JP2002105335A - Flame-retardant resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition whose flame retardance has achieved at a high level with a halogen-free flame retardant. SOLUTION: This flame retardant resin composition comprising (A) a thermoplastic resin (such as a polyester-based resin) and (B) a flame retardant, characterized in that (B) the flame retardant comprises (B1) a polyphenylene oxide- based resin, (B2) a phosphate (such as a condensed phosphate), and (B3) the salt of a nitrogen-containing cyclic compound with at least one acid selected from sulfuric acid, sulfonic acids and boric acid. The nitrogen-containing cyclic compound includes melamine and melamine condensate. The sulfuric acid includes non-condensed sulfuric acid and condensed sulfuric acid [(pyro)sulfuric acid], and the sulfonic acids include alkyl sulfonic acids and aryl sulfonic acids. (B) The flame retardant is added in an amount of, for example, 10 to 300 pts.wt. per 100 pts.wt. of (A) the thermoplastic resin.

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 inventors of the present invention have conducted intensive studies to achieve the above object, and as a result, have found that polyphenylene oxide resins, phosphates, and sulfuric acid, sulfonic acid or borate of a nitrogen-containing cyclic compound can be used. It has been found that when a flame retardant is constituted by combining the above, the thermoplastic resin can be made flame-retardant at a high level, and the present invention has been completed.

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 at least one selected from a polyphenylene oxide resin (B1), phosphates (such as condensed phosphate) (B2), a nitrogen-containing cyclic compound, and sulfuric acid, sulfonic acid, and boric acid. And a salt (B3) with an acid. Examples of the thermoplastic resin (A) include polyester resins, polyamide resins, vinyl resins, olefin resins, and acrylic resins.
1,4-cyclohexane dimethylene terephthalate, C
Polyalkylene acrylate resins such as _2-4 alkylene terephthalate and C _2-4 alkylene naphthalate are included. The nitrogen-containing cyclic compound salt (B3) is a salt of an amino group-containing triazine compound (melamine, melamine condensate, etc.) and an acid such as non-condensed sulfuric acid, condensed sulfuric acid, sulfonic acid, non-condensed boric acid, Is also good. In the salt of the nitrogen-containing cyclic compound (B3), the ratio of the nitrogen-containing cyclic compound to the acid is about the former / the latter (molar ratio) = 1/5 to 5/1. The proportion of the flame retardant (B) is the same as that of the thermoplastic resin (A) 10
For example, about 10 to 300 parts by weight with respect to 0 parts by weight. The flame retardant (B) is a phosphate ester (B
2) With respect to 100 parts by weight, the polyphenylene oxide-based resin (B1) may contain 10 to 500 parts by weight or the nitrogen-containing cyclic compound salt (B3) 5 to 1000 parts by weight. . 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 (poly) phosphoric acid, salts of a nitrogen-containing cyclic compound with 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 antioxidant, an inorganic 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, naphthalenedicarboxylic acids such as phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid and 2,6-naphthalenedicarboxylic acid, and 4,4′-diphenyl) A dicarboxylic acid having about 8 to 16 carbon atoms, such as dicarboxylic acid, 4,4'-diphenyl ether dicarboxylic acid, 4,4'-diphenylmethane dicarboxylic acid, and 4,4'-diphenyl ketone 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 6 to 14 carbon atoms, and 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.). Hydroquinone, resorcinol, biphenol, 2,2-bis (4
-Hydroxyphenyl) propane, 2,2-bis- (4
Aromatic diols such as-(2-hydroxyethoxy) 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, oxybenzoic acid, oxynaphthoic acid, hydroxyphenylacetic acid,
Oxycarboxylic acids such as glycolic acid and oxycaproic acid and derivatives thereof are included.

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 resins include a polybutylene terephthalate resin containing a butylene terephthalate unit as a main component (for example, polybutylene terephthalate, polybutylene terephthalate copolyester) and a polyethylene terephthalate resin containing an ethylene terephthalate unit as a main component ( For example, polyethylene terephthalate, polyethylene terephthalate copolyester) is included. 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 and polytetramethylene glycol), C _6-12 aliphatic dicarboxylic acids ( Adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, etc.),
Examples include aromatic dicarboxylic acids (phthalic acid, isophthalic acid, diphenyldicarboxylic acid, etc.), oxycarboxylic acids (oxybenzoic acid, oxynaphthoic acid, etc.). The polyester resin may have not only a linear structure but also a branched structure, or may be crosslinked, as long as the melt moldability and the like are not impaired. 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 And aliphatic diamines such as nonamethylenediamine; bis (4-
Aminocyclohexyl) methane, bis (4-amino-3)
Alicyclic diamines such as -methylcyclohexyl) methane; Further, an aromatic diamine such as phenylenediamine and meta-xylylenediamine may be used in combination.
These diamines can be used alone or in combination of two or more.

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. Aminocarboxylic acids can be used alone or in combination of two or more.

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) , Nonamethylenediamine, etc.), and polyamides obtained from aromatic and aliphatic dicarboxylic acids (eg, terephthalic acid and adipic acid) and aliphatic diamines (eg, hexamethylenediamine). These polyamides can be used alone or in combination of two or more.
Preferred polyamides include non-aromatic and aliphatic polyamides (nylon 6, nylon 66, nylon 610, nylon 612, nylon 11, nylon 12, etc.), semi-aromatic polyamides (nylon MXD6, nylon 9T, etc.), semi-aromatic Polymerized polyamide (nylon 6T / 6,
Nylon 6T / 66, Nylon 6T / 12, Nylon 6
I / 6, nylon 6I / 66, nylon 6T / 6I, nylon 6T / 6I / 6, nylon 6T / 6I / 66, nylon 6T / M5T, and the like.

(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. In particular, polyester resins (polyalkylene arylates such as PBT resins and PET resins) And the like are preferred.

[Flame Retardant (B)] In the present invention, the flame retardant (B) is a polyphenylene oxide resin (B1)
By comprising the phosphoric acid ester (B2) and a salt of a nitrogen-containing cyclic compound (sulfate, sulfonate, borate, etc.) (B3), high properties can be obtained without deteriorating the properties of the thermoplastic resin. Can provide flame retardancy.

[Polyphenylene oxide resin (B
1)] When the flame retardant is constituted by using the polyphenylene oxide resin (B1), the flame retardancy is lower than when the flame retardant is constituted only by the phosphates (B2) and the salt of the nitrogen-containing cyclic compound (B3). 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-methoxy-1,4-phenylene) oxide,
Poly (2-methyl-6-hydroxyethyl-1,4-phenylene) oxide, poly (2-methyl-6-chloroethyl-1,4-phenylene) oxide, poly (2,3,
Poly (mono, di or tri C _1-6 alkyl-phenylene) such as 6-trimethyl-1,4-phenylene) oxide
Oxide, poly (2-methyl-6-phenyl-1,4-
Poly (mono C _1-6 alkyl mono- C _6-10 aryl, such as phenylene) oxide - phenylene) oxide, poly (such as 2,6-diphenyl-1,4-phenylene) oxide poly (mono- or di-C _{6- 10} Aryl-phenylene)
Oxides and the like.

