JPH09255877A - Flame-retardant resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition excellent in flame retardancy, impact resistance and heat resistance, hardly causing bleedout of flame retardant and useful for electrical equipment parts for connectors, relays, etc., and parts, etc., for automobiles by adding a specific amount of a specific polyphosphate to a thermoplastic resin. SOLUTION: This flame-retardant resin composition contains (A) 100 pts.wt. thermoplastic resin and (B) 1-100 pts.wt. polyphosphonate comprising a recurring unit of formula I [R<1> is H or a 1-5C alkyl; Ar is a phenyl (substituted with an organic residue not containing halogen), e.g. 1,4-phenylene, 1,3-phenylene, a group of formula II or a group of formula III], having >=10000 number-average molecular weight expressed in terms of standard polystyrene and >=90wt.% solubility to an organic solvent which is acetone, chloroform, dimethylformamide, dimethylsulfoxide or tetrahydrofuran.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a flame-retardant resin composition using a novel high molecular weight polyphosphate. More specifically, it has excellent flame retardancy, impact resistance, heat resistance, and little bleed-out of flame retardant, and electrical / electronic device parts such as connectors, relays, switches, case members, transformer members, coil bobbins, automobile parts, The present invention relates to a flame-retardant thermoplastic resin composition suitable for machine parts.

[0002]

2. Description of the Related Art Polyesters represented by polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polycyclohexane dimethylene terephthalate, etc., or thermoplastic resins such as polycarbonate, polyamide, polyphenylene oxide, etc. make full use of their excellent characteristics. As an injection molding material, it is being used in a wide range of fields such as mechanical parts, electric parts, and automobile parts. On the other hand, since these thermoplastic resins are inherently flammable, in order to be used as industrial materials, in addition to the general balance of chemical and physical properties, fire safety, that is, flame retardancy is required. Often.

As a method of imparting flame retardancy to a thermoplastic resin, a method of compounding a halogen-based organic compound as a flame retardant and an antimony compound as a flame retardant auxiliary into the resin is generally used. However, this method has a problem that a large amount of smoke is generated during combustion.

Accordingly, in recent years, it has been strongly desired to use a flame retardant containing no halogen in order to overcome the disadvantages of these halogen-based flame retardants.

Heretofore, a method of blending a phosphorus compound has been widely known as a method of flame-retarding a thermoplastic resin without using a halogen-based flame retardant. For example, techniques for flame-retarding by adding an aromatic phosphate or an aromatic phosphate oligomer are disclosed in JP-A-48-90348 and JP-A-48-91147. Further, in European Patent Publication EP491986, there is disclosed a method of adding a resorcin type aromatic phosphate oligomer to a flame-retardant PBT type alloy molded article. The method of adding a phosphate, melamine cyanurate and an inorganic filler is disclosed in Japanese Patent Publication No. 6-5045.
63 discloses a method of adding a resorcin-type aromatic bisphosphate to a blend of polybutylene terephthalate and polycarbonate or a blend of polybutylene terephthalate and polyetherimide.

[0006]

A flame-retardant resin composition for injection molding, particularly for machine parts, electric / electronic parts and automobile parts has excellent flame retardancy, mechanical performance and heat resistance. Not only that, it is required to suppress the bleed-out in which the flame retardant contained in a large amount in the resin composition oozes to the surface of the molded article. In particular, when it is used as a connector component, the flame-retardant resin composition is required to have excellent impact resistance, heat resistance, and the property that the bleed-out of the flame retardant is small. However, when a resin composition containing a conventional resorcinol-type aromatic bisphosphate or resorcinol-type aromatic phosphate oligomer is formed into a molded article, the heat resistance is lowered by the plasticizing effect of these compounds,
In addition, bleeding out of these compounds oozing on the surface of the molded product became a problem.

Therefore, the present invention uses a non-halogen flame retardant to impart a high degree of flame retardancy to a thermoplastic resin, and at the same time,
An object of the present invention is to obtain a thermoplastic resin injection-molded product having good impact resistance and heat resistance, and having less bleed-out of a flame retardant.

[0008]

[Means for Solving the Problems] In view of the above situation, the present inventors have conducted extensive studies and as a result, have found that a thermoplastic resin containing a high molecular weight polyphosphate obtained under specific reaction conditions is highly flame retardant. It has been found that the composition has good properties, good impact resistance and heat resistance, and has little bleed out of the flame retardant.

