Further, a triazole salt corresponding to the triazine compound salt can also be used.

The above-mentioned organic phosphates can be used alone or in combination of two or more.

The ratio of the nitrogen-containing cyclic compound to the organic phosphoric acid is not particularly limited. For example, the former / the latter (molar ratio) = 1/20 to 20/1, preferably 1/10 to 10
/ 1 (for example, 1/5 to 10/1), especially 1/2 to 8 /
It is about 1. The equivalent ratio between the amino group of the nitrogen-containing cyclic compound and the site capable of forming a salt of organic phosphoric acid is not particularly limited, and is, for example, about 10/1 to 1/2, preferably 5/1.
About 1/1, especially about 4/1 to 1/1.

The method for producing an organic phosphate of such a nitrogen-containing cyclic compound (particularly, an amino group-containing triazine compound) is not particularly limited. For example, a solution or dispersion containing the nitrogen-containing cyclic compound and an organic phosphoric acid is used. A liquid (aqueous solution or suspension such as a water-acetone mixed system or a water-alcohol mixed system) is heated to an appropriate temperature (for example, about 50 to 100 ° C).
And the resulting precipitate is separated and dried.

In the present invention, since the flame retardant is constituted by using an organic phosphate, not only can the thermoplastic resin (such as a polyester resin) be highly flame-retarded, but also the resin composition may be colored. Absent.

[Use ratio of flame retardant] The flame retardant of the present invention comprises:
By combining polyphenylene oxide, phosphates, and an organic phosphate of a nitrogen-containing cyclic compound, the characteristics of the thermoplastic resin (such as a polyester resin) are not reduced (for example, there is no risk of coloring or bleeding out). High flame retardancy can be imparted, and the amount of flame retardant added can be reduced. The ratio of the flame retardant to the thermoplastic resin is about 10 to 300 parts by weight, preferably about 20 to 250 parts by weight, and more preferably about 30 to 200 parts by weight, based on 100 parts by weight of the thermoplastic resin.

The proportion of each component of the flame retardant can be appropriately selected within a range in which the flame retardancy can be imparted. For example, the proportion of the polyphenylene oxide resin is 10 to 500 parts by weight with respect to 100 parts by weight of the phosphates. Parts, preferably 10-3
The amount is about 00 parts by weight (for example, 10 to 200 parts by weight), and more preferably about 30 to 300 parts by weight (for example, 30 to 200 parts by weight). The proportion of the organic phosphate of the nitrogen-containing cyclic compound is, for example, about 5 to 1,000 parts by weight, about 5 to 500 parts by weight, and more preferably about 5 to 300 parts by weight, based on 100 parts by weight of the phosphoric esters. The ratio (weight ratio) of the organic phosphate of the nitrogen-containing cyclic compound to the polyphenylene oxide-based resin is 1/99 to 90/10, preferably 5/95 to 70/30, and more preferably 10/90.
About 60/40.

[Additives] The flame-retardant resin composition of the present invention comprises:
If necessary, various additives (for example, other flame retardants (or flame retardant auxiliaries), styrene resins, antioxidants, stabilizers, anti-dripping agents, etc.) may be included. The total content of the additives is based on 100 parts by weight of the thermoplastic resin.
It is 0.01 to 50 parts by weight, preferably 0.1 to 40 parts by weight, and more preferably about 1 to 35 parts by weight.

As the flame retardant auxiliary, for example, a resinous flame retardant, a nitrogen-containing flame retardant, an inorganic flame retardant and the like can be used.

[Resinous Flame Retardant Aid (D1)] As the resinous flame retardant (or flame retardant), a resin having an aromatic ring having a hydroxyl group and / or an amino group in a main chain or a side chain, Aromatic resins such as polyarylate resins, aromatic epoxy resins, and polycarbonate resins are exemplified.

(1) Resin Having an Aromatic Ring Having a Hydroxyl Group and / or Amino Group in the Main Chain or Side Chain Examples of the resin having an aromatic ring in the main chain include a novolak resin and an aralkyl resin. Examples of the resin having a ring in the side chain include an aromatic vinyl resin.

(1-1) Novolak resin The novolak resin has a repeating unit represented by the following formula (3).

[0080]

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(Wherein R ^{7 to} R ⁹ are the same or different,
Represents a hydrogen atom, an alkyl group or an aryl group, and q represents an integer of 1 or more.) Examples of the alkyl group include C, such as methyl, ethyl, butyl, t-butyl, hexyl, octyl, nonyl, and decyl.
_Examples thereof include a _1-20 alkyl group, preferably a C _1-12 alkyl group. Examples of the aryl group include a C _6-20 aryl group and a substituted aryl group (particularly a C _1-4 alkyl-substituted aryl group) exemplified in the above-mentioned R ^{1 to} R ⁴ .

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

The aldehydes include, for example, aliphatic aldehydes such as formaldehyde, acetaldehyde and propionaldehyde, and aromatic aldehydes such as phenylacetaldehyde. Preferred aldehydes include formaldehyde.
Further, condensates of formaldehyde such as trioxane and paraformaldehyde can also be used. The ratio of phenols to aldehydes is the former / the latter = 1 / 0.5 to 1 /
It is about 1 (molar ratio).

The condensation reaction between phenols and aldehydes is usually performed in the presence of an acid catalyst. Examples of the acid catalyst include an inorganic catalyst (for example, hydrochloric acid, sulfuric acid, phosphoric acid, etc.) and an organic catalyst (p-toluenesulfonic acid, oxalic acid, etc.).

Further, as the novolak resin, a high ortho-novolak resin having an ortho / para ratio of 1 or more may be used. As a method of methylene bond of novolak resin,
For the hydroxyl group of each aromatic ring, (i) when bonded at ortho positions, (ii) when bonded at ortho position and para position, (iii) when bonded at para position There are cases.

The ortho / para ratio is defined as the number of methylene bonds M _p bonded in para positions, the number of methylene bonds M _OP bonded in ortho and para positions, and the number of methylene bonds bonded in ortho positions. When M _O , it is expressed by the following equation.

[0087] ortho / para ratio = [M _O + (1/2)
M _OP ] / [M _P + (１ ／) M _OP ] For example, the ortho / para ratio can be calculated from the above equation from the number of methylene bonds obtained from ¹³ C-NMR spectrum measurement.

In particular, novolak resins include ortho /
Para ratio is 1 or more, for example, 1 to 20 (particularly 1 to 15)
Novolak resin having a high degree, that is, a so-called high ortho novolak resin is preferably used.

The novolak resin having an ortho / para ratio of 1 or more can be used, for example, in the presence of at least one catalyst selected from (1) metal salts, metal oxides, metal hydroxides and amine compounds; After the condensation reaction, a method of reacting a phenol with an aldehyde by adding an acid catalyst [for example, JP-A-55-90523, JP-A-57-51714, and JP-A-59-80418] Gazette, JP-A-62-230815, U.S. Pat.
No. 3700], (2) non-polar solvent (for example,
Aromatic hydrocarbons such as xylene, toluene and benzene,
Phenols and aldehydes in an alicyclic hydrocarbon such as cyclohexane) under pressure (for example, JP-A-6-345837, Macromol.
Chem. 182,2973 (1981)] and (3) a method of reacting phenols and aldehydes in the absence of a catalyst by strictly controlling the production method and conditions [see, for example, JP-A-10-19]
5158, JP-A-10-204139, etc.), and (4) a method in which a metal phenolate such as magnesium bromide or magnesium methylate of phenol is reacted with an aldehyde in the above-mentioned nonpolar solvent [for example, US Pat. Patent No. 4097463, Macromolec
ules, 17, 19 (1984)]. The ratio of phenols and aldehydes is the former / latter = 1
/0.3 to 1/1 (molar ratio).

Examples of the metal salt catalyst include polyvalent metal salts of organic acids (for example, aliphatic carboxylic acids such as acetic acid, naphthenic acid and oxalic acid, and sulfonic acids such as methanesulfonic acid) (for example, Zn, Mg). , Mn, Cd, Ca, C
o, Pb, Cu, Ni, Al, etc.).
Examples of the metal oxide and the metal hydroxide include polyvalent metal oxides and polyvalent metal hydroxides (for example, Zn, Mg,
Oxides and hydroxides such as Mn, Cd, Ca, Co, Pb, Cu, Ni, and Al). Examples of the amine compound include an aliphatic amine (for example, dimethylamine, diethylamine, and the like). These catalysts can be used alone or in combination of two or more.