As the copolymer of polyphenylene oxide, a copolymer having two or more monomer units of the homopolymer (for example, 2,6-dimethyl-1,4-phenylene oxide unit and 2,3,6- Trimethyl-1,4
A random copolymer having a phenylene oxide unit), a benzene formaldehyde resin (a formaldehyde condensate of a benzene ring-containing compound such as a phenol resin) or an alkylbenzene formaldehyde resin with an alkylphenol such as cresol or p-tert-butylphenol. Polyphenylene oxide copolymer composed of an alkylphenol-modified benzene formaldehyde resin block obtained by the above method and a polyphenylene oxide block as a main structure, and a modified graft copolymer in which a styrene-based polymer is grafted on polyphenylene oxide or a copolymer thereof. Polymers.

These polyphenylene oxide resins may be used alone or in combination of two or more.

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

Examples of the phosphate include aliphatic phosphates [trimethyl phosphate, triethyl phosphate, tripropyl phosphate, triisopropyl phosphate, tributyl phosphate, triisobutyl phosphate, pentaerythritol phosphate (for example, Greater Lakes Chemical NH-1197, Char
-Guard 329, such Bishikurorin ester compounds described in JP-A-2001-106889) phosphoric acid tri C _1-10 alkyl esters and the like; phosphoric acid di C _1-10 alkyl ester corresponding to the phosphoric acid triester and Mono-C _1-10 alkyl phosphate, etc.], aromatic phosphate [triphenyl phosphate, tricresyl phosphate, trixylyl phosphate, diphenyl cresyl phosphate, tri (isopropylphenyl) phosphate, diphenylethyl phosphite] Tri C _6-20 aryl esters such as jill], aliphatic-
Aromatic phosphates (eg, methyldiphenyl phosphate, phenyldiethyl phosphate, etc.) and the like can be mentioned.

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 - phosphonate diester; C _6-10 aryl - phosphonate monoester (e.g., 10-hydroxy-9,10-dihydro-9-oxa-10-phospha-phenanthrene -1
0-oxide); phosphonocarboxylic acid triesters such as phosphonocarboxylic acid esters (C _1-4 alkoxycarbonyloxy C _1-4 alkyl phosphonic acid diesters corresponding to the above alkyl phosphonic acid diesters such as dimethyl methoxycarbonylmethylphosphonate) ] And various phosphonic acid esters. Further, a metal salt of phosphorous acid or phosphonocarboxylic acid which may be substituted with an alkyl or aryl group (for example, Ca, Mg, Zn, B
a, Al salts, etc.).

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). Phosphinic acid esters (C _1-6 alkyl phosphinates such as methyl phosphinate, C _6-10 aryl phosphinates such as phenyl phosphinate,
9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10- _C1-30alkyl or _C6-20aryl substituted-9,10-dihydro-9-oxa-10-phosphaphenanthrene Cyclic phosphinic acid esters such as -10-oxide).
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 phosphate ester include a condensed phosphate ester having an aromatic ring, and examples thereof include a compound 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 or more. In the formula (1), p is preferably an integer of 1 to 30. The aryl groups represented by R ^{1 to} R ⁴ include:
A C _6-20 aryl group such as a phenyl and naphthyl group is _exemplified , 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 D residue). AD residue, bisphenol S residue, etc.).

The compound represented by the above formula (1) includes
For example, resorcinol phosphates [resorcinol bis (diphenyl phosphate), resorcinol bis (dicresyl phosphate), resorcinol bis (dicylenyl phosphate)], hydroquinone phosphates [hydroquinone bis (diphenyl phosphate), 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 compounds 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).

Further, the monomer-type or polymer-type phosphoric acid ester includes a phosphoric acid ester amide including a bonding mode of the phosphoric acid amide. For example, piperidinoji C _6-20
Aryl phosphate, pipecolinodi C _6-20 aryl phosphate, C _2-6 alkylenediamine diyl tetra C
_6-20 aryl phosphate (for example, piperazinediyltetraaryl phosphate in which the aryl group is a phenyl, cresyl, xylyl group or the like) and the like.

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

[Salt of nitrogen-containing cyclic compound (B3)] The salt of nitrogen-containing cyclic compound (B3) is a salt of a nitrogen-containing cyclic compound and at least one acid selected from sulfuric acid, sulfonic acid and boric acid. is there.

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.
It may have other hetero atoms such as sulfur and oxygen other than nitrogen. Such nitrogen-containing heterocycles include imidazole, thiadiazole, thiadiazoline, furazane,
Triazole, thiadiazine, pyrazine, pyrimidine,
Examples include 5- or 6-membered unsaturated nitrogen-containing heterocycles having a plurality of nitrogen atoms as ring constituent atoms, such as pyridazine, triazine, and purine. Among such heterocycles,
A 5- or 6-membered unsaturated nitrogen-containing ring having a plurality of nitrogen atoms as ring constituent atoms is preferred, and triazole and triazine are particularly preferred.

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 condensates (particularly melam, melem, etc.) and the like].

The nitrogen-containing cyclic compound may form a salt with sulfuric acid, sulfonic acid or boric acid at a nitrogen atom portion (imino group) constituting the ring, but usually forms at least one amino group substituted on the ring. It is preferable to form a salt with an acid (sulfuric acid, sulfonic acid, boric acid). When having a plurality of amino groups, all amino groups may form a salt with the acid, for example, a part forms a salt with sulfuric acid, and the remaining part forms a salt with sulfonic acid or boric acid. It may be formed.

The sulfuric acid which forms a salt with the nitrogen-containing cyclic compound includes peroxomonosulfuric acid, sulfuric acid (orthosulfuric acid),
Non-condensed sulfuric acid such as sulfurous acid; condensed sulfuric acid such as pyrosulfuric acid; Preferred sulfuric acid is (pyro) sulfuric acid (orthosulfuric acid and pyrosulfuric acid). The sulfuric acid may be used alone or in combination of two or more.

Examples of the sulfonic acid that forms a salt with the nitrogen-containing cyclic compound include alkylsulfonic acids (such as methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butanesulfonic acid, and ethanedisulfonic acid) and arylsulfonic acids (benzenesulfonic acid). Acid, toluenesulfonic acid, naphthalenesulfonic acid, benzenedisulfonic acid, etc.). Preferred sulfonic acids are C _1-10 alkyl sulfonic acids and C _6-12 aryl sulfonic acids. The sulfonic acids may be used alone or in combination of two or more.

Examples of the boric acid that forms a borate with the nitrogen-containing compound include non-condensed boric acid such as orthoboric acid and metaboric acid, and condensed boric acid such as tetraboric acid and boric anhydride. Preferred boric acids are non-condensed boric acids (such as orthoboric acid). Boric acid may be used alone or in combination of two or more.

(Sulfates of Nitrogen-Containing Cyclic Compounds) As sulfates of nitrogen-containing cyclic compounds, sulfates of amino group-containing triazine compounds such as non-condensed sulfates (melamine sulfates (melamine sulfate, melamine sulfate, guanyl sulfate) Melamine), non-condensed melamine sulfates such as melamine sulfite corresponding to melamine sulfate; melem salts, melam salts, melon salts, guanamine salts, etc. corresponding to the above non-condensed melamine sulfate)], condensed sulfate [melamine pyrosulfate] (Eg, melamine pyrosulfate, dimelamine pyrosulfate), melem salts corresponding to melamine pyrosulfate, melam salts (eg, melam pyrosulfate, dimelam pyrosulfate), melon salts, guanamine salts, etc.]. Further, a triazole salt corresponding to the triazine salt can also be used. Preferred sulfates include (pyro) melamine sulfates such as melamine sulfate, dimelamine sulfate and melamine pyrosulfate, and (pyro) sulfuric acid melams such as melam sulfate and dimelam pyrosulfate.