That is, the present invention relates to (A) a thermoplastic resin 1
100 parts by weight, (B) is composed of a repeating unit represented by the following general formula (1), has a number average molecular weight converted by standard polystyrene of 10,000 or more as measured by gel permeation chromatography, and 20 Solubility at 90 ° C in at least one organic solvent selected from acetone, chloroform, dimethylformamide, dimethylsulfoxide and tetrahydrofuran is 90
A flame-retardant resin composition containing 1 to 100 parts by weight of polyphosphate in an amount of at least wt%.

[0010]

Embedded image

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The thermoplastic resin (A) of the present invention is a synthetic resin which exhibits fluidity when heated and can be molded by utilizing this. Specific examples thereof include polyester, liquid crystal polyester, polycarbonate, polyamide, wholly aromatic polyamide, wholly aromatic polyester, polyimide, polybenzimidazole, polyketone, polyether ether ketone, polyether ketone, polyether sulfone, and polyphenylene oxide. , Phenoxy resin, polyphenylene sulfide, phenol resin, phenol-formaldehyde resin, polypropylene, polyethylene, olefin polymers such as polystyrene, ethylene / propylene copolymer, ethylene / 1-butene copolymer, ethylene / propylene / non-conjugated diene Copolymer, ethylene / ethyl acrylate copolymer, ethylene / glycidyl methacrylate copolymer, ethylene / vinyl acetate / glycidyl methacrylate copolymer And ethylene / propylene-g-maleic anhydride copolymer, olefinic copolymers such as ABS, polyester polyether elastomers, and one or more mixtures selected from elastomers such as polyester polyester elastomers. Polyester, liquid crystal polyester, polycarbonate, polyamide, polyphenylene sulfide, polyethylene, polypropylene,
One or a mixture of two or more selected from polystyrene, ABS, polyphenylene oxide, phenoxy resin, phenol resin and phenol-formaldehyde resin is preferable, and more preferably polyester, polyethylene, polypropylene, ABS, polyamide, polycarbonate, phenoxy resin, polyphenylene sulfide. ,
One or a mixture of two or more selected from phenolic resins.

The polyphosphate of the present invention comprises the repeating unit represented by the general formula (1) as described above.

In the general formula (1), R ¹ is preferably the same or different hydrogen atom or an alkyl group having 1 to 5 carbon atoms,
More preferably, it is a C1-C5 alkyl group. Here, specific examples of the alkyl group having 1 to 5 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, and the like. , N-propyl is preferable, and methyl is more preferable.

Ar is not particularly limited as long as it is a phenyl group or a phenyl group substituted with a halogen-free organic residue, and structures represented by the following general formulas (2) to (7) are preferable.

[0015]

Embedded image (X represents a direct bond, O, S, SO ₂ , CH ₂ and CHPh, and Ph represents a phenyl group.) The polyphosphate of the present invention was measured by gel permeation chromatography and converted to standard polystyrene. Those having a number average molecular weight (Mn) of 10,000 or more are indispensable in terms of moldability, suppression of decrease in heat resistance of the thermoplastic resin composition and suppression of bleed-out.

Further, the polyphosphate of the present invention has a temperature of 20 ° C.
Has a solubility of 90 in at least one organic solvent selected from acetone, chloroform, dimethylformamide, dimethylsulfoxide, and tetrahydrofuran.
wt% or more.

Here, the solubility of polyphosphate shows the value measured as follows. Ie polyphosphate 1
g, acetone, chloroform, dimethylformamide,
Dimethyl sulfoxide, tetrahydrofuran 100 ml
Each of them was dissolved in the solution, stirred for 6 hours at 20 ° C., the solution-insoluble portion was recovered by filtration, and the solvent-insoluble polyphosphate was weighed by drying at 100 ° C. under vacuum. = (1-weight of solvent insoluble part) /
1 g × 100 was calculated. Among acetone, chloroform, dimethylformamide, dimethylsulfoxide, and tetrahydrofuran, the solubility in the most soluble organic solvent was used as the index of the solubility of polyphosphate.

The solubility of the polymer here also reflects the degree of crosslinking of the polymer. That is, since the crosslinked polyphosphate has a molecular structure substantially similar to that of the thermosetting resin, it becomes a material that swells in various solvents and does not melt and flow even when heated. Therefore, polyphosphate having a low solubility has a high cross-linking property, so that the manufacturability, moldability, and impact resistance of the resin composition when blended with a thermoplastic resin are significantly lowered. From this point of view, it is essential that the solubility of polyphosphate at 20 ° C. in at least one organic solvent selected from acetone, chloroform, dimethylformamide, dimethylsulfoxide, and tetrahydrofuran is 90 wt% or more.