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

The above-mentioned phenols, dioxybenzenes, naphthols, bisphenols, alkylbenzenes (eg, toluene, ethylbenzene, xylene, mesitylene, etc.), anilines, furfurals, ureas, triazines (eg, , Cyanuric acid, isocyanuric acid, melamine, guanamine, acetoguanamine, benzoguanamine, etc.), terpenes, cashew nuts, rosins and the like. In particular, aminotriazine novolaks modified with triazines are preferred co-condensates. Such aminotriazine novolaks convert phenols, triazines and formaldehydes into basic catalysts (ammonia, triethylamine, triethanolamine, etc.).
And / or a method of co-condensing in the presence or absence of an acidic catalyst (such as oxalic acid) [for example, DIC Techni
cal Review No. 3, p47 (199
7), JP-A-8-253557 and JP-A-10-2
No. 79657]. Aminotriazine novolak is available from Dainippon Ink and Chemicals, Inc. under the trade name "Phenolite".

The bisphenols include bisphenol A, bisphenol D, bisphenol A
D, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) butane, 2,2′-dihydroxydiphenylmethane, 2,2′-diethyl-4 Dihydroxydiarylalkanes such as 4,4'-dihydroxydiphenylmethane; dihydroxydiarylcycloalkanes such as 1,1-bis (4-hydroxyphenyl) cyclohexane; dihydroxyaryl such as 1,4-bis (4-hydroxyphenylisopropyl) benzene Alkylbenzenes; dihydroxydiaryl sulfones such as bis (4-hydroxyphenyl) sulfone and bis (3,5-dimethyl-4-hydroxyphenyl) sulfone; bis (4-hydroxyphenyl) ether, bis (3,5-
Dimethyl-4-hydroxyphenyl) ether, 4,
Dihydroxydiaryl ethers such as 4'-dihydroxydiphenyl ether; 4,4'-dihydroxybenzophenone, 3,3 ', 5,5'-tetramethyl-
Dihydroxydiaryl ketones such as 4,4'-dihydroxybenzophenone; dihydroxydiaryl sulfides such as bis (4-hydroxyphenyl) sulfide and bis (3-methyl-4-hydroxyphenyl) sulfide; bis (4-hydroxyphenyl) Dihydroxydiaryl sulfoxides such as sulfoxide; 4,
Dihydroxydiphenyls such as 4'-dihydroxydiphenyl and the like can be used.

In addition, some or all of the phenolic hydroxyl groups of the novolak resin (random novolak resin and high ortho novolak resin) may be converted to phosphorus compounds (for example, phosphoric acid, phosphorous acid, organic phosphonic acid, organic phosphinic acid, etc.). System acids and their anhydrides, halides,
Salts or esters (especially, aliphatic esters), and boron compounds (for example, boric acids such as boric acid, organic boronic acids, organic borinic acids, and anhydrides, halides, salts, or esters thereof) A modified novolak resin (for example, a phosphate-modified novolak resin, a boric acid-modified novolak resin, and the like) modified with at least one member selected from the group consisting of: The hydroxyl group of the novolak resin is
Usually, it is modified as a phosphate or borate.

Further, a part or all of the hydrogen atoms of the phenolic hydroxyl group of the novolak resin (random novolak resin and high-ortho novolak resin) may be a metal ion, a silyl group or an organic group (alkyl group, alkanoyl group,
A modified novolak resin modified (or substituted) with a benzoyl group or the like can also be used.

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

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

(1-2) Aralkyl Resin The aralkyl resin used in the present invention has a structural unit represented by the following formula (4).

[0099]

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(Wherein, Ar represents an aromatic group, Z ² and Z ³ are the same or different and represent an alkylene group, R ¹⁰ represents a hydrogen atom or an alkyl group, X represents a hydroxyl group, an amino group, or The aromatic group represented by Ar is an aromatic group having 6 to 20 carbon atoms, for example, a phenylene group (o-phenylene group, m-substituted amino group).
-Phenylene group, p-phenylene group), naphthylene group and the like, preferably phenylene group (particularly p-phenylene group).

[0102] The alkylene group represented by Z ² and Z ^3, methylene, ethylene, propylene, tetramethylene, C _1-6 alkylene group such as hexamethylene (preferably C _{1 -4} alkylene group, in particular C _1-2 Alkylene group). Examples of the alkyl group represented by R ¹⁰ include the aforementioned R
^The C _1-20 alkyl groups (especially C _1-4 alkyl groups) exemplified in the section of ^{7 to} R ⁹ can be mentioned.

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.

A phenol aralkyl resin in which X is a hydroxyl group is often used as the aralkyl resin. Preferred phenol aralkyl resins include resins having Z ² and Z ³ as methylene groups, Ar as a phenylene group, R ¹⁰ as a hydrogen atom, and a p-xylene-substituted phenol represented by the following formula (5) as a repeating unit. included.

[0104]

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The aralkyl resin is generally represented by the following formula (6)
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.

YZ ² -Ar-Z ³ -Y (6) (in the formula, Y represents an alkoxy group, an acyloxy group, a hydroxyl group or a halogen atom. Ar, Z ² and Z ³ are the same as above). In (6), the alkoxy group represented by Y includes a methoxy, ethoxy, propoxy, butoxy group, etc.
_1-4 alkoxy groups are included. The acyloxy group includes an acyloxy group having about 2 to 5 carbon atoms, such as an acetoxy group. The halogen atom includes chlorine, bromine, iodine and the like.

As the compound represented by the above formula (6),
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 the phenols include the phenols and alkyl phenols exemplified in the section of the novolak resin. 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 (6) to phenols or anilines is, for example, the former / latter = 1/1
To about 1/3 (molar ratio), preferably 1/1 to 1/2.
It is about 5 (molar ratio).

The reaction of the compound of the formula (6) 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 aralkyl ethers are used as the compound of the formula (6), the reaction can be performed in the presence of a catalyst, and when aralkyl halides are used, the reaction can be performed in the absence of a catalyst. Examples of the catalyst include Friedel-Crafts catalysts such as dimethyl sulfate, diethyl sulfate, tin chloride, and aluminum chloride.

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

In the above reaction, in addition to phenols and / or anilines, aldehydes (benzaldehyde, etc., in addition to the aldehydes exemplified in the section of the novolak resin), and oxybenzoic acids (for example, p-oxybenzoic acid) A p-oxybenzoic acid alkyl ester such as methyl p-oxybenzoate, ethyl p-oxybenzoate, etc.), oxybenzenes (dioxybenzene, trioxybenzene, etc.), naphthols (for example, 1-naphthol, 2 -Naphthol, 1,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, hydroxynaphthoic acid, hydroxynaphthoic acid alkyl ester, etc., bisphenols (bisphenols exemplified in the section of the novolak tree, bisphenol F, bisphenol S) , Bisfe Lumpur - sulfone), anilines, furfurals, may be used in combination co condensation component such as illustrated alkylbenzenes and ureas as a copolymer component in the section on the novolak resin.

Further, as the aralkyl resin, at least a part of the hydroxyl group or amino group represented by X is
Modified aralkyl resins modified with at least one selected from the phosphorus compounds and boron compounds exemplified in the section of the novolak resin (for example, phosphoric acid-modified phenol aralkyl resin, phosphoric acid-modified aniline aralkyl resin, boric acid-modified phenol) Aralkyl resins, boric acid-modified aniline aralkyl resins, etc.) can also be used. The hydroxyl group of the aralkyl resin is usually modified as a phosphoric acid ester or a boric acid ester, and the amino group is usually modified as a phosphoric acid amide or a boric acid amide.

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

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

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.).

(1-3) Aromatic vinyl resin As the aromatic vinyl resin, for example, a resin having a structural unit represented by the following formula (7) can be used.

[0119]

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(In the formula, R ¹¹ is a hydrogen atom or a C _1-3 alkyl group, R ¹² is an aromatic ring, and r is an integer of 1 to 3.) In the formula (7), preferred C _1-3 Examples of the alkyl group include a methyl group. Also, as the aromatic ring,
For example, a C _6-20 aromatic ring such as a benzene and naphthalene ring can be mentioned. The aromatic ring is a substituent (for example, a hydroxyl group; an alkyl group exemplified in the above-mentioned R ^{7 to} R ⁹ ;
Or the alkoxy group exemplified in the section of Y).