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.

(Sulfonate of Nitrogen-Containing Cyclic Compound) Examples of the sulfonate of the nitrogen-containing cyclic compound include alkyl sulfonates of amino group-containing triazine compounds [alkylamine sulfonates (melamine methanesulfonate, melamine ethanesulfonate). , Melamine butanesulfonate,
Melamine ethanedisulfonic acid, etc.), melam salt, melem salt, melon salt, melamine-melam-melem double salt, guanamine salt corresponding to the above-mentioned alkylsulfonic acid melamine salt,
Acetoguanamine salt, benzoguanamine salt, etc.), aryl sulfonates of amino group-containing triazine compounds [melamine arylsulfonates (melamine benzenesulfonate, melamine toluenesulfonate, etc.), and melam salts corresponding to the above-mentioned melamine salts of arylsulfonic acids. , Melem salt, melon salt, melamine / melam / melem double salt, guanamine salt, acetoguanamine salt, benzoguanamine salt, etc.)]. Preferred sulfonic acid salts include melamine methanesulfonate, melam methanesulfonate, melem methanesulfonate, melamine melamine-melam-melem double salt, melamine benzenesulfonate, melam benzenesulfonate, melem benzenesulfonate, melene benzenesulfonate, benzene Melamine sulfonate, melam, melem double salt, melamine p-toluenesulfonate, melam p-toluenesulfonate, melem p-toluenesulfonate, p-
And melamine, melam and melem double salts of toluenesulfonic acid. As a sulfonate of such a nitrogen-containing cyclic compound (triazine compound), for example, melam methanesulfonate is available from Nissan Chemical Industries, Ltd. as “MMS-20”.
"0".

(Borate of Nitrogen-Containing Cyclic Compound) As the borate of the nitrogen-containing cyclic compound, a borate of an amino group-containing triazine compound, for example, a non-condensed borate [melamine orthoborate (mono-borate monoborate)] Or melamine salts such as trimelamine), corresponding to the above-mentioned melamine salts, such as melem salts, melam salts, melon salts, double salts of melamine, melam and melem, and guanamine salts; etc .; metaborates corresponding to the aforementioned orthoborates Acid salt], polyborate [condensed melamine borate (melamine anhydride borate, melamine tetraborate, etc.), melem salt, melam salt, melon salt, melamine melam.
Double salt, guanamine salt] and the like. Preferred borates are non-condensed melamines such as melamine orthoborate.

The method for producing a borate of a nitrogen-containing cyclic compound (for example, an amino group-containing triazine compound) is not particularly limited. For example, a solution or dispersion (water alone) containing the nitrogen-containing cyclic compound and boric acid is used. System, an aqueous solution or suspension of a water-acetone mixed system, a water-alcohol mixed system, or the like) at an appropriate temperature (for example, about 50 to 100 ° C.), and the resultant precipitate is separated and dried. Methods (JP-A-54-47750, JP-A-8-283008)
For example, the method described in Japanese Patent Application Laid-Open Publication No. H10-209, etc.). Further, it can also be obtained by a method of maintaining a mixture of a nitrogen-containing cyclic compound and boric acid at high temperature and high humidity (such as the method described in JP-A-11-79720). As a borate of such a nitrogen-containing cyclic compound (triazine compound), for example, “melapur”, Jose
"STORFLAM MLB" from ph Storey & Co LTD, Budenhei
m Available from Iberica Comercial as "BUDIT 313".

The above-mentioned sulfates, sulfonates and borates can be used alone or in combination of two or more.

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

Salts of these nitrogen-containing cyclic compounds (B3)
May be treated with a surface modifier such as an epoxy compound, a coupling agent (such as a silane compound, a titanate compound, or an aluminum compound) or a chromium compound. Further, the salt (B3) of the nitrogen-containing cyclic compound may be a metal, glass, a cyanuric acid salt of a triazine derivative, a thermosetting resin (for example, a phenol resin, a urea resin, a melamine resin, an aniline resin, a furan resin, a xylene resin or (A co-condensation resin, an unsaturated polyester resin, an alkyd resin, a vinyl ester resin, a diallyl phthalate resin, an epoxy resin, a polyurethane resin, a silicon resin, a polyimide, etc.), a thermoplastic resin, or the like. Among these treatments, usually, a coating treatment with a thermosetting resin (for example, a phenol resin or an epoxy resin) is performed. For example, as a method of coating with a salt of a nitrogen-containing cyclic compound (B3), JP-A-52-125489, JP-A-62-1704, and JP-A-63-110254.
JP, JP-A-8-53569, JP-A-8-53
574, JP-A-2000-169120, JP-A-2001-131293, and the like can be referred to. The ratio between the salt (B3) of the nitrogen-containing cyclic compound and the coating component is not particularly limited. % By weight (for example, 0.1 to 8% by weight).

In the present invention, the above-mentioned sulfates and sulfonates,
Since the flame retardant is formed using a borate or the like, not only can the thermoplastic resin (such as a polyester-based resin) be highly flame-retarded, but also there is no risk that the resin composition will be colored.

[Use ratio of flame retardant] The flame retardant of the present invention comprises:
By combining a polyphenylene oxide resin (B1), a phosphate ester (B2) and a salt of a nitrogen-containing cyclic compound (B3), the properties of a thermoplastic resin (such as a polyester resin) are not reduced (for example, High flame retardancy can be imparted (without fear of coloring or bleed-out), 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 as long as the flame retardancy can be imparted. For example, the proportion of the polyphenylene oxide resin (B1) can be selected from phosphate esters (B
2) 10 to 500 parts by weight, preferably 10 to 300 parts by weight (for example, 10 to 200 parts by weight), more preferably 30 to 300 parts by weight (for example, 30 to 200 parts by weight) with respect to 100 parts by weight. It is about. The proportion of the salt (B3) of the nitrogen-containing cyclic compound is determined by the proportion of the phosphates (B2)
For 100 parts by weight, for example, 5 to 1000 parts by weight,
It is about 5 to 500 parts by weight, more preferably about 5 to 300 parts by weight. The ratio (weight ratio) of the salt (B3) of the nitrogen-containing cyclic compound and the polyphenylene oxide resin (B1) is as follows:
1/99 to 90/10, preferably 3/97 to 80/2
0, more preferably about 5/95 to 70/30.

[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, resinous flame retardant, nitrogen-containing flame retardant, 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).

[0081]

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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.

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

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

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 at the para position, the number of methylene bonds M _OP bonded at the ortho position and the para position, and the number of methylene bonds bonded at the ortho position. When M _O , it is expressed by the following equation.

[0088] 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 added, for example, in the presence of at least one catalyst selected from (1) metal salts, metal oxides, metal hydroxides and amine compounds, or further added. After the condensation reaction, a method of reacting a phenol with an aldehyde by adding an acid catalyst [for example, JP-A-55-90523, JP-A-57-51714, and JP-A-59-80418] Gazette, JP-A-62-230815, 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 it is necessary to reduce the amount of the remaining catalyst by treatment such as washing with water. Is desirable. The high orthonovolak resin obtained by the method (3) is
Since no catalyst is used, removal of the catalyst is not required, and this is a preferable high ortho novolak resin.