Such a polyphosphate can be produced by the method shown below. That is, a phosphorus compound represented by the following general formula (8) and an aromatic biphenol represented by the following general formula (9) are used in the presence or absence of a catalyst at a temperature of 100 ° C or higher and 250 ° C or lower in the first stage of polymerization. After heating at 50 ° C., the second stage of polymerization is continued under reduced pressure at 250
It can be produced by heating at a polymerization temperature of ℃ or less.

[0020]

Embedded image (However, X represents a halogen atom, R ¹ represents a hydrogen atom which is the same or different, or an alkyl group having 1 to 5 carbon atoms. Ar represents a phenyl group or a phenyl group substituted with a halogen-free organic residue. The phosphorus compound used in the present invention is represented by the above formula (8). In formula (8), R ¹ is preferably the same or different hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and more preferably an alkyl group having 1 to 5 carbon atoms. Here, specific examples of the alkyl group having 1 to 5 carbon atoms include methyl, ethyl, n-propyl, isopropyl, and n.
-Butyl, sec-butyl, tert-butyl, n-pentyl and the like can be mentioned, but methyl, ethyl and n-propyl are preferable, and methyl is more preferable. X represents a halogen atom, and specific examples thereof include chloride and bromide.

The aromatic biphenol used in the present invention is represented by the above formula (9), and Ar is not particularly limited as long as it is a phenyl group or a phenyl group substituted with a halogen-free organic residue. No, but general formula (2)
The structures represented by (7) to (7) are preferable.

[0022]

[Chemical 6] Further, in the present invention, the ratio of the aromatic biphenol to the phosphorus compound is preferably 1-fold mol or more and 1.1-fold mol or less, and more preferably 1-fold mol or more and 1.05 or less from the viewpoint of the molecular weight of the obtained polyphosphate. It is not more than twice the molar amount.

Further, in the production method of the present invention, heating is performed at a temperature of 100 ° C. to 250 ° C. in the first stage of polymerization.

The polymerization temperature at this time is usually 100 ° C. or higher and 250 ° C. or lower, preferably 100 ° C. or higher and 240 ° C. or lower, more preferably from the viewpoint of reaction rate, suppression of sublimation of the aromatic bisphenol used, and suppression of crosslinking reaction. Is 100 ° C
It is above 230 ° C.

The polymerization temperature at this stage is preferably 100 to 250 ° C., but if it is within this temperature range, the polymerization temperature may be maintained at a constant temperature or continuously raised.

When the polymerization temperature is continuously raised, the heating rate is not particularly limited, but a rapid increase in the polymerization temperature is
In general, 100 ° C./min or less is preferable, and 50 ° C. is more preferable because it causes crosslinking of the polymer due to the heat of polymerization.
/ Min.

The polymerization time at this stage varies significantly depending on the polymerization temperature and the presence or absence of a catalyst, but is usually 0.1.
~ 50 hours, preferably 0.2-20 hours, more preferably 0.5-10 hours.

The polymerization at this stage is preferably bulk polymerization in order to make the molecular weight of the obtained polymer sufficient. That is, it is preferable not to use an organic solvent other than the phosphorus compound and the aromatic bisphenol.

In the present invention, a catalyst may be used in the polymerization of the phosphorus compound and the aromatic bisphosphate. As a catalyst, an empty p is commonly called "Lewis acid".
There is no particular limitation as long as it is a catalyst having a metal having an orbit as a central atom. Specific examples include magnesium chloride, aluminum chloride, diethylaluminum, diethylzinc, and the like, with magnesium chloride being particularly preferred.

In the production method of the present invention, the desired polyphosphate can be produced by subsequently heating in the second stage of polymerization under reduced pressure at a polymerization temperature of 250 ° C. or lower.

The degree of reduced pressure in the second stage of polymerization is usually 0.1 mmHg or more and 10 from the viewpoint of the degree of polymerization of the obtained polymer.
It is 0 mmHg or less, preferably 0.1 mmHg or more and 50 mmHg or less, and more preferably 0.1 mmHg or more and 10 mmHg or less.

The polymerization temperature in the second stage of the polymerization of the present invention is 250 ° C. or lower from the viewpoint of inhibiting the progress of the crosslinking reaction,
The temperature is preferably 240 ° C or lower, more preferably 220 ° C or lower.

The polymerization temperature at this stage is 250 ° C.
The polymerization temperature may be maintained at a constant temperature or continuously raised as long as it is below this temperature.

When the polymerization temperature is continuously raised, the rate of temperature increase is not particularly limited, but a rapid increase in the polymerization temperature is
In general, 100 ° C./min or less is preferable, and 50 ° C. is more preferable because it causes crosslinking of the polymer due to the heat of polymerization.
/ Min.