In the formula (7), the hydrogen atom of the hydroxyl group may be protected by an organic group (protecting group) such as a metal ion, a silyl group or an alkyl group, an alkanoyl group and a benzoyl group.

The resin obtained from such a derivative has, for example, a structural unit represented by the following formula (8).

[0123]

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(Wherein R ¹¹ is the same as described above. R ¹³ is —O
H, —OSi (R ¹⁴ ) ₃ and —OM (M is a metal cation;
OR ¹⁴ and OCOR ¹⁴ , wherein R ¹⁴ is an alkyl group or aryl having 1 to 5 carbon atoms. S is an integer of 1 to 3. In the above formula, M may be either a monovalent alkali metal cation (eg, sodium, lithium, potassium), or a divalent alkaline earth metal cation (eg, magnesium, calcium) or a transition metal cation.

The substituent R ^{13 in the} above formula may be located at any one of the ortho, meta and para positions. Further, in addition to the substituent R ¹³ , the pendant aromatic ring may be a C _1-4
May be substituted with an alkyl group.

The aromatic vinyl resin includes a homo- or copolymer of an aromatic vinyl monomer having a hydroxyl group corresponding to the structural unit (8), a copolymer with another copolymerizable monomer, and the like. It is.

As the aromatic vinyl monomer, for example,
Examples include hydroxyl group-containing aromatic vinyl monomers such as vinyl phenol, dihydroxystyrene, and vinyl naphthol. These aromatic vinyl monomers can be used alone or in combination of two or more.

Other copolymerizable monomers include, for example,
(Meth) acrylic monomer [(meth) acrylic acid,
(Meth) acrylic acid esters (for example, C _1- (meth) acrylic acid such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate; ₁₈ alkyl esters,
Hydroxyl-containing monomers such as 2-hydroxyethyl (meth) acrylate, glycidyl (meth) acrylate), (meth) acrylamide, (meth) acrylonitrile, etc.], styrene monomers (for example, styrene,
Vinyltoluene, α-methylstyrene, chlorostyrene, vinylnaphthalene, vinylcyclohexane, etc.),
Polymerizable polycarboxylic acids (fumaric acid, maleic acid, etc.),
Maleimide monomers (maleimide, N-alkylmaleimide, N-phenylmaleimide, etc.), diene monomers (isoprene, 1,3-butadiene, 1,4-hexadiene, dicyclopentadiene, etc.), vinyl monomers (for example, vinyl acetate , Vinyl esters such as vinyl propionate; vinyl ketones such as methyl vinyl ketone and methyl isopropenyl ketone; vinyl ethers such as vinyl isobutyl ether and vinyl methyl ether; N-vinyl carbazole, N-vinyl pyrrolidone;
Nitrogen-containing vinyl monomers such as N-vinylimidazole). One or two or more of these copolymerizable monomers can be used.

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

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

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

(2) Polyarylate resin The polyarylate resin has the following formula (9) [-O-Ar-OC (O) -A ¹ -C (O)-] (9) Represents an aromatic group, and A ¹ represents an aromatic, alicyclic, or aliphatic group.).

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

The polyarylate resin can be obtained by reacting an aromatic polyol component with a polycarboxylic acid component (such as an aromatic polycarboxylic acid component, an aliphatic polycarboxylic acid component, or an alicyclic polycarboxylic acid component). . The polycarboxylic acid component usually contains at least an aromatic polycarboxylic acid component.

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

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

Examples of the polycyclic aromatic diol include bis (hydroxyaryl) s (bisphenols), for example,
Bis (hydroxyaryl) cycloalkyl such as 4,4′-dihydroxybiphenyl, 2,2′-biphenol, dihydroxydiarylalkanes and bis (hydroxyaryl) C _1-6 alkane such as bisphenol F in the novolak resin; Alkanes [eg, bis (hydroxyaryl) C _3-12 cycloalkanes such as bis (hydroxyphenyl) cyclohexane]; bis (hydroxyaryl) carboxylic acids [eg bis-4,4
-(Hydroxyphenyl) butanoic acid and the like, and bis (hydroxyaryl) C _2-6 carboxylic acid and the like]. Further, other polycyclic aromatic diols include compounds having a bis (hydroxyaryl) skeleton, for example,
Di (hydroxyphenyl) ether, di (hydroxyphenyl) ketone, di (hydroxyphenyl) sulfoxide, di (hydroxyphenyl) thioether, bis (C _1-4 alkyl-substituted hydroxyphenyl) alkane exemplified in the above-mentioned novolak resin [For example, screw (3-
Methyl-4-hydroxyphenyl) methane, bis (3-
Methyl-4-hydroxyphenyl) propane, bis (3,5-dimethyl-4-hydroxyphenyl) methane, bis (3,5-dimethyl-4-hydroxyphenyl) propane, etc.], terpene diphenols (for example, 1, 4-di (C _1-4 alkyl-substituted hydroxyphenyl) -p-menthane and the like are also included.

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

Preferred aromatic polyols include bisphenols such as bis (hydroxyaryl) C _1-6
Alkanes (for example, bisphenol A, bisphenol F, bisphenol AD, etc.) are included.

The aromatic polyol may be used in combination with an aliphatic or alicyclic polyol. Examples of the aliphatic polyol include C _2-10 aliphatic polyols such as the aliphatic alkylene diols exemplified in the section of the polyester resin. In addition, the aliphatic polyol includes 1,4
Also included are aliphatic polyols having a _C3-10 aliphatic ring such as cyclohexanedimethanol. The alicyclic polyol includes a C _3-10 alicyclic polyol such as cyclohexanediol.

As the aromatic polycarboxylic acid, for example,
Dicarboxylic acids such as monocyclic aromatic dicarboxylic acids and polycyclic aromatic dicarboxylic acids, or reactive derivatives thereof [eg, aromatic polycarboxylic acid halides (such as aromatic polycarboxylic acid chlorides), and aromatic polycarboxylic acids] Esters (alkyl esters, aryl esters, etc.), aromatic polycarboxylic anhydrides, etc.].

Examples of the monocyclic aromatic dicarboxylic acid include benzene dicarboxylic acids such as phthalic acid, phthalic anhydride, isophthalic acid and terephthalic acid, and aryl dicarboxylic acids having about 8 to 20 carbon atoms such as naphthalenedicarboxylic acid. . The benzenedicarboxylic acid and naphthalenedicarboxylic acid (particularly, benzenedicarboxylic acid) may be substituted with one or two C _1-4 alkyl groups.

Examples of the polycyclic aromatic dicarboxylic acids include bis (arylcarboxylic acids), for example, bis (carboxyaryl) C _1-6 alkane such as biphenyldicarboxylic acid and bis (carboxyphenyl) methane; bis (carboxyphenyl) A) bis (carboxyaryl) C _3-12 cycloalkane such as cyclohexane; bis (carboxyaryl) ketone such as bis (carboxyphenyl) ketone; bis (carboxyaryl) sulfoxide such as bis (carboxyphenyl) sulfoxide; bis (carboxyphenyl) A) bis (carboxyaryl) ethers such as ethers; bis (carboxyaryl) thioethers such as bis (carboxyphenyl) thioether;

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

Examples of the aliphatic polycarboxylic acid (monomer) include, in addition to the aliphatic dicarboxylic acids exemplified in the section of the polyester resin, C _2-20 aliphatic dicarboxylic acids such as oxalic acid and malonic acid. It may be a dicarboxylic acid having a C _3-10 aliphatic ring such as carboxymethylcyclohexane. Examples of the alicyclic polycarboxylic acid include cyclohexane-1,4-dicarboxylic acid and cyclohexane-1,3.
_-C3-20 alicyclic dicarboxylic acids such as dicarboxylic acids.

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

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

Further, the terminal of the polyarylate resin may be blocked (bonded) with alcohols, carboxylic acids, etc. (particularly, monohydric alcohols, monovalent carboxylic acids, etc.). Examples of the monohydric alcohol that blocks the terminal of the polyarylate resin include, for example, monovalent aryl alcohols (monohydric alcohols which may be substituted with a C _1-10 alkyl group and / or a C _6-10 aryl group). Phenols, for example, phenol, an alkylphenol having a C _1-4 alkyl group such as 1 to 2 methyl groups at the o, m, or p positions; o,
arylphenols having a phenyl, benzyl, cumyl group or the like at the m or p position), monovalent alkyl alcohols (C such as methanol, ethanol, propanol, butanol, hexanol, stearyl alcohol, etc.)
_1-20 alkyl monoalcohols) and monovalent aralkyl alcohols (C _7-20 aralkyl monoalcohols such as benzyl alcohol and phenethyl alcohol).