The above-mentioned phenols, dioxybenzenes, naphthols, bisphenols, alkylbenzenes (eg, toluene, ethylbenzene, xylene, mesitylene, etc.), anilines, furfurals, ureas, triazines (eg, , Cyanuric acid, isocyanuric acid, melamine, guanamine, acetoguanamine, benzoguanamine, etc.), co-condensates with co-condensation components such as terpenes, cashew nuts and rosins. In particular, aminotriazine novolaks modified with triazines are preferred co-condensates. Such aminotriazine novolaks can co-form phenols, triazines, and formaldehyde in the presence or absence of a basic catalyst (such as ammonia, triethylamine, triethanolamine) and / or an acidic catalyst (such as oxalic acid). Condensation method [for example, DIC Tech
In the case of the “Nical 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) sulfoxide Dihydroxydiaryl sulfoxides; 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 resins (random novolak resins and high ortho-novolak resins) are 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, silyl group or 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 , more preferably 300 to 80.
00 (especially 300 to 5000).

(1-2) Aralkyl Resin As the aralkyl resin used in the present invention, a resin having a structural unit represented by the following formula (4) can be used. Also, as the aralkyl resin, JP-A-2000-35
No. 1822, phenol biphenyl aralkyl type resins, phenol phenylene aralkyl type resins, phenol diphenyl ether aralkyl type resins, naphthalene-containing aralkyl type resins (such as naphthol aralkyl type resins), and phenol anthracene aralkyl type resins. Can be used.

[0100]

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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.

As the aralkyl resin, a phenol aralkyl resin in which X is a hydroxyl group is often used. 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.

[0105]

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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 described 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 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 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 above-mentioned novolak tree branch, bisphenol F, bisphenol S) , Bisfe Lumpur - sulfone), anilines, furfurals, exemplified alkylbenzenes as a copolymer component in the paragraph of the novolak resin may be used together with co-condensation component, such as ureas and triazines.

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

[0120]

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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 1-3.) 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.

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

[0124]

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(In the formula, R ¹¹ is the same as described above. R ¹³ is —O
H, -OSi (R ¹⁴⁾ ₃ and -OM (M is a metal cation, O
R 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 (eg, sodium, lithium, potassium) cation, or a divalent alkaline earth metal (eg, magnesium, calcium) cation 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), or a copolymer with another copolymerizable monomer. 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.

Examples of 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). These copolymerizable monomers can be used alone or in combination of two or more.

The ratio (weight ratio) of the vinyl monomer to the copolymerizable monomer is, for example, 10/90 to 100/0, preferably 30/70 to 100/0, and more preferably 5/100.
It is about 0/50 to 100/0.

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 polymerization method, a transesterification method (eg, an acetate method, a phenyl ester method, etc.), an acid chloride method, a direct method, or a polyaddition method. It can be produced using a polymerization method or an interfacial polymerization method.

The polyarylate resin 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 benzenediols (eg, resorcinol, hydroquinone, etc.) and bisphenols (eg, bis (hydroxyaryl) C _1-6 alkane (eg, bisphenol A, bisphenol F, bisphenol AD, etc.) ] 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 chloride), and aromatic polycarboxylic acids] Esters (alkyl esters, aryl esters, etc.), aromatic polycarboxylic anhydrides, etc.].

Examples of the monocyclic aromatic ring 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 acid 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 bisphenols and / or benzenediols, for example, bisphenols (bisphenol A, bisphenol AD, bisphenol F, etc.) and / or benzenediols. (Resorcinol, hydroquinone, etc.) and benzenedicarboxylic acid (isophthalic acid, terephthalic acid, etc.) polyester, bisphenols and / or benzenediols and bis (arylcarboxylic acid) s [for example, bis (carboxyphenyl) methane, bis ( And (bis (carboxyaryl) C _1-4 alkyl such as carboxyphenyl) ethane and bis (carboxyphenyl) propane. These polyarylate resins can be used alone or in combination of two or more.

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

The terminal of the polyarylate resin may be blocked (bonded) with an alcohol, a carboxylic acid, etc. (particularly, a monohydric alcohol, a monovalent carboxylic acid, 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 which block (bond) the terminal of the polyarylate resin include monovalent aliphatic 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).

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

The number average molecular weight of the epoxy resin is, for example, 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 curing agents (eg, aliphatic amines such as ethylenediamine, aromatic amines such as metaphenylenediamine and xylylenediamine), polyaminoamide curing agents, and acid and acid anhydride curing agents. It may be used after being cured by a curing agent such as.

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, 1 to 30 parts by weight, preferably 3 to 25 parts by weight, more preferably about 5 to 20 parts by weight, per 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 and (poly)
Salts with phosphoric acid, (b) salts of a nitrogen-containing cyclic compound with a heterocyclic compound having a hydroxyl group, (c) polyphosphoramide, (d) cyclic ureas and the like are included.

(A) Salt of nitrogen-containing cyclic compound with (poly) phosphoric acid Salts of nitrogen-containing cyclic compound with phosphoric acid include salts of nitrogen-containing cyclic compound with inorganic phosphoric acid and organic phosphoric acid. It is.

(A-1) Salt of Nitrogen-Containing Cyclic Compound and Inorganic Phosphoric Acid As the nitrogen-containing cyclic compound, the same compounds as in the above (B3) can be used.

Examples of the inorganic phosphoric acid include peroxophosphoric acid,
Orthophosphoric acid, metaphosphoric acid, phosphorous acid (phosphonic acid),
Non-condensed phosphoric acid such as hypophosphorous acid (phosphinic 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).

[0170]

Embedded image

(Wherein, t represents an integer of 2 or more) In the above formula, t is preferably an integer of 2 to 200,
More preferably, it is an integer of 3 to 100. Examples of such polyphosphoric acid include pyrophosphoric acid, triphosphoric acid, and tetraphosphoric acid.

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.

The 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 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 a nitrogen-containing cyclic compound include polyphosphate of an amino group-containing triazine compound [melamine pyrophosphate (melamine pyrophosphate, dimelamine pyrophosphate), and triphosphate 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 sulfur-containing polyacids and double salts are described in JP-A-10-81691, JP-A-10-306081, and JP-A-10-108.
No. 306082 can be referred to.

(A-2) Organic phosphate of nitrogen-containing cyclic compound As the nitrogen-containing cyclic compound, the same compounds as in the above (B3) can be used. Examples of the organic phosphoric acid include partial esters of non-condensed phosphoric acid (particularly, orthophosphoric acid and phosphonic acid) exemplified in the section of the inorganic phosphoric acid, and phosphoric acid (phosphonic acid) or hypophosphorous acid substituted with an organic group (Phosphinic acid)
And the like. 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 phenol). Examples of the alcohols include the monohydric alcohols (particularly, C _1-10) exemplified by the polyarylate resin method.
Aliphatic monol); C _1-10 aliphatic polyols such as glycerol and pentaerythritol in addition to the aliphatic polyols exemplified in the section of the polyester resin; C _2-10 aliphatic polyols having a hetero atom such as nitrilotrimethanol; cyclopentanol, C _5-8 alicyclic monool (preferably C _5-6 cycloalkanol) such as cyclohexanol; cyclohexane C _5-8 alicyclic diol (preferably C _5-6 cycloalkane diols such as diol ); Monohydric phenols such as trimethylphenol, naphthol, and hydroxybiphenyl, in addition to the phenols exemplified in the section of the novolak resin; polyhydric phenols such as benzenediol, naphthalene diol, and bisphenol.