The lower limit of the polymerization temperature at this stage is
There is no particular limitation, but in order to obtain a polymer having a sufficient molecular weight, it is preferably 150 ° C. or higher, more preferably 180 ° C. or higher.
℃ or above.

The polymerization time in the second stage of polymerization varies remarkably depending on the polymerization temperature and the presence or absence of a catalyst, but is usually 0.1 to 50 hours, preferably 0.2 to 20 hours, more preferably 0.5 to 10 hours.

In the present invention, after completion of the second stage of polymerization,
Furthermore, the thermal stability of the polyphosphate can be improved by adding a monohydric or higher alcohol or amine compound to block the end of the polyphosphate.

There is no particular limitation as long as it is a monohydric or higher alcohol or amine compound, that is, a compound having at least one hydroxyl group in the molecule or a compound having at least one amino group in the molecule. Examples include methanol, ethanol, propanol, butanol, phenol, 2,6-dimethylphenol, xylenol, ethylene glycol, propylene glycol, butanediol. Specific examples of the monovalent or higher amine compound include aniline, phenylenediamine, hexamethylenediamine, ethylenediamine, propylenediamine and butylenediamine.

The amount of the monohydric or higher alcohol or amine compound added is preferably 1 wt% or less, more preferably 0.5 wt% or less, based on the phosphorus compound.

The reaction temperature at this time is not particularly limited as long as it is 250 ° C. or less, but from the viewpoint of promptly promoting the reaction between the polymer terminal and the monovalent or higher alcohol or amine compound and suppressing the crosslinking reaction of the polymer. The temperature is preferably 250 ° C. or lower, more preferably 220 ° C. or lower.

The reaction at this time can be carried out under reduced pressure or under normal pressure. However, from the viewpoint of promptly proceeding the reaction between the polymer terminal and the monovalent or higher alcohol or amine compound, the reaction can be carried out under reduced pressure. It is preferable to carry out.

The degree of pressure reduction when performed under reduced pressure is 0.1 mm.
Hg or more and 100 mmHg or less, preferably 0.1
mmHg or more and 50 mmHg or less, more preferably 0.
It is 1 mmHg or more and 10 mmHg or less.

The polyphosphate thus obtained may be discharged from the polymerization apparatus as it is and used as it is, or may be used after being discharged or washed with a solvent or purified by reprecipitation.

The addition amount of the polyphosphate of the present invention is usually 1 to 100 parts by weight, preferably 2 to 80 parts by weight, and more preferably 3 to 100 parts by weight of the thermoplastic resin.
70 parts by weight.

The flame retardancy of the flame-retardant resin composition of the present invention is further improved by adding a salt of cyanuric acid or isocyanuric acid. The salt of cyanuric acid or isocyanuric acid is an adduct of cyanuric acid or isocyanuric acid with a triazine-based compound, and usually has a composition of 1: 1 (molar ratio), and optionally 1: 2 (molar ratio). It is an adjunct that has. Of the triazine compounds, those that do not form a salt with cyanuric acid or isocyanuric acid are excluded.

The triazine compound means a compound represented by the following general formula (10).

[0047]

Embedded image (However, in the above formula, R ² , R ³ , R ⁴ , and R ⁵ are the same or different hydrogen alkyl groups, aralkyl groups, cycloalkyl groups, or -CONH ₂ ; and R is -NR ² in the above formula. R ³ or -NR ⁴ R ⁵ the same group or independently hydrogen and those, an aryl group, an alkyl group, an aralkyl group, a cycloalkyl group, -NH ₂ or -CO,
It is a group selected from NH ₂ . In the general formula (10), R ² , R ³ , R ⁴ , and R ⁵ are the same or different hydrogen, an aryl group, an alkyl group, an aralkyl group, a cycloalkyl group, or —CONH ₂ . Here, an aryl group having 6 to 15 carbon atoms, an alkyl group having 1 to 10 carbon atoms, an aralkyl group having 7 to 16 carbon atoms, and a cycloalkyl group having 4 to 15 carbon atoms are preferable. . R is the same group as —NR ² R ³ or —NR ⁴ R ⁵ in the above formula, or independently of these, hydrogen, an aryl group, an alkyl group, an aralkyl group, a cycloalkyl group, —NH ₂ , or — CO
NH ₂ , wherein the aryl group has 6 to 15 carbon atoms, and the alkyl group has 1 carbon atom.
, An aralkyl group having 7 to 16 carbon atoms, and a cycloalkyl group having 4 to 15 carbon atoms are preferable.