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

Further, the polyarylate resin may constitute a polymer alloy with another resin, for example, a polyester, polyamide, polycarbonate or the like. The polymer alloy includes not only a simple mixture but also a polymer alloy obtained by a transesterification reaction or a polymer alloy containing a compatibilizer.

The number average molecular weight of the polyarylate resin is as follows:
For example, about 300 to 30 × 10 ⁴ , preferably 500
About 10 × 10 ⁴ , more preferably 500 to 5 × 1
0 is about ^4.

(3) Aromatic epoxy resin The aromatic epoxy resin includes an ether epoxy resin (for example, a bisphenol epoxy resin, a novolak epoxy resin, etc.), an amine epoxy resin using an aromatic amine component, and the like. It is.

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

Novola constituting novolak type epoxy resin
As a rack resin, an alkyl group (for example,
C_1-20Alkyl group, preferably methyl group, ethyl group, etc.
C _1-4Novolak which may be substituted by an alkyl group)
Resin (eg, phenol novolak resin, cresol
A novolak resin). preferable
Novolak type epoxy resin has C_1-2Alkyl group
Glycidyl ether of novolak resin which may be replaced
Is included.

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

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

Epoxy resins include amine-based curing agents (for example, aliphatic amines such as ethylenediamine, aromatic amines such as metaphenylenediamine and xylylenediamine), polyaminoamide-based curing agents, acids and acid anhydride-based curing agents. It may be used after being cured by a curing agent such as a curing agent.

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

(4) 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 includes an alicyclic compound (such as the alicyclic diol exemplified in the section of the polyester resin), a bisphenol compound, and the like. In addition, at least one of the dihydroxy compound and the carbonate is an aromatic compound.

Examples of the bisphenol compound include bisphenols exemplified in the section of the novolak resin (particularly, bis (hydroxyaryl) C _1-6 alkane, bis (hydroxyaryl) C _4-10 cycloalkane, 4,4′-dihydroxy Diphenyl ether; 4,4'-dihydroxydiphenyl sulfone; 4,4'-dihydroxydiphenyl sulfide; 4,4'-dihydroxydiphenyl ketone, etc.).

The resinous flame-retardant aids can be used alone or in combination of two or more.

Preferred resinous flame retardant aids include resins having an aromatic ring having a hydroxyl group and / or an amino group in the main chain or side chain, bisphenol resins (polyarylate resins, epoxy resins (or phenoxy resins)). ), Polycarbonate resins, etc.).

The content of the resinous flame retardant aid is, for example, about 1 to 30 parts by weight, preferably about 3 to 25 parts by weight, more preferably about 5 to 20 parts by weight based on 100 parts by weight of the thermoplastic resin. You can choose from a range.

[Nitrogen-containing flame retardant (D2)] Examples of the nitrogen-containing flame retardant include (a) a nitrogen-containing cyclic compound, sulfuric acid,
Salts with boric acid, inorganic phosphoric acid or a heterocyclic compound having a hydroxyl group, (b) polyphosphoramide, (c) cyclic ureas and the like are included.

(A) Salt of nitrogen-containing cyclic compound As the nitrogen-containing cyclic compound, the same compounds as in the above (B3) can be used.

(A-1) Sulfate of Nitrogen-Containing Cyclic Compound Having Amino Group Examples of the sulfuric acid include non-condensed sulfuric acid such as peroxomonosulfuric acid, sulfuric acid and sulfurous acid, and condensed sulfuric acid such as pyrosulfuric acid.

Examples of the sulfate of the nitrogen-containing cyclic compound include sulfates of a triazine compound having an amino group, for example, non-condensed sulfates such as melamine sulfates (melamine sulfate, dimelamine sulfate, guanylmelamine sulfate, etc.) and melamine sulfate. Non-condensed melamine sulfates such as melamine sulfite; melem salts and melam salts corresponding to the non-condensed melamine sulfate;
Melon salts, guanamine salts, etc.)], condensed sulfates [melamine pyrosulfates (melamine pyrosulfate, dimelamine pyrosulfate, etc.), melem salts corresponding to melamine pyrosulfates, melam salts, melon salts, guanamine salts, etc.] Can be illustrated. Further, a triazole salt corresponding to the triazine salt can also be used.

Incidentally, melamine sulfate is described in, for example,
It can be obtained by the method described in JP-A-231517. Dimelam pyrosulfate is, for example, ACS Sympo
siumSeries No. 425 "Fire and Polymers", Chapter 15,
211-238 (American Chemical Society, Washi
ngton DC, 1990) and JP-A-10-306082.

(A-2) Borate of nitrogen-containing cyclic compound As boric acid, non-condensed boric acid such as orthoboric acid and metaboric acid, and condensed boric acid such as tetraboric acid and boric anhydride can be used.

The borate of the nitrogen-containing cyclic compound includes:
Borates of amino group-containing triazine compounds, for example, non-condensed borates [melamine orthoborates (melamine orthoborates such as mono to trimeramine orthoborates), melem salts corresponding to the melamine salts, melam salts,
Orthoborates such as melon salts and guanamine salts; metaborates corresponding to the above-mentioned orthoborates], polyborates [melamine condensed borate (melamine anhydrous borate, melamine tetraborate, etc.), corresponding to the melamine salts] Melem salt, melam salt, melon salt, guanamine salt]. Melamine borate is disclosed in, for example, JP-A-54-4
It can be obtained by the method described in JP-A-7750 or JP-A-11-79720.

(A-3) Inorganic Phosphate of Nitrogen-Containing Cyclic Compound Examples of the inorganic phosphoric acid include peroxoic acid, orthophosphoric acid, metaphosphoric acid, phosphorous acid (phosphonic acid) and hypophosphorous acid (phosphinic acid). Non-condensed phosphoric acid and polyphosphoric acid can be used. A preferred inorganic phosphoric acid is polyphosphoric acid.

The polyphosphoric acid includes condensed phosphoric acids represented by the following formula (10).

[0173]

Embedded image

(In the formula, t represents an integer of 2 or more) In the above formula, t is preferably an integer of 2 to 10, more preferably an integer of 3 to 8. Examples of such polyphosphoric acid include pyrophosphoric acid, triphosphoric acid, and tetraphosphoric acid.

Further, the polyphosphoric acid includes polymetaphosphoric acid (HPO ₃ ) _n (where n is an integer of 2 or more),
Hypophosphoric acid, phosphoric anhydride (diphosphorus pentoxide) and the like are also included.

It is to be noted that polyphosphoric acid having a plurality of sites capable of forming a salt has at least a portion of which is partially salted with another amino group-containing compound such as amine or urea (partial salt such as ammonium polyphosphate or urea polyphosphate). ) May be formed.

Non-condensed phosphates of nitrogen-containing cyclic compounds include triazine salts (melamine salts such as melamine orthophosphate and melamine phosphonate; melem salts, melam salts, melon salts, guanamine salts and the like corresponding to the above melamine salts). Is included. Further, a triazole salt or the like corresponding to the triazine salt can also be used.

Examples of the polyphosphate of the nitrogen-containing cyclic compound include polyphosphates of amino group-containing triazine compounds [melamine pyrophosphate (melamine pyrophosphate, dimelamine pyrophosphate), and triphosphates corresponding to these melamine pyrophosphate salts. Melamine polyphosphates such as salts and tetraphosphates; melem salts, melam salts, melon salts, guanamine salts and the like corresponding to the above melamine polyphosphate salts]. Further, a triazole salt or the like corresponding to the triazine salt can also be used. The polyphosphate may contain a sulfur atom derived from sulfuric acid. In addition, polyphosphates include melamine / melam / melem double salt of polyphosphate, melamine / melam / melem double salt of metaphosphate, and melamine / melam / polylaminate of polyacid containing sulfur atom, oxygen atom, etc. in addition to phosphorus atom. Melem double salt is also included. Details of the polyacid or double salt containing a sulfur atom are described in JP-A-10-306082.
Can be referred to. These polyphosphates may be treated with a surface modifier such as an epoxy compound, a silane compound, a titanate compound, and a chromium compound.

The inorganic phosphates can be used alone or in combination of two or more.