Examples of such phosphate esters 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 _1-10 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 _1-10 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 _1-10 alkylphosphinic acids such as methylethylphosphinic acid and diethylphosphinic acid; Hosufinikoji C _1-6 aliphatic carboxylic acids, such as phosphinyl co carboxylic acid [Hosufinikoji acetate; _1-10 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 is a cyclic organic phosphoric acid (eg, 9,10-dihydro-10-hydroxy-1).
0-oxo-9-oxa-10-phosphaphenanthrene).

The organic phosphate can form a salt with the nitrogen-containing cyclic compound at a part or all of the 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 method for producing an organic phosphate of such a nitrogen-containing cyclic compound (particularly, an amino group-containing triazine compound) is not particularly limited, and examples thereof include a solution containing the nitrogen-containing cyclic compound and an organic phosphoric acid. The dispersion (aqueous solution or suspension such as water alone, water-acetone mixed system, water-alcohol mixed system, etc.) is heated to an appropriate temperature (for example, 50 to 50).
(About 100 ° C.), and the resulting precipitate is separated and dried.

The above-mentioned (poly) phosphates (inorganic phosphates, organic phosphates) can be used alone or in combination of two or more.

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

(B) Salt of Nitrogen-Containing Cyclic Compound with Heterocyclic Compound Having a Hydroxyl Group As the nitrogen-containing cyclic compound, the same compounds as in the above (B3) can be used.

The heterocyclic compound having a hydroxyl group includes at least one hydroxyl group and at least one hydroxyl group.
And a heterocyclic ring having two nitrogen atoms as ring heteroatoms. 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 a triazine compound corresponding to the above-mentioned nitrogen cyclic compound, 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 a nitrogen-containing cyclic compound and a 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.

(C) Polyphosphoramide The phosphoric acid amides exemplified by the phosphoric acid [inorganic phosphoric acid (non-condensed phosphoric acid and polyacid containing a phosphorus atom, etc.), organic phosphoric acid and the like] ] And -N = C =
A compound having a unit represented by N- or -N = C (-N <) ₂ (such as a cyanamide derivative) is calcined and condensed in the presence of urea and / or urea phosphate as a binder. And an amide nitrogen-containing polymer compound. As the phosphoric acid, non-condensed phosphoric acid (such as orthophosphoric acid and metaphosphoric acid), polyphosphoric acid, and partial esters of phosphoric acid (such as ammonium polyphosphate and urea phosphate) are preferable. As the cyanamide derivative, melamine and the like are preferable. Triazines (especially 1,3,5-triazines), guanidines (dicyandiamide, guanidine,
And guanylurea. Polyphosphoramides can be used alone or in combination of two or more. Regarding polyphosphoramide, for example, Japanese Patent Application Laid-Open No. Hei 7-1384
No. 63 can be referred to. Such polyphosphoramides are disclosed in JP-B-53-2170 and JP-B-53-154.
No. 78, Japanese Patent Publication No. 55-49004,
It can be produced by a method described in, for example, JP-A-1-126091, JP-A-10-81691, U.S. Pat. The polyphosphoramides are “Sumisafe PM” (manufactured by Sumitomo Chemical Co., Ltd.), “Tien S” (manufactured by Taihei Chemical Industry Co., Ltd.), and “Apinon MPP”
[Miwa Chemical Co., Ltd.], “Melapur” [DS
M), "Exolit" [Clariant],
It is commercially available as "AMARD" [manufactured by Albright & Wilson].

(D) Cyclic urea compound The cyclic urea compound has at least one urea unit -N
It has HCONH- 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. Examples of the cyclic urea compound include a cyclic monoureide and a cyclic diureide. Further, the cyclic ureas also include cyclic thioureas corresponding to the cyclic urea. These cyclic ureas can be used alone or in combination of two or more.

Examples of the cyclic monoureide include alkylene urea [C _1-10 alkylene urea (preferably C _1-6 alkylene urea) such as methylene urea, ethylene urea, and crotonylidene urea (CDU)], and alkenylene urea (vinylene urea). and C _2-10 alkenylene urea such cytosine), [such as C _2-10 alkynylene urea (preferably C _2-6 alkynylene urea) alkynylene urea, such arylene urea (Imesachin) ureido dicarboxylic acid (parabanic acid, Dimethylparabanic acid, barbituric acid,
5,5-diethylbarbituric acid, dilituric acid, dialluic acid, alloxan, alloxanic acid, isocyanuric acid, uramil, etc.), ureido of β-aldehyde acid (uracil,
5-methyluracil (thymine), dihydrouracil, urazole, benzyleneurea, etc., ureide of α-oxyacid [hydantoin, 5,5-dimethylhydantoin, 1,1-methylenebis (5,5-dimethylhydantoin), allantoin, etc. And the derivatives thereof.

As the cyclic diureide, for example, uric acid,
3-methyluric acid, pseudouric acid, acetylene urea (glycoluril), diureide of α-hydroxy acid [1,1-
Methylenebis (5,5-dimethylhydantoin), allantoin, etc.], diurea such as p-urazine, diureide of dicarboxylic acid (alloxanthin, purpuric acid, etc.), and derivatives thereof.

Examples of the cyclic thioureas include ethylene thiourea, thiobarbituric acid, dithiourazole, thiohydantoin, dithiohydantoin and the like.

Of these cyclic ureas, cyclic diureides having two urea units as ring constituent units (including cyclic thioureas having two urea units), particularly acetylene urea, uric acid, and derivatives thereof are preferable. .

The acetylene urea or a derivative thereof includes, for example, a compound represented by the following formula (11).
Uric acid or a derivative thereof includes a compound represented by the following formula (12).

[0201]

Embedded image

(Wherein, R ^{14 to} R ²¹ are the same or different and each represent a hydrogen atom, an alkyl group, an alkenyl group, an alkoxy group, an acyl group, an acyloxy group, a cycloalkyl group, an aryl group, an arylalkyl group, etc.) As the alkyl group, a _C1-8 (preferably _C1-4 ) alkyl group, as the alkenyl group, a _C2-8 (preferably _C2-4 ) alkenyl group, and as the alkoxy group, a _C1-8 (preferably _C2-4 ) alkenyl group
_{1- 8} (preferably C _1-4) alkoxy group, the acyl group, C _1-8 (preferably C _{1 -4)} acyl group, the acyloxy group, C _1-8 (preferably C _1-4 ) As the acyloxy group and the cycloalkyl group, C _5-16 (preferably C _5-16 )
_5-8 ) As the cycloalkyl group and the aryl group, C _6-12
(Preferably C _6-10 ) aryl group and arylalkyl group include C _6-12 (preferably C _6-10 ) aryl-C
Examples thereof include _1-8 (preferably C _1-4 ) alkyl groups. As acetylene urea, uric acid or a derivative thereof, R ¹⁴ to
Compounds in which R ²¹ is a hydrogen atom or a C _1-4 alkyl group such as a methyl group (eg, acetylene urea, uric acid, 3-methyl uric acid, etc.) are preferred.

The cyclic urea compound (particularly, the acetylene urea or uric acid derivative) also includes a salt. The salt is not particularly limited as long as it can form a salt with a cyclic urea,
Examples include the sulfuric acid, sulfonic acid and boric acid exemplified in the above section (B3), the (poly) phosphoric acid and triazine compounds exemplified in the above section (a), and salts with at least one selected from metals and the like. However, a triazine compound and / or a salt with a metal are particularly preferable. These salts can be used alone or in combination of two or more.