Specific examples of R ² , R ³ , R ⁴ and R ⁵ are hydrogen, phenyl group, p-toluyl group, α-naphthyl group, β-naphthyl group, methyl group, ethyl group and n-propyl group. Group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, hydroxymethyl group, methoxymethyl group, benzyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, 2-methyl-1-pentyl group, Examples thereof include 4-methyl-1-cyclohexyl group and amide group, and among them, hydrogen, phenyl group, methyl group, hydroxymethyl group, methoxymethyl group, benzyl group and amide group are preferable.

A specific example of R is an amino group,
Amide group, methylamino group, dimethylamino group, ethylamino group, diethylamino group, mono (hydroxymethyl) amino group, di (hydroxymethyl) amino group, mono (methoxymethyl) amino group, di (methoxymethyl) amino group, Phenylamino group, diphenylamino group, hydrogen, phenyl group, p-toluyl group, α-naphthyl group, β
-Naphthyl group, methyl group, ethyl group, n-propyl group,
Isopropyl group, n-butyl group, sec-butyl group, t
tert-butyl group, benzyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, 2-methyl-1-
Examples thereof include a pentyl group and a 4-methyl-1-cyclohexyl group, among which hydrogen, an amino group, an amide group, a methyl group, a mono (hydroxymethyl) amino group, a di (hydroxymethyl) amino group, and a mono (methoxymethyl) group An amino group, a di (methoxymethyl) amino group, a phenyl group, and a benzyl group are preferred.

Of the salts of the compound represented by the general formula (10) with cyanuric acid or isocyanuric acid, particularly preferable examples are melamine, mono (hydroxymethyl) melamine, di (hydroxymethyl) melamine and tri (hydroxy). Methyl) melamine, benzoguanamine, acetoguanamine, 2-amido-4,6-diamino-1,
Salts of 3,5-triazine are mentioned, and salts of melamine, benzoguanamine and acetoguanamine are particularly preferable.

The salt of the compound represented by the general formula (10) with cyanuric acid or isocyanuric acid is prepared by forming a mixture of the compound represented by the general formula (10) with cyanuric acid or isocyanuric acid into an aqueous slurry. It is a powder obtained by mixing and forming both salts into fine particles, and filtering and drying this slurry, which is different from a simple mixture. This salt does not need to be completely pure, and the unreacted compound represented by the formula (10), cyanuric acid, or isocyanuric acid may remain. The form of this salt is not particularly limited, but it is preferable to use the one obtained as a powder as fine as possible from the viewpoint of mechanical strength and surface property of the molded article obtained from the composition of the present invention. It is particularly preferable that the average particle size before blending with the resin is 100 μm. If the salt has poor dispersibility, a dispersant such as tris (β-hydroxyethyl) isocyanurate may be used in combination.

In the present invention, a salt consisting of such a triazine compound and cyanuric acid or isocyanuric acid can be added if necessary, and the amount of the above salt used is 100 parts by weight of the thermoplastic resin. For 1 to
The amount is 100 parts by weight, preferably 2 to 80 parts by weight, more preferably 3 to 70 parts by weight. If the amount of the above salt used is less than 1 part by weight, the flame retardancy-improving effect is not recognized.
If it exceeds 100 parts by weight, the mechanical properties and surface appearance of the molded product are impaired, which is not preferable.

The flame retardancy of the resin composition of the present invention can be further improved by adding a non-halogen flame retardant.

As such a non-halogen flame retardant,
There is no particular limitation as long as it is a flame retardant containing no halogen, but a flame retardant containing phosphorus is preferable, and specifically, those represented by the following general formulas (11) and (12) can be preferably mentioned.

[0055]

Embedded image (However, the above formulas R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ ,
R ¹² and R ¹³ represent the same or different hydrogen atoms or alkyl groups having 1 to 5 carbon atoms. In addition, Ar ¹ , Ar ² and A
r ³ , Ar ⁴ , Ar ⁵ , Ar ⁶ and Ar ⁷ represent the same or different phenyl groups or phenyl groups substituted with halogen-free organic residues. Z is a direct bond, O, S, SO ₂ , C (CH ₃ ) ₂ , CH ₂ , CHP.
h and Ph represents a phenyl group. ) First, the structure of the flame retardant represented by the formula (11) will be described. In the formula (11), R ^{6 to} R ¹³ represent the same or different hydrogen or an alkyl group having 1 to 5 carbon atoms. Here, specific examples of the alkyl group having 1 to 5 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, Examples thereof include a 2-pentyl group, a 3-pentyl group and a neopentyl group, but hydrogen, a methyl group and an ethyl group are preferable, and hydrogen is particularly preferable.