The ratio between the nitrogen-containing cyclic compound and the inorganic phosphoric acid is not particularly limited. For example, the former / the latter (molar ratio) =
1/20 to 20/1, preferably 1/10 to 10/1
(For example, 1/5 to 10/1), particularly about 1/2 to 8/1. The equivalent ratio between the amino group of the nitrogen-containing cyclic compound and the salt-formable site of the inorganic phosphoric acid is not particularly limited,
For example, about 10/1 to 1/2, preferably 5/1 to 1
/ 1, especially about 4/1 to 1/1.

(A-4) Salt of Nitrogen-Containing Cyclic Compound and Heterocyclic Compound Having a Hydroxyl Group A heterocyclic compound having a hydroxyl group has at least one hydroxyl group and at least one nitrogen atom as a heteroatom of the ring. And a heterocyclic ring.
Examples of the hetero ring include a hetero ring corresponding to the nitrogen-containing cyclic compound. Preferred nitrogen-containing rings are, as described above, 5- or 6-membered unsaturated nitrogen-containing rings having a plurality of nitrogen atoms as ring constituent atoms, particularly triazine.

Examples of the triazine compound include triazine compounds corresponding to the above-mentioned nitrogen cyclic compounds, and the hydroxyl group may be a 2-position, 3-position, 4-position, 5-position, 2,4
-Position, 3,5-position, 4,5-position, 2,4,6-position, 4,
It may be substituted at an appropriate position such as the 5,6-position.
Preferred hydroxyl group-containing triazine compounds are hydroxyl group-containing 1,3,5-triazines, particularly cyanuric acid such as cyanuric acid or isocyanuric acid, ammeline, ammelide, and derivatives thereof.

Examples of the salt of the nitrogen-containing cyclic compound with the heterocyclic compound having a hydroxyl group include salts of triazines with cyanuric acid or a derivative thereof, for example, melamine salts of cyanuric acid such as melamine cyanurate; And melamine salts, melam salts, melon salts, guanamine salts (eg, guanamine cyanurate, acetoguanamine cyanurate, benzoguanamine cyanurate, etc.).

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

The ratio between the nitrogen-containing cyclic compound and the heterocyclic compound having a hydroxyl group is not particularly limited.
For example, the former / the latter (molar ratio) = 1/2 to 3/1, preferably about 1/1 to 2/1.

(B) Polyphosphoramide As the polyphosphoramide, the inorganic phosphate (a-3)
And phosphoric acids such as the organic phosphoric acid exemplified in the above-mentioned organic phosphate (B3), and -N = C = N- or -N. = C
An amide nitrogen obtained by calcining and condensing a compound having a unit represented by (-N <) ₂ (such as a cyanamide derivative) in the presence of urea and / or urea phosphate as a binder is used. Containing high molecular compounds. As the phosphoric acid, non-condensed phosphoric acid (orthophosphoric acid, metaphosphoric acid, etc.), polyphosphoric acid, partial ester of phosphoric acid (ammonium polyphosphate, urea phosphate, etc.) are preferred,
As the cyanamide derivative, triazines such as melamine (especially 1,3,5-triazines), and various amidine compounds such as dicyandiamide, guanidine, and guanylurea are preferable. Polyphosphoramides can be used alone or in combination of two or more. As for polyphosphoramide, for example, JP-A-7-138463 can be referred to. Such polyphosphoramides are disclosed in
It can be produced by the method described in JP-A-1-39271 and JP-B-53-2170. The polyphosphoramide obtained by the condensation reaction of ammonium polyphosphate and melamine is commercially available as "Sumisafe PM" from Sumitomo Chemical Co., Ltd. (C) Cyclic Urea The cyclic urea is not particularly limited as long as it has at least one urea unit as a constituent unit of a ring, and may be any of a monocyclic compound, a condensed ring with an aromatic hydrocarbon ring, a bridged ring and the like. There may be. Such cyclic ureas include various cyclic ureido compounds, for example, alkylene urea [methylene urea, ethylene urea, C _1-10 alkylene urea such as CDU nitrogen (preferably C _1-6 alkylene urea) and the like],
Alkenylene urea (C such as vinylene urea and cytosine)
_2-10 etc. alkenylene urea), [such as C _2-10 alkynylene urea and acetylene urea (preferably C _2-6 alkynylene urea) alkynylene urea, such arylene urea (Imesachin) ureido or a derivative of a dicarboxylic acid (parabanic Acid, dimethylparabanic acid, barbituric acid,
5,5-Diethylbarbituric acid, dilituric acid, dialluric acid, alloxanic acid, alloxanthine, isocyanuric acid, uramil, purpuric acid, etc., ureide of β-aldehyde acid or a derivative thereof (uracil, 5-methyluracil (thymine) ), Dihydrouracil, urazole, benzyleneurea, etc.), ureides of α-oxy acids or derivatives thereof (hydantoin, 5,5-dimethylhydantoin,
Hydantoins such as 1,1, -methylenebis (5,5-dimethylhydantoin) and allantoin, and cyclic diureido (uric acid, 3-methyluric acid, pseudouric acid, glycoluril; diurea such as p-urazine) and the like. No. Also, cyclic thioureas (ethylene thiourea, thiobarbituric acid, dithiourazole, thiohydantoin, dithiohydantoin, etc.) corresponding to the cyclic urea can be used. Further, among the compounds exemplified in the section of the hydroxyl group-containing heterocyclic compound, compounds having an enol form of urea as a constituent unit (that is, compounds in which tautomers have a urea unit, such as ammeline and ammelide), and the like. Can also be used. These cyclic ureas can be used alone or in combination of two or more.

[Inorganic flame retardant auxiliary (D3)] Examples of the inorganic flame retardant auxiliary (or flame retardant) include a metal salt of an inorganic acid and red phosphorus.

(1) Metal Salts of Inorganic Acids The inorganic acids constituting the salts include oxyacids [oxygen acids such as nitric acid, chloric acid (perchloric acid, chloric acid, chlorous acid, hypochlorous acid, etc.)] , Phosphoric acid, sulfuric acid, boric acid, chromic acid, antimonic acid, etc.], halogen acids (eg, hydrochloric acid), and carbonic acid. The phosphoric acid, sulfuric acid and boric acid may be any of a non-condensed type and a condensed type. Phosphorus exemplified in the section of the organic phosphate (B3) or the nitrogen-containing flame retardant auxiliary (D2). Acid, sulfuric acid, boric acid can be used.

Preferred inorganic acids are phosphoric acid and boric acid.

Metals which form salts with inorganic acids include alkali metals (such as potassium and sodium); alkaline earth metals (such as magnesium, calcium and barium); transition metals (Group 3A metals such as scandium); Group 4A metals; Group 5A metals such as vanadium; chromium,
Group 6A metals such as molybdenum and tungsten; Group 7A metals such as manganese; Group 8 metals such as iron, cobalt, nickel and palladium; and Group 1B metals such as copper and silver), and Group 2B metals (zinc , Cadmium, mercury, etc.),
Examples include a Group 3B metal (such as aluminum), a Group 4B metal (such as tin and lead), and a Group 5B metal (such as antimony and bismuth). These metals can be used alone or in combination of two or more.

(1-1) Phosphoric acid metal salt Phosphoric acid includes non-condensed phosphoric acid and condensed phosphoric acid (polyphosphoric acid)
And the like, and non-condensed phosphoric acid is particularly preferred.

The metal is preferably a polyvalent metal, for example, an alkaline earth metal, a transition metal, a metal of Groups 2B to 3B of the periodic table, particularly an alkaline earth metal.

Examples of the metal salt of phosphoric acid include, in addition to the salt of phosphoric acid and a polyvalent metal, a hydrogen phosphate corresponding to the polyvalent metal phosphate. A child (eg, hydroxo, halogen, etc.) may be coordinated.

Examples of metal salts of phosphoric acid include pyrophosphate (Ca ₂ P ₂ O _{7 and the} like) and polymetaphosphate (Ca ₃
(P ₃ O ₉ ) ₂ ), anhydrous phosphates (Ca ₂ (P
₄ O ₁₂ ), Ca ₅ (P ₃ O ₁₀ ) _2, etc.) and Ca ₅ (P
Condensed phosphates such as O ₄ ) ₃ (OH) and Ca ₅ (PO ₄ ) ₃ (F, Cl) may be used, but hydrogen phosphate is preferably used.