Examples of the salt-forming metal include alkali metals (eg, sodium, potassium, lithium, etc.) and alkaline earth metals (eg, calcium, magnesium,
Barium, etc.), zinc, aluminum, transition metals (eg, iron, copper, cobalt, manganese, etc.).

The ratio between the cyclic urea compound and the salt-forming component is not particularly limited. For example, the former / the latter (molar ratio) = 1/5 to 4/1, preferably 1/3 to 2/1, more preferably 1/3 to 2/1. Preferably it is about 1/2 to 1/1.

These nitrogen-containing flame retardant aids (D2) are treated with a surface modifier such as an epoxy compound, a coupling agent (silane compound, titanate compound, aluminum compound, etc.), a chromium compound or the like. You may. The nitrogen-containing flame retardant (D2) may be a metal, glass, a cyanuric acid salt of a triazine derivative, a thermosetting resin (for example, a phenol resin, a urea resin, a melamine resin, an aniline resin, a furan resin, a xylene resin, or the like). (A co-condensation resin, an unsaturated polyester resin, an alkyd resin, a vinyl ester resin, a diallyl phthalate resin, an epoxy resin, a polyurethane resin, a silicon resin, a polyimide, etc.), a thermoplastic resin, or the like. Of these treatments, usually, a coating treatment with a thermosetting resin (for example, a phenol resin or an epoxy resin) is performed. For example, as a coating treatment method of the nitrogen-containing flame retardant aid (D2),
JP-A-52-125489, JP-A-62-217
No. 04, JP-A-63-110254, JP-A-8-53569, JP-A-8-53574,
JP-A-2000-169120, JP-A-2001-1
Reference can be made to JP-A-31293. The ratio between the nitrogen-containing flame retardant aid (D2) and the coating component is not particularly limited. For example, the coating component is 0.1 to 20% by weight of the coated nitrogen-containing flame retardant aid, preferably 0.1 to 10%. weight%
(For example, 0.1 to 8% by weight).

[Inorganic flame retardant auxiliary (D3)] Examples of the inorganic flame retardant auxiliary (or flame retardant) include metal salts of inorganic acids and red phosphorus.

(1) Metal Salts of Inorganic Acids The inorganic acids constituting the salts include oxyacids [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 (such as hydrochloric acid) and carbonic acid can be used. The phosphoric acid, sulfuric acid and boric acid may be any of non-condensed type and condensed type, and the sulfuric acid or borate (B
3) or sulfuric acid exemplified in the section of nitrogen-containing flame retardant auxiliary (D2),
Boric acid and (poly) phosphoric acid can be used.

Preferred inorganic acids are phosphoric acid and boric acid.

Metals that form salts with inorganic acids include alkali metals (eg, potassium, sodium); alkaline earth metals (eg, magnesium, calcium, barium); transition metals (eg, 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 the inorganic phosphoric acids [non-condensed phosphoric acid, condensed phosphoric acid (polyphosphoric acid) and the like] exemplified in the section of the nitrogen-containing flame retardant aid (D2). And non-condensed phosphoric acid is particularly preferable.

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 the phosphoric acid metal salt 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 ), Ca ₅ (PO ₄ ) ₃ (OH),
A condensed phosphate such as Ca ₅ (PO ₄ ) ₃ (F, Cl) may be used, but it is preferable to use a hydrogen phosphate.

Examples of such hydrogen phosphates include alkaline earth metal hydrogen phosphates such as magnesium hydrogen orthophosphate (such as dibasic magnesium phosphate) and calcium hydrogen orthophosphate (such as calcium dibasic phosphate); Hydrogen phosphate of a metal of Group 2B of the periodic table such as zinc hydrogen oxyphosphate; hydrogen phosphate of a metal of Group 3B of the periodic table such as aluminum hydrogen phosphate; phosphorus of a metal of Group 4B of the periodic table such as tin hydrogen phosphate Non-condensed hydrogen phosphates such as oxyhydrogen salts. Of these, a substantially anhydrous metal hydrogen phosphate, particularly an alkaline earth metal hydrogen phosphate (such as dibasic calcium phosphate (CaHPO ₄ )) is preferred.

(1-2) Boric acid metal salt Boric acid includes condensed boric acid such as pentaboric acid and octaboric acid, and basic boric acid, in addition to boric acid exemplified in the section B3. It is.

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 [alkaline 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. Examples of such zinc borate include, for example, “Firebreak” ZB from Borax,
Available as 415 or 500.

As the metal salt of an inorganic acid other than phosphoric acid and boric acid (oxygen acid and the like), various metal salts corresponding to the above-mentioned metal phosphate and metal borate 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 for coating and stabilizing the surface of red phosphorus with a metal, a metal (iron, nickel, copper, aluminum, zinc, manganese,
(Tin, titanium, zirconium, etc.) or an alloy thereof. Another method for coating the surface of red phosphorus is to treat the red phosphorus with a solution of a metal salt (a salt of aluminum, magnesium, zinc, titanium, copper, silver, iron, nickel, etc.) and apply a metal phosphorus compound to the surface of the red phosphorus. Methods of forming and stabilizing are also included.

In particular, 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-00-169120, JP-A-9-67467, JP-A-6-115914, JP-A-5-229
806, JP-A-3-259996, JP-A-2-209991, JP-A-1-150309, JP-A-62-1704, and JP-A-52-12
No. 5489, EP296501A1, EP2
No. 49723A2 can be referred to.

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

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 to other flame-retardant auxiliaries, such as 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), boron phosphate, expandable graphite, lignins, and the like.

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

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

The silicon-containing flame retardant includes (poly) organosiloxane. 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 (such as pentaerythritol), oligomeric polyhydric alcohols (such as dipentaerythritol and tripentaerythritol), esterified polyhydric alcohols, substituted alcohols, and the like. Cellulose (cellulose, hemicellulose, lignocellulose, pectocellulose, adipocellulose, etc.), saccharides (monosaccharides, polysaccharides, etc.) and the like can be mentioned.

As the metal oxide, for example, 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 aids 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,
Styrene, vinyltoluene, α-methylstyrene, etc.)
A styrene monomer and a vinyl monomer (for example, unsaturated nitriles such as acrylonitrile,
Copolymers with (meth) acrylic acid esters, (meth) acrylic acid, α, β-monoolefinically unsaturated carboxylic acids such as maleic anhydride or acid anhydrides or esters thereof; styrene-based graft copolymers And styrene-based block copolymers.

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, And a styrene-acrylonitrile graft polymerized 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 (SB
S) 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 styrene resin is not particularly limited, and is, for example, 5 × 10 ³ to 200 × 10 ⁴ , preferably 1 × 10 ^{4 to} 150 × 10 ⁴ , 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-based resin can be selected, for example, from a range of 1 to 30 parts by weight, preferably about 5 to 20 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 for maintaining heat resistance stably for a long period of time. Antioxidants or stabilizers include, for example, phenol (such as hindered phenols), amine (such as hindered amines), phosphorus, sulfur, hydroquinone, quinoline antioxidants (or stabilizers), inorganic And phosphorus-based stabilizers.

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.

[0242] 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.