Ar ¹ , Ar ² , Ar ³ and Ar ⁴ represent the same or different phenyl groups or phenyl groups substituted with a halogen-free organic residue. Specific examples thereof include a phenyl group, a tolyl group, a xylyl group, a cumenyl group, a mesityl group, a naphthyl group, an indenyl group, and an anthryl group, and a phenyl group, a tolyl group, a xylyl group, a cumenyl group, and a naphthyl group are preferable. Especially, a phenyl group, a tolyl group and a xylyl group are preferable.

Z is a direct bond, O, S, SO ₂ , C
(CH ₃ ) ₂ , CH ₂ and CHPh are represented, and Ph represents a phenyl group.

The flame retardant represented by the above formula (11) is generally manufactured according to the following chemical formula (13).

[0059]

Embedded image Next, the flame retardant represented by the above formula (12) will be described. In the above formula (12), Ar ⁵ , Ar ⁶ and Ar ⁷ represent the same or different phenyl groups or phenyl groups substituted with a halogen-free organic residue. Specific examples thereof include a phenyl group, a tolyl group, a xylyl group, a cumenyl group, a mesityl group, a naphthyl group, an indenyl group, and an anthryl group, and a phenyl group, a tolyl group, a xylyl group, a cumenyl group, and a naphthyl group are preferable. Especially, a phenyl group, a tolyl group and a xylyl group are preferable.

The flame retardant represented by the above formula (12) can be generally produced according to the following chemical formula (13).

[0061]

Embedded image In the present invention, such a non-halogen flame retardant can be added, if necessary, within a range that does not impair the effects of the present invention. The addition amount at that time is usually 100 parts by weight of the thermoplastic resin. On the other hand, it is 1 to 100 parts by weight, preferably 2 to 80 parts by weight, more preferably 3 to 70 parts by weight.

When the resin composition of the present invention is further added with a fluororesin, the drop (drip) of droplets during combustion is suppressed. Examples of such fluororesins include polytetrafluoroethylene, polyhexafluoropropylene, (tetrafluoroethylene / hexafluoropropylene) copolymer, (tetrafluoroethylene / perfluoroalkylvinyl ether) copolymer, and (tetrafluoroethylene / Ethylene) copolymer, (hexafluoropropylene / propylene) copolymer, polyvinylidene fluoride, (vinylidene fluoride / ethylene) copolymer and the like. Among them, polytetrafluoroethylene, (tetrafluoroethylene / (Perfluoroalkyl vinyl ether) copolymer, (tetrafluoroethylene / hexafluoropropylene) copolymer, (tetrafluoroethylene / ethylene) copolymer, and polyvinylidene fluoride are preferred. Polytetrafluoroethylene, (tetrafluoroethylene / ethylene) copolymer are preferable.

In the present invention, a fluororesin can be added if necessary, but the addition amount is usually 0.01 to 10 per 100 parts by weight of the thermoplastic resin from the viewpoint of moldability. Parts by weight, preferably 0.1 to 5 parts by weight, more preferably 0.2 to 3 parts by weight.

It has also been found that the flame-retardant resin composition of the present invention, when used in combination with a hindered phenol-based stabilizer, maintains extremely good heat resistance even when exposed to high temperatures for a long period of time. Examples of such stabilizers include triethylene glycol-bis [3- (3-t-butyl-5)
-Methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis [3- (3,5
-Di-t-butyl-4-hydroxyphenyl) propionate], pentaerythrityl-tetrakis [3-
(3,5-di-t-butyl-4-hydroxyphenyl)
Propionate], 2,2-thio-diethylenebis [3
-(3,5-di-t-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-
Di-t-butyl-4-hydroxyphenyl) propionate, 3,5-di-t-butyl-4-hydroxybenzylphosphonate diethyl ester, 1,3,5-trimethyl-2,4,6-tris (3,5 -Di-t-butyl-4-hydroxybenzyl) benzene, bis or tris (3-t-butyl-6-methyl-4-hydroxyphenyl) propane, N, N'-hexamethylenebis (3,5-di- t-butyl-4-hydroxy-hydrocinnamamide), N, N'-trimethylenebis (3,5-
Di-t-butyl-4-hydroxy-hydrocinnamide) and the like.

In the present invention, such a hindered phenol-based stabilizer can be added if necessary, and the amount of the hindered phenol-based stabilizer added is usually 100 parts by weight of the thermoplastic resin. Against 0.01-3
The amount is preferably 0.01 to 1 part by weight, more preferably 0.03 to 0.5 part by weight.