Examples of such hydrogen phosphates include magnesium hydrogen orthophosphate (eg, magnesium hydrogen phosphate, magnesium dihydrogen phosphate), calcium hydrogen orthophosphate (eg, calcium dihydrogen phosphate, dibasic calcium phosphate) and the like. Alkaline earth metal hydrogen phosphates; transition metal hydrogen phosphates such as manganese hydrogen phosphate (manganese (III) hydrogen phosphate), iron hydrogen phosphate (Fe (H ₂ PO ₄ ) ₃ etc.); Periodic Table 2B metal phosphates such as zinc hydrogen hydride and cadmium hydrogen phosphate; Periodic Table 3B metal phosphates such as aluminum hydrogen phosphate; Periodic table such as tin hydrogen phosphate Non-condensed hydrogen phosphates such as hydrogen phosphates of Group 4B metals. Of these, substantially anhydrous metal hydrogen phosphate,
Particularly preferred are alkaline earth metal hydrogen phosphates (magnesium dihydrogen phosphate, calcium dihydrogen phosphate, dibasic calcium phosphate (CaHPO ₄ ), etc.).

(1-2) Metal salts of boric acid As boric acid, non-condensed boric acid such as orthoboric acid and metaboric acid; condensed boric acid such as pyroboric acid, tetraboric acid, pentaboric acid and octaboric acid; In addition, basic boric acid and the like are preferable.

As the metal, an alkali metal or the like may be used, but an alkaline earth metal, a transition metal, and a polyvalent metal of Group 2B of the periodic table are preferable.

The metal borate is usually a hydrated salt, for example, a non-condensed borate [alkali earth metal non-condensed borate such as calcium orthoborate and calcium metaborate; manganese orthoborate, copper metaborate Transition metal non-condensed borates such as zinc metaborate and cadmium metaborate; non-condensed borates (particularly metaborates) of Group 2B metals of the periodic table; condensed borates (trimagnesium tetraborate) And alkaline earth metal condensed borates such as calcium pyroborate; transition metal condensates such as manganese tetraborate and nickel diborate; and metals of Group 2B of the periodic table such as zinc tetraborate and cadmium tetraborate. Condensed borates, etc.); basic borates (eg, basic zinc borates, basic cadmium borates, etc., Group 2B metals such as basic borates). That. In addition, a hydrogen borate salt (for example, manganese hydrogen orthoborate) corresponding to these borates can also be used. Particularly preferred are Group 2B metal borates (non-condensed or condensed borates) of the Periodic Table, particularly zinc borates.

As metal salts of inorganic acids other than phosphoric acid and boric acid (oxygen acids and the like), various metal salts corresponding to the above-mentioned metal phosphates and metal borates can be used.

(2) Red Phosphorus Usually, red phosphorus that has been subjected to a stabilization treatment (stabilized red phosphorus) is preferably used. In particular, red phosphorus obtained by a method of pulverizing red phosphorus without pulverizing the red phosphorus and forming a highly crushed surface having high reactivity with water and oxygen on the surface of the red phosphorus,
Further, the surface of red phosphorus is used alone or in combination of two or more with a resin (eg, a thermosetting resin, a thermoplastic resin), a metal, a metal compound (eg, a metal hydroxide, a metal oxide, etc.). Coated red phosphorus 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 of 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, using a method in which red phosphorus is finely divided without forming a crushed surface on the surface of red phosphorus, a coating of a metal component (metal hydroxide or metal oxide) and a coating of a resin are combined to form a plurality of layers. Red phosphorus which is coated, in particular, coated with a metal component film and then multiply coated with a resin coating, is preferred.
These stabilized red phosphorus are excellent in heat stability and hydrolysis resistance, and the generation of phosphine by the decomposition reaction in the presence of moisture or at high temperature is extremely low. And from the viewpoint of safety when producing molded articles.

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

As 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.

These inorganic flame retardant aids can be used alone or in combination of two or more. Inorganic flame retardant aids (especially,
The content of the metal salt of an inorganic acid) is, for example, the thermoplastic resin 1
The amount can be selected from the range of about 0.5 to 30 parts by weight, preferably about 2 to 20 parts by weight, more preferably about 3 to 15 parts by weight with respect to 00 parts by weight.

The flame-retardant resin composition of the present invention further imparts flame-retardant properties, so that other flame-retardant auxiliaries, for example, amines, sulfur-containing flame-retardant auxiliaries, and silicon-containing flame-retardant auxiliaries. , An alcohol-based flame-retardant auxiliary, a metal oxide, a metal hydroxide, a metal stannate (eg, zinc duzate), and an expandable graphite.

Examples of the amines include ureas, guanidines, triazine compounds (eg, melamine, melam, melem, melon, ammeline, melamine formaldehyde resin, guanamine, acetoguanamine, benzoguanamine, etc.).

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

[0210] 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.).

Examples of the metal oxide include molybdenum oxide, tungsten oxide, titanium oxide, zirconium oxide, tin oxide, copper oxide, zinc oxide, aluminum oxide,
Examples include nickel oxide, iron oxide, manganese oxide, antimony trioxide, antimony tetroxide, and antimony pentoxide.

Examples of the metal hydroxide include aluminum hydroxide, magnesium hydroxide, tin hydroxide and zirconium hydroxide.

These other flame-retardant auxiliaries can be used alone or in combination of two or more.

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

[Styrene Resin] The resin composition of the present invention may further contain a styrene resin. As the styrene resin, for example, a styrene monomer (for example,
Homo- or copolymers of styrene, vinyl toluene, α-methyl styrene, chlorostyrene, etc .; styrene monomers and vinyl monomers (eg, unsaturated nitriles such as acrylonitrile, (meth) acrylates, (meth) ) Copolymers with α, β-monoolefinically unsaturated carboxylic acids such as acrylic acid and maleic anhydride or acid anhydrides or esters thereof; styrene-based graft copolymers, styrene-based block copolymers, etc. No.

Preferred styrene resins include polystyrene (GPPS), styrene-methyl methacrylate copolymer, styrene- (meth) acrylic acid copolymer, styrene-maleic anhydride copolymer, and 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.
As the block copolymer, a copolymer composed of a polystyrene block and a diene or olefin block (for example, styrene-butadiene-styrene (SBS))
Block copolymer, styrene-isoprene block copolymer, styrene-isoprene-styrene (SIS) block copolymer, hydrogenated styrene-butadiene-styrene (SEBS) block copolymer, hydrogenated styrene-
Isoprene-styrene (SEPS) block copolymer)
And the like.

The number average molecular weight of the styrenic resin is not particularly limited, and is, for example, 5 × 10 ³ to 200 × 10 ⁴ , preferably 1 × 10 ^{4 to} 150 × 10 ⁴ , and more preferably 1 × 10 ^{4 to} 150 × 10 ⁴ .
It can be selected from a range of about 10 ^{4 to} 100 × 10 ⁴ .

The styrenic resins can be used alone or in combination of two or more. The content of the styrene resin can be selected, for example, from a range of 1 to 30 parts by weight, preferably 5 to 20 parts by weight, particularly about 7 to 15 parts by weight based on 100 parts by weight of the thermoplastic resin.

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

Examples of the phenolic antioxidants include hindered phenols, for example, C-atoms such as 1,6-hexanediol-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate]. _2-10 alkylenediol-bis [3- (3,5-di-branched C _3-6 alkyl-
4-hydroxyphenyl) propionate];
Triethylene glycol - bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate] di- or Toriokishi C _2-4 alkylene diol such as - bis [3- (3,5-di - branched C _3-6 alkyl-4-
Hydroxyphenyl) propionate]; for example, C _3-8 alkylene triol such as glycerin tris [3- (3,5-di -t- butyl-4-hydroxyphenyl) propionate] - bis [3- (3,5-di -Branch C
_3-6 alkyl-4-hydroxyphenyl) propionate]; for example, pentaerythritol tetrakis [3-
(3,5-di-t-butyl-4-hydroxyphenyl)
C _4-8 alkylene tetrols tetrakis such propionate] [3- (3,5-di - branched C _3-6 alkyl -
4-hydroxyphenyl) propionate] and the like.