The phosphorus-based stabilizer (or antioxidant) includes, 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-5-methylphenyl) pentaerythritol diphosphite, bis (2
6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (nonylphenyl) pentaerythritol diphosphite, bis (2,4-dicumylphenyl) pentaerythritol diphosphite, etc.], triphenyl Phosphate stabilizers (for example,
4-phenoxy-9-α- (4-hydroxyphenyl)
-P-cumenyloxy-3,5,8,10-tetraoxa-4,9-diphosphaspiro [5.5] undecane, tris (2,4-di-t-butylphenyl) phosphate, etc.), diphosphonite stabilizers [for example, Tetrakis (2,4-di-t-butylphenyl) -4,4'-biphenylenediphosphonite, tetrakis (2,4-di-t-butyl-5-methylphenyl) -4,4'-biphenyl Range phosphonite, etc.]. The organic phosphorus-based stabilizer usually has a branched C _3-6 alkylphenyl group (particularly, a t-butylphenyl group).

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

The inorganic phosphorus-based stabilizer includes, for example, inorganic phosphoric acid (phosphoric acid, phosphorous acid, phosphonic acid, phosphinic acid,
Pyrophosphoric acid, tripolyphosphoric acid, polyphosphoric acid, polyphosphorous acid, phosphonocarboxylic acid, nitrogen-containing phosphoric acid, etc.), and acidic metal salts thereof.

The acidic metal salts of inorganic phosphoric acid include, for example,
Alkali metal hydrogen phosphates (eg, LiH_TwoPO_Four,
NaH_TwoPO_Four, NaH_TwoPO_Four・ 2H_TwoO, Na_TwoH_TwoP_TwoO
₇, KH_TwoPO_Four, K_TwoH_TwoP_TwoO₇(Pyro) phosphate water
Alkali metal salts), inorganic alkaline hydrogen phosphate alkaline earth metals
(For example, Ca (H_TwoPO_Four)_Two, Ca (H_TwoPO_Four)_Two・ H _Two
O, CaH_TwoP_TwoO₇, Mg (H_TwoPO_Four)_Two, MgH_TwoP_TwoO₇
(Pyro) hydrogen alkaline earth metal salts), inorganic
Aluminum hydrogen phosphate salts (for example, Al (H_TwoPO_Four)
_ThreeEtc.).

These antioxidants or stabilizers can be used alone or in combination of two or more. The content of the antioxidant or the stabilizer may be, for example, 0.1 to 100 parts by weight of the thermoplastic resin.
01 to 5 parts by weight, preferably 0.05 to 2.5 parts by weight,
Particularly, it can be selected from a range of about 0.1 to 1 part by weight.

Further, the flame retardant resin composition of the present invention may contain an anti-dripping agent such as a fluororesin. With the anti-dripping agent, dripping of the fire and the melt during combustion can be suppressed. 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 diameter is, for example, about 10 to 5000 μm.
Preferably it may be about 100 to 1000 μm, more preferably about 100 to 700 μm.

The content of the 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 (plate-like filler, granular filler, etc.).

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

Of the non-fibrous fillers, 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 are powdered or granular fillers, particularly glass beads, milled fibers, kaolin, talc, mica and the like. , And glass flakes.

Particularly preferred fillers include glass-based fillers, for example, 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 1 to 60% by weight, preferably about 1 to 50% by weight, and more preferably 1 to 45% 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 surface of the thermoplastic resin during combustion. In addition, even when a non-halogen flame retardant containing a polyphenylene oxide resin is used, even if a small amount is used, thermoplasticity can be obtained by combining a phosphate ester and a salt of a nitrogen-containing cyclic compound (sulfate, borate, etc.). The resin can be effectively made flame-retardant, and there is no possibility of bleed-out. In particular,
Since a sulfate, sulfonate, or borate 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 (eg, 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. Furthermore, as a method for producing pellets by an extruder, (1) a method for mixing a glass-based filler component after first melt-mixing components except for a glass-based filler,
(2) a production method in which components other than the phosphate ester and the glass filler are first melt-mixed, and then the glass filler and the phosphate ester are simultaneously mixed (at the same feed position); (3) phosphoric acid After melt-mixing components other than the ester and the glass-based filler first, a production method or the like in which the glass-based filler and the phosphate ester are sequentially mixed (at separate feed positions) can be adopted. In the production of pellets by this extruder, a small amount of aromatic compounds and halogen compounds (benzene, toluene, xylene, chlorobenzene, trichlorobenzene, chloroform, trichloroethylene, etc.)
May be compounded at the time of extrusion as a dispersing aid. This dispersing aid is removed from the kneaded resin through the vent of the extruder. 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, salts of nitrogen-containing cyclic compounds, inorganic flame retardants, etc.) and resinous components (thermoplastic resin, polyphenylene oxide resin, resinous resin, etc.) It is convenient to once prepare a masterbatch by melt-mixing with a fuel 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 (such as a polyester resin) and a non-resinous component, and (2) a masterbatch composed of a polyphenylene oxide resin and a phosphate. A master batch composed of (3) a polyphenylene oxide resin and a non-resinous component (phosphates, salts of a nitrogen-containing cyclic compound, and an inorganic flame retardant),
(4) A masterbatch composed of a thermoplastic resin, a polyphenylene oxide resin, and non-resinous components (phosphates, salts of a nitrogen-containing cyclic compound, and an inorganic flame retardant), and the like.

The masterbatch may contain various additives, for example, a fluorine-based resin, an antioxidant, an organic or inorganic phosphorus-based stabilizer, and a filler, if necessary.

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

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

[0269]

According to the present invention, at least one selected from the group consisting of a thermoplastic resin, a polyphenylene oxide resin, a phosphate ester, a nitrogen-containing cyclic compound, and sulfuric acid, sulfonic acid and borate is used. Since a flame retardant composed of a salt with an acid is used in combination, it is possible to achieve flame retardancy even in a small amount without using a halogen-based flame retardant, and it is possible to suppress deterioration of resin characteristics. Further, a molded article having improved flame retardancy can be obtained by such a resin composition.

[0270]

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

The resin composition was evaluated for flame retardancy and blooming properties by the following tests.

(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. ：: No exudation is observed at all △: Slight exudation is observed ×: Remarkable exudation is observed

[Polyester Resin A] A-1: Polybutylene terephthalate [Duranex, intrinsic viscosity = 1.0, manufactured by Polyplastics Co., Ltd.] A-2: Polyethylene terephthalate [Velpet EF]
G10, manufactured by Kanebo Co., Ltd.] A-3: Polybutylene terephthalate [Duranex, intrinsic viscosity = 0.83, Polyplastics Co., Ltd.]
A-4: 12.5 mol% isophthalic acid-modified polybutylene terephthalate [Duranex, manufactured by Polyplastics Co., Ltd.]

[Polyphenylene oxide resin B] B-1: Poly (2,6-dimethyl-1,4-phenylene) oxide (intrinsic viscosity = 0.3) B-2: Poly (2,6-dimethyl-1) , 4-phenylene) oxide (intrinsic viscosity = 0.45) B-3: poly (2,6-dimethyl-1,4-phenylene) oxide [PPE polymer YPX-100F, manufactured by Mitsubishi Gas Chemical Co., Ltd.]

[Bisphenolic 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, manufactured by Toto Kasei Co., Ltd.] C-4: Bisphenol A type epoxy resin [Epicoat 1004K, manufactured by Yuka Shell Epoxy Co., Ltd.]

[Styrene 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.] D-4: Polystyrene [Toyostyrol GP14]
L, manufactured by Toyo Styrene Co., Ltd.]