Further, the resin composition of the present invention has periodic table II to
Addition of a hydrate of a metal oxide, a metal hydroxide or a metal hydroxide containing a group V metal as a central atom can improve flame retardancy. Specific examples of such compounds include aluminum hydroxide, aluminum hydroxide hydrate, magnesium hydroxide, magnesium hydroxide hydrate, zinc hydroxide, zinc hydroxide hydrate, boric acid, and antimony oxide. , Zinc tin hydroxide, hydrate of zinc tin hydroxide, zinc tin oxide, hydrotalcite, dawsonite and the like.

The amount of such a hydrate of metal oxide, metal hydroxide or metal hydroxide added is usually 1 to 100 parts by weight, preferably 2 parts by weight per 100 parts by weight of the thermoplastic resin.
The amount is from 80 to 80 parts by weight, more preferably from 3 to 70 parts by weight.

With respect to the resin composition of the present invention, phosphorus-based or sulfur-based antioxidants, heat stabilizers, ultraviolet absorbers, lubricants, mold release agents, and dyes, etc. One or more conventional additives such as colorants including pigments can be added.

Although not particularly required, by further adding a fibrous and / or granular filler to the composition of the present invention, strength, rigidity, heat resistance, etc. can be significantly improved. .

Specific examples of such fillers include glass fiber, carbon fiber, metal fiber, aramid fiber, asbestos, potassium titanate whiskers, wollastonite, glass flakes, glass beads, talc, mica, clay,
Examples thereof include calcium carbonate, barium sulfate, titanium oxide and aluminum oxide, and among them, chopped strand type glass fiber is preferably used. The addition amount of these is 5 to 1 with respect to 100 parts by weight of the thermoplastic resin.
It is preferably 40 parts by weight, particularly preferably 5 to 100 parts by weight.

The resin composition of the present invention is usually produced by a known method. For example, thermoplastic resin, polyphosphate,
A method of melt-mixing a triazine-based compound with a salt of cyanuric acid or isocyanuric acid and other necessary additives in an extruder, or after mechanically mixing particulates evenly and mechanically and simultaneously with an injection molding machine. Examples include molding methods

[0072]

The effects of the present invention will be described in more detail with reference to the following examples. However, the present invention is not limited to these examples.

The measurement items described in the examples and comparative examples were according to the following methods.

The effects of the present invention will be described in more detail with reference to the following examples. Here, all parts are parts by weight. The measuring method of each characteristic is as follows.

(1) Number average molecular weight (Mn) A differential refractometer WATERS410 manufactured by WATERS was used as a detector.
And using MODEL510 high performance liquid chromatography. The measurement conditions are THF as an eluent,
0.1 ml of a solution having a column temperature of 39 ° C. and a sample concentration of 1 to 2 mg / ml was injected. As the column, Ultrastyra Gel 100A filled with polystyrene porous swelling gel manufactured by WATERS was connected in series, and the eluent was 0.5 ml / mi.
n and the column pressure was 500 psi. The polymer molecular weight was converted by comparison with a calibration curve using standard polystyrene.

(2) Measurement of glass transition temperature (Tg) Using PERKIN-ELMER DSC-7, under nitrogen atmosphere, sample amount 10 mg, -100 ° C to 20 ° C /
Tg was determined by the midpoint method from the inflection point of the peak observed when the measurement was performed under the temperature rising condition of min.

(3) 25% weight loss temperature (Td (25
%)) 50 ° C to 800 ° C using Seiko Denshi TG / DTA
Was raised at 20 ° C./min, and the temperature at which the thermal loss reached 25 wt% was defined as Td (25%).

(4) Production of flame-retardant resin composition and preparation of test pieces Polyphosphate, a salt of cyanuric acid or isocyanuric acid, and a non-halogen flame retardant other than polyphosphate and other additives are mixed, Melt kneading was carried out at a resin temperature of 260 ° C. using a 10 mmΦ single screw extruder. After drying the obtained pellets, it was supplied to a Sumitomo Nestal injection molding machine, Promat 40/25 (manufactured by Sumitomo Heavy Industries, Ltd.) under the conditions of a cylinder temperature of 290 ° C and a mold temperature of 80 ° C.
A mold notch impact test piece having an 8 "thickness x 2 1/2" length was prepared and Izod impact strength was measured. Further, under the same conditions, a tensile test piece specified in ASTM D-638 was prepared, and the deflection temperature under load at a load of 1.82 MPa was measured. Further, press molding was performed to obtain a flame retardant evaluation sample and a flame retardant bleed-out evaluation sample based on UL94.