[0222] The amine-series antioxidant, a hindered amine, for example, tri- or tetra-C _1-3 alkyl piperidine or methoxy derivative thereof (4-position, benzoyloxy, phenoxy and the like may be substituted 2,2 , 6,
6-tetramethylpiperidine, etc.), bis (tri, tetra or pentaC _1-3 alkylpiperidine) C _2-20 alkylenedicarboxylic acid ester [for example, bis (2,2,
6,6-tetramethyl-4-piperidyl) oxalate, malonate corresponding to oxalate, adipate,
Sebacate, terephthalate, etc .; bis (1,2,2,2)
6,6-pentamethyl-4-piperidyl) sebacate], 1,2-bis (2,2,6,6-tetramethyl-
4-piperidyloxy) ethane, phenylnaphthylamine, 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, bis or tris (branched C _3-6 alkylphenyl) phosphite [ For example, bis or tris (2-t-butylphenyl) phenyl phosphite, tris (2,4-di-t-butylphenyl) phosphite, tris (2-t-butylphenyl) phosphite
-Butyl-4-methylphenyl) phosphite, tris (2,4-di-t-amylphenyl) phosphite and the like], tris (2-cyclohexylphenyl) phosphite, bis (C _1-9 alkylaryl) pentaerythritol Diphosphite [for example, bis (2,4-di-t
-Butylphenyl) pentaerythritol diphosphite, bis (2,4-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2
6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (nonylphenyl) pentaerythritol diphosphite, etc.], triphenyl phosphate stabilizers (for example, 4-phenoxy-9)
-Α- (4-hydroxyphenyl) -p-cumenyloxy-3,5,8,10-tetraoxa-4,9-diphosphapiro [5,5] undecane, tris (2,4-di-t
-Butylphenyl) phosphate, etc.), diphosphonite-based stabilizers (for example, tetrakis (2,4-di-t-
Butyl) -4,4'-biphenylenediphosphonite and the like. Phosphorus stabilizers are usually branched C
_{It has a 3-6} alkylphenyl group (particularly a 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.

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

The fluororesin may be used in the form of particles. The average particle size 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 fluorine-based resin is, for example, 100% in total of the thermoplastic resin and the polyphenylene oxide-based resin.
About 0.01 to 10 parts by weight, preferably about 0.1 to 5 parts by weight, more preferably 0.1 to 3 parts by weight with respect to parts by weight.
It is about parts by weight.

[Filler] The flame-retardant resin composition of the present invention comprises:
In order to further improve the mechanical strength, rigidity, heat resistance, electrical properties, and the like, it may be modified with a filler.
The filler includes a fibrous filler and a non-fibrous filler (a plate-like filler, a particulate filler, and the like).

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.).

Of the non-fibrous fillers, the plate-like fillers include:
For example, glass flake, mica, graphite, various metal foils and the like can be exemplified.

Examples of the particulate filler include carbon black, silica, quartz powder, glass beads, glass powder, milled fiber (for example, 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; sulfuric acids of metals such as calcium sulfate and barium sulfate Metal powders such as salts and silicon carbide are included.

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, mica and the like. , And glass flakes.

Particularly preferred fillers include glass fibers having high strength and rigidity (such as chopped strands).

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, if necessary, a sizing agent or a surface treatment agent may be used. 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 amount of the functional surface treating agent or sizing agent used in combination is 5% by weight or less, preferably about 0.05 to 2% by weight, based on the filler.

The flame retardant of the present invention can make the resin highly flame retardant, probably because it promotes carbonization of the thermoplastic resin surface during combustion. Further, even when using a non-halogen flame retardant containing a polyphenylene oxide resin, by combining with a phosphate ester and an organic phosphate of a nitrogen-containing cyclic compound,
Even a small amount can effectively render the thermoplastic resin flame-retardant, and there is no risk of bleed-out. In particular, since an organic phosphate of a nitrogen-containing cyclic compound is used as the flame retardant component, the flame retardant effect can be greatly improved without coloring the resin composition.

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. .

[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 be a thermoplastic resin (such as a polyester resin).
And a flame retardant and, if necessary, an anti-dripping agent and other additives by a conventional method. For example, (1) mixing each component, kneading and extruding with a single-screw or twin-screw extruder to prepare pellets, and then molding, (2) once preparing pellets (master batch) having different compositions. Mixing (diluting) the pellets in a predetermined amount
And subjecting it to molding to obtain a molded article of a predetermined composition, (3)
A method of directly charging one or more of each component to a molding machine can be adopted. In addition, in the preparation of a composition used for a molded article, a powder or granules obtained by crushing a part or all of a thermoplastic resin, and other components (a flame retardant or the like) are mixed and melt-kneaded. This is advantageous for improving dispersion.

From the viewpoint of handling, non-resinous components (phosphates, organic phosphates of nitrogen-containing cyclic compounds, inorganic flame retardants, etc.) and resinous components (thermoplastic resins, polyphenylene oxide resins, It is convenient to once prepare a masterbatch by melt-mixing with a resinous flame-retardant auxiliary agent). In particular, when red phosphorus is used as the inorganic flame retardant, a master batch is often prepared. When a masterbatch is composed of resinous components, a thermoplastic resin is often used for the masterbatch.

The masterbatch includes, for example, (1) a masterbatch composed of a thermoplastic resin (eg, a polyester resin) and a non-resinous component, and (2) a polyphenylene oxide resin and a phosphate ester. Master batch composed of (3) polyphenylene oxide resin and non-resinous components (phosphate esters, organic phosphates of nitrogen-containing cyclic compounds, and inorganic flame retardants), (4) heat A masterbatch composed of a plastic resin, a polyphenylene oxide resin, and non-resinous components (phosphates, organic phosphates of nitrogen-containing cyclic compounds, and inorganic flame retardants) is exemplified.

The masterbatch may contain various additives, for example, a fluorine resin, an antioxidant, a phosphorus 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, packaging materials and cases.

[0247]

According to the present invention, a halogen-based flame retardant is used because a thermoplastic resin is combined with a flame retardant composed of a polyphenylene oxide resin, an organic phosphate of a phosphate and a nitrogen-containing cyclic compound. Without doing
Flame retardancy can be achieved even in a small amount, and deterioration of resin properties can be suppressed. Further, a molded article having improved flame retardancy can be obtained by such a resin composition.

[0248]

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 flame resistance of the resin composition was evaluated by the following test.

(Flammability Test) Flammability was evaluated based on UL94 at a test piece thickness of 1.6 mm.

(Blooming property test) A 1.6 mm thick test piece was heated at 150 ° C for 5 hours, and the surface of the test piece was visually observed for bleed-out of the flame retardant.
Evaluation was made according to the following criteria.

A: No exudation was observed at all. X: Remarkable exudation was observed. [Polyester resin A] A-1: Polybutylene terephthalate [Duranex, intrinsic viscosity = 1.0, Polyplastics Co., Ltd.] A-2: Polyethylene terephthalate [Bellpet EF]
G10, manufactured by Kanebo Co., Ltd.] [Polyphenylene oxide resin B] B-1: Poly (2,6-dimethyl-1,4-phenylene) oxide (intrinsic viscosity = 0.3) [Bisphenol resin C] C- 1: Polycarbonate [Panlite L1225, manufactured by Teijin Chemicals Ltd.] C-2: Polyarylate [Polyarylate U100, manufactured by Unitika Ltd.] C-3: Phenoxy resin [Phenotote YP-50, Toto Kasei Co., Ltd.] [Styrene-based resin D] D-1: polystyrene [Toyostyrol GP G2]
00C, manufactured by Toyo Styrene Co., Ltd.] D-2: Acrylonitrile-styrene copolymer [Sebian DP611, manufactured by Daicel Chemical Industries, Ltd.] D-3: Acrylonitrile-butadiene-styrene copolymer [Sebian JD, Daicel Chemical Industries, Ltd.] [Phosphoric esters E] E-1: Resorcinol bis (di-2,6-xylenyl phosphate) [PX200, manufactured by Daihachi Chemical Industry Co., Ltd.] E-2: Resorcinol bis (diphenyl) Phosphate) E-3: Hydroquinone bis (di-2,6-xylenyl phosphate) [PX201, manufactured by Daihachi Chemical Industry Co., Ltd.] E-4: Bisphenol-A bis (di-2,6-xylenyl) Phosphate) [Organic phosphate F of triazine compound] F-1: Melamine salt of phenylphosphonic acid Water-soluble phenylphosphonic acid To a (concentration of 10% by weight), an aqueous suspension of melamine (concentration of 10% by weight) (phenylphosphonic acid / melamine = 1/1 (molar ratio)) was added, and the mixture was stirred at 80 ° C. for 6 hours to form a precipitate. Obtained by filtration, dried and pulverized in a lab mill.