[Phosphate 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) [Leophos RDP, Ajinomoto Fine Techno Co., Ltd.
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) [Phirol Flex BDP,
E-5: Biphenol bis (di-2,6-xylenyl phosphate) [PX202, manufactured by Daihachi Chemical Industry Co., Ltd.]

[Salt F of Triazine Compound F] F-1: Melamine sulfate [Apinone-901, Sanwa Chemical Co., Ltd.] F-2: Dimelamine sulfate [according to Example 3 of JP-A-8-231517] Synthesized compound] F-3: Dimelam pyrosulfate [JP-A-10-306082]
Compounds Synthesized According to Reference Example 2 of Japanese Patent Application Publication No. H05-63] F-4: Melamine borate F-5: Melam methanesulfonate [MMS-200, manufactured by Nissan Chemical Industries, Ltd.] F-6: Melamine sulfate sulfate Melamine sulfate (F-1) 500 g was suspended in 1000 ml of water, 15 g of phenol and 27 g of 37% formalin were added, and the mixture was heated to 80 ° C. and stirred with 10 g of 85% phosphoric acid.
Was added. After heating and stirring for 1 hour at the same temperature,
Washed with water. Next, the filtrate was vacuum-dried at 140 ° C. for 3 hours to obtain 530 g of coated melamine sulfate. The melamine sulfate content was 96% by weight.

F-7: 500 g of coated methanesulfonic acid melam polyphosphoramide (F-5) was added to 1000 ml of water.
Suspended in an epoxy resin [Yuka Shell Epoxy Co., Ltd.]
20 g of Epicoat 801] and 10 g of a curing agent [Versamide 150] manufactured by Henkel Hakusui Co., Ltd.
The pH was adjusted to 5 with phosphoric acid. Next, the mixture was heated to 60 ° C., heated and stirred for 2 hours, then allowed to cool, filtered, and washed with water, and the filtrate was vacuum-dried at 140 ° C. for 3 hours to obtain 520 g of melam coated methanesulfonic acid. The melam methanesulfonate content was 88% by weight.

[Flame Retardant Aid G] G-1: Zinc borate [Firebreak ZB, manufactured by Borax Japan Co., Ltd.] G-2: Calcium monohydrogen phosphate anhydrous: Average particle size = about 30 μm [Tahei Chemical Co., Ltd.] G-3: Novolak type phenolic resin [Sumilite Resin PR53647, manufactured by Sumitomo Durez Co., Ltd.] G-4: Red phosphorus [Nova Excel 140, manufactured by Rin Kagaku Kogyo] G-5: Melamine cyanurate [MC610, manufactured by Nissan Chemical Industries, Ltd.]

[Antioxidant H] H-1: pentaerythritol-tetrakis [3-
(3,5-di-t-butyl-4-hydroxyphenyl)
Propionate] [Irganox 1010, manufactured by Ciba-Geigy Corporation]

[Phosphorus Stabilizer I] I-1: Bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite [ADEKA STAB PEP36, manufactured by Asahi Denka Kogyo Co., Ltd.] 2: tetrakis (2,4-di-t-butylphenyl) -4,4′-biphenylenediphosphonite [Sandstub P-EPQ, manufactured by Sando Co., Ltd.] I-3: calcium dihydrogen phosphate

[Anti-Dripping Agent J] J-1: Polytetrafluoroethylene

[Filler K] K-1: Glass fiber (chopped strand of 10 μm in diameter and 3 mm in length) K-2: Glass fiber (chopped strand of 13 μm in diameter and 3 mm in length) K-3: talc

Examples 1 to 45 and Comparative Examples 1 to 16 The above components were mixed in the proportions (parts by weight) shown in Tables 1 to 7, and kneaded and extruded with an extruder to prepare a resin composition. This resin composition was molded into a test product (130 × 13 ×
1.6 mm), and the flammability and the blooming property were evaluated.

Tables 1 to 7 show the results.

[0288]

[Table 1]

[0289]

[Table 2]

[0290]

[Table 3]

[0291]

[Table 4]

[0292]

[Table 5]

[0293]

[Table 6]

[0294]

[Table 7]

As is clear from Tables 1 to 7, in the examples, the thermoplastic resin is highly flame-retarded without exuding the flame retardant in the examples as compared with the comparative examples.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08L 71/12 C08L 71/12 C09K 21/10 ZAB C09K 21/10 ZAB 21/12 21/12 F term ( Reference) 4F071 AA02 AA14 AA23 AA31 AA43 AA46 AA51 AA54 AA68 AC14 AC15 AC17 AH07 AH12 AH17 BB03 BB05 BB06 4H028 AA30 AA31 AA35 AB02 BA06 4J002 BB001 BC021 BC061 BD001 CG01 001 001 001 001 001 001 FD133 FD136 FD137 GM00 GN00 GQ00

Claims (20)

[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 a salt (B3) of a nitrogen-containing cyclic compound and at least one acid selected from sulfuric acid, sulfonic acid and boric acid. 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 thermoplastic resin (A) is polyethylene terephthalate or a copolyester containing ethylene terephthalate as a main component. 6. The flame-retardant resin composition according to claim 1, wherein the phosphate ester (B2) is a condensed phosphate ester. 7. The flame-retardant resin composition according to claim 1, wherein the nitrogen-containing cyclic compound is an amino-containing triazine compound. 8. The flame-retardant resin composition according to claim 1, wherein the nitrogen-containing cyclic compound is at least one selected from melamine and a melamine condensate. 9. The method according to claim 1, wherein in the salt of the nitrogen-containing cyclic compound (B3), the ratio of the nitrogen-containing cyclic compound to the acid is the former / the latter (molar ratio) = 1/5 to 5/1. Flammable resin composition. 10. The salt (B3) of a nitrogen-containing cyclic compound,
The flame-retardant resin composition according to claim 1, which is coated with a thermosetting resin. 11. The method according to claim 1, wherein the flame retardant (B) is poly (mono- or di-C).
_1-6 alkyl-phenylene) oxide (B1), condensed phosphate (B2), and (pyro) sulfuric acid, sulfonic acid or borate of at least one nitrogen-containing cyclic compound selected from melamine, melam and melem ( The flame-retardant resin composition according to claim 1, which is constituted by B3). 12. 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). 13. The flame retardant (B) is composed of 10 to 500 parts by weight of a polyphenylene oxide resin (B1) and 100 to 500 parts by weight of a phosphate ester (B2), and a salt of a nitrogen-containing compound (B3) 5 to 5 parts. 2. The flame-retardant resin composition according to claim 1, comprising 1,000 parts by weight. 14. 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. 15. A salt of a nitrogen-containing cyclic compound with (poly) phosphoric acid (1), a salt of a nitrogen-containing cyclic compound with a heterocyclic compound having a hydroxyl group (2), a polyphosphoramide (3), The flame-retardant resin composition according to claim 1, which comprises at least one selected from a group consisting of a cyclic urea compound and a cyclic urea compound. 16. 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. 17. The flame-retardant resin composition according to claim 1, further comprising a styrene resin. 18. The flame-retardant resin composition according to claim 1, further comprising at least one selected from the group consisting of a hindered phenol antioxidant, a phosphorus antioxidant, an inorganic phosphorus stabilizer, a fluorine resin and a filler. object. 19. A method for producing a flame-retardant resin composition by mixing a thermoplastic resin with the flame retardant according to claim 1. 20. A molded article formed from the resin composition according to claim 1.