F-2: Dimelamine salt of phenylphosphonic acid An aqueous solution of phenylphosphonic acid (concentration of 10% by weight) was added to an aqueous suspension of melamine (concentration of 10% by weight) (phenylphosphonic acid / melamine = 1/2 (mol) Ratio)), and the mixture was stirred at 80 ° C. for 6 hours, and the resulting precipitate was obtained by filtration, dried, and pulverized by a lab mill.

F-3: Dimelamine salt of pentaerythritol bis (phosphate) F-4: Melamine salt of 3-phenylphosphinicopropionic acid Water-acetone solution of 3-phenylphosphinicopropionic acid (water / acetone = 70) / 30 (weight ratio)) (concentration 1
0% by weight) and a water suspension of melamine (concentration 10% by weight)
(3-phenylphosphinicopropionic acid / melamine =
1/1 (molar ratio)), and the mixture was stirred at 70 ° C. for 6 hours, and the resulting precipitate was collected by filtration, dried, and pulverized by a lab mill.

F-5: Hexamelamine salt of nitrilotris (methylene phosphonic acid) An aqueous solution of melamine (concentration: 10% by weight) was added to an aqueous solution of nitrilotris (methylene phosphonic acid) (concentration: 10% by weight). (Methylenephosphonic acid) / melamine = 1/6 (molar ratio), and the mixture was stirred at 80 ° C. for 3 hours, and the resulting precipitate was collected by filtration, dried, and pulverized by a lab mill.

F-6: 1-hydroxyethylidene-1,
Tetramelamine salt of 1-diphosphonic acid Aqueous suspension of melamine (concentration 10% by weight) (1-hydroxyethylidene-1,1) was added to an aqueous solution (concentration 10% by weight) of 1-hydroxyethylidene-1,1-diphosphonic acid. -Diphosphonic acid / melamine = 1/4 (molar ratio))
A compound obtained by stirring at 0 ° C. for 3 hours, collecting a generated precipitate by filtration, drying, and pulverizing in a lab mill.

[Flame Retardant Aid G] G-1: Zinc borate [Firebreak ZB, manufactured by Pollux Japan K.K.] G-2: Calcium monohydrogen phosphate anhydrous: Average particle size = about 30 μm [Tahei Chemical Industry G-3: Novolak-type phenolic resin [Sumilite Resin PR53195, manufactured by Sumitomo Durez Co., Ltd.] G-4: Red phosphorus [Nova Excel 140, manufactured by Rin Kagaku Kogyo] [Antioxidant H H-1: pentaerythritol-tetrakis [3-
(3,5-di-t-butyl-4-hydroxyphenyl)
[Propionate] [Irganox 1010, manufactured by Ciba Geigy Co., Ltd.] [Phosphorus stabilizer I] I-1: bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite [ADEKA STAB PEP36; Asahi Denka Kogyo Co., Ltd.] I-2: Tetrakis (2,4-di-t-butylphenyl) -4,4′-biphenylenediphosphonite [Sandstub P-EPQ, manufactured by Sando Co., Ltd.] Anti-ripping agent J] J-1: polytetrafluoroethylene [filler K] K-1: glass fiber (chopped strand having a diameter of 10 μm and a length of 3 mm) Examples 1 to 22 and Comparative Examples 1 to 9 The resin compositions were mixed at the ratios (parts by weight) shown in Tables 1 to 3 and melted and kneaded with a Labo Plastomill to prepare a resin composition. A test molded product (130 × 13 × 1.6 mm) was prepared from this resin composition by press working, and the flammability and blooming properties were evaluated.

Tables 1 to 3 show the results.

[0259]

[Table 1]

[0260]

[Table 2]

[0261]

[Table 3]

As is clear from Tables 1 to 3, in the examples, the flame retardant was composed of a polyphenylene oxide resin, a phosphoric acid ester, and an organic phosphate of a nitrogen-containing cyclic compound in comparison with the comparative example. Therefore, the thermoplastic resin can be highly flame-retarded without exuding the flame retardant.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08K 5/13 C08K 5/13 5/16 5/16 5/49 5/49 5/52 5/52 5 / 521 5/521 5/5313 5/5313 5/5373 5/5373 5/5399 5/5399 C08L 71/12 C08L 71/12 F term (reference) 4F071 AA14 AA22 AA26 AA28 AA31 AA41 AA42 AA43 AA44 AA45 AA50 AA51 AA54 AA78 AB05 AB25 AC11 AC13 AC17 AH04 AH07 AH12 AH17 BB03 BB05 BB06 4J002 BB03W BB12W BB151 BB17W BC02Z BD12U BE02W BF01W BF02W BF03W BG01W BG04W BG05W BG06W CC04Y CD05Y CD06Y CD13Y CE00Y CF03W CF05W CF06W CF07W CF08W CF16Y CF19W CG00Y CG01Y CH07X CL01W CL03W CL05W DA059 DE199 DF039 DG039 DH008 DH029 DH048 DH058 DK009 EJ029 EJ039 ET018 EU188 EV268 EW046 EW126 EW136 EW157 EY018 FD010 FD136 FD137 FD138 FD139 GG02 GM00 GN00 GQ00

Claims (16)

[Claims] 1. A flame-retardant resin composition comprising a thermoplastic resin (A) and a flame retardant (B), wherein the flame retardant is a polyphenylene oxide resin (B1), a phosphate ester (B2) ) And an organic phosphate of a nitrogen-containing compound (B
Flame-retardant resin composition constituted by 3). 2. The flame-retardant resin according to claim 1, wherein the thermoplastic resin (A) is at least one selected from a polyester resin, a polyamide resin, a vinyl resin, an olefin resin, and an acrylic resin. Composition. 3. The thermoplastic resin (A) according to claim 1, wherein the thermoplastic resin (A) has at least one unit selected from 1,4-cyclohexane dimethylene terephthalate, C _2-4 alkylene terephthalate and C _2-4 alkylene naphthalate. The flame-retardant resin composition according to claim 1, which is a polyester. 4. The flame-retardant resin composition according to claim 1, wherein the thermoplastic resin (A) is polybutylene terephthalate or a copolyester containing butylene terephthalate as a main component. 5. The flame-retardant resin composition according to claim 1, wherein the phosphate ester (B2) is a condensed phosphate ester. 6. Organic phosphate of a nitrogen-containing compound (B3)
Is a salt of at least one selected from melamine and a melamine condensate and at least one selected from non-condensed phosphoric acid partial esters, organic phosphonic acids and organic phosphinic acids. Composition. 7. The method according to claim 1, wherein the flame retardant (B) is poly (mono- or di-C).
The flame-retardant resin composition according to claim 1, comprising _1-6 alkyl-phenylene) oxide (B1), a condensed phosphate (B2), and an organic phosphate (B3) of a melamine condensate. 8. The flame-retardant resin composition according to claim 1, comprising 10 to 300 parts by weight of the flame retardant (B) based on 100 parts by weight of the thermoplastic resin (A). 9. The flame retardant (B) is a phosphate ester (B)
2) A polyphenylene oxide resin of 10 to 500 parts by weight and an organic phosphate (B3) of a nitrogen-containing compound of 5 to 1000 parts by weight per 100 parts by weight.
The flame-retardant resin composition according to the above. 10. A resin having an aromatic ring having a hydroxyl group and / or an amino group in a main chain or a side chain,
The flame-retardant resin composition according to claim 1, comprising at least one resin selected from a polyarylate resin, an aromatic epoxy resin, and a polycarbonate resin. 11. A salt (1), a polyphosphoramide (2), and a cyclic urea compound (3) of a nitrogen-containing cyclic compound and sulfuric acid, boric acid, inorganic phosphoric acid, or a heterocyclic compound having a hydroxyl group. The flame-retardant resin composition according to claim 1, which comprises at least one selected from the group consisting of: 12. The flame-retardant resin composition according to claim 1, further comprising at least one selected from a metal borate, a metal hydrogen phosphate, and red phosphorus. 13. The flame-retardant resin composition according to claim 1, further comprising a styrene resin. 14. The flame-retardant resin composition according to claim 1, further comprising at least one selected from a hindered phenolic antioxidant, a phosphorus-based stabilizer, a fluororesin, and a filler. 15. A method for producing a flame-retardant resin composition by mixing a thermoplastic resin with the flame retardant according to claim 1. 16. A molded article formed from the resin composition according to claim 1.