(5) Bleed-out evaluation of flame retardant Tensile test Dumbbells were placed in a gear oven at 100 ° C for 24 hours.
Time processed. The amount of phosphorus on the surface of the dumbbell before and after the treatment was measured by fluorescent X-ray, and the peak intensity of phosphorus was measured. The peak intensity ratio before and after treatment (phosphorus peak intensity after treatment / phosphorus peak intensity before treatment) was used as an index of bleed-out.

(6) Production of polyphosphate The polyphosphate used in the present invention was produced by the following method.

Reference Example 1 Polyphosphate synthesized from 2,6-dimethylphenylphosphoric acid dichloride-hydroquinone (A-1) 2,6-Dimethylphenylphosphoric acid dichloride (A-1) 2,6-dimethylphenylphosphoric acid dichloride was attached to a polycondensation test tube equipped with a three-one motor. Two
40.9 mmol) and 2,6-dimethylphenylphosphoric acid dichloride in equimolar amounts of hydroquinone and 0.1 mmol of magnesium chloride as a catalyst, and 1
The temperature was raised from 00 ° C to 150 ° C over 1 hour, and then reacted for 1 hour. Thereafter, the degree of vacuum is 10 mmHg and the polymerization temperature is 150.
The temperature was raised from 220 ° C. to 220 ° C. over 1 hour, and the reaction was performed for 4 hours.

¹ H-NMR: 7.2 ppm (aromatic phenyl), 2.2 ppm (2,6-dimethyl) IR spectrum: 1300 cm ⁻¹ (P═O), 1190
cm ^-1, obvious that ^{980cm -1 (P-O-C} ) or more and an object thereof by the method of the present invention from the spectral data 2,6-dimethylphenyl phosphate dichloride over hydroquinone type polyphosphate is obtained Is. Therefore, according to the polymerization method of the present invention, 2,6
-It is clear that the reaction between dimethylphenylphosphoric acid dichloride and various biphenols resulted in polyphosphate by de-HCl reaction.

In A-2, resorcin was used instead of hydroquinone.

For comparison, a polyphosphate (B-1) having a crosslinked structure having a solubility in an organic solvent of less than 90 wt% was synthesized by the method shown in Reference Example 2.

Reference Example 2 Polyphosphate (B-1) Synthesized from Phenyl Phosphorus Dichloride-Hydroquinone A phenylphosphonic dichloride (240.9 mmo) was attached to a test tube equipped with a three-one motor and equipped with a navel for polycondensation.
1) and phenylphosphoric acid dichloride, equimolar hydroquinone and 0.1 mmol of magnesium chloride as a catalyst were added, and the mixture was heated from 100 ° C to 160 ° C over 1 hour.
And then reacted for 2 hours. Decompression degree 10mm after that
Hg, the polymerization temperature was changed from 160 ° C. to 290 ° C. over 1 hour, and the reaction was performed for 2 hours.

Table 1 shows a series of results regarding the synthesis of A-1, A-2 and B-1.

[0087]

[Table 1]

(7) Non-Halogen Flame Retardant Other than Polyphosphate The abbreviations and structures of the non-halogen flame retardants used in Examples and Comparative Examples other than the polyphosphates synthesized above are shown below.

[0089]

Embedded image

(8) Cyanuric acid salt When observed with an electron microscope, the cyanuric acid salt used in this example was found to have an average particle size (average value of 100 solids) of less than 100 μm.

Examples 1 to 7 and Comparative Examples 1 to 3 Using PBT as the thermoplastic resin, the polyphosphate of the present invention (A-1, A-2, B-1) produced in Reference Example,
A salt of cyanuric acid or isocyanuric acid, a non-halogen flame retardant other than polyphosphate, and other additives are mixed, and a resin temperature of 2 is used by using a 10 mmΦ single screw extruder.
Melt kneading was carried out at 60 ° C. The compounding recipe and the results are shown in Table 2.

[0092]

[Table 2]

From the comparison of Examples 1 and 2 and Comparative Examples 1 and 2, flame retardancy can be imparted by addition of the polyphosphate of the present invention, and further, reduction of impact strength and deflection temperature under load is small and difficult. It can be seen that there is little bleed out of the fuel. Further, from the comparison of Examples 3 and 4 and Comparative Example 3, it is understood that the flame retardancy is further improved by using the polyphosphate of the present invention in combination with the salt of the triazine compound and cyanuric acid or isocyanuric acid. Further, it is clear from Examples 5 to 7 that the effects of the present invention can be obtained even if a small amount of the polyphosphate of the present invention and a flame retardant or an antioxidant other than polyphosphate are used in combination.

On the other hand, when low molecular weight type aromatic bisphosphates (C1, C2) are used as the flame retardant, flame retardancy can be imparted, but the deflection temperature under load is lowered, and the flame retardant causes bleed-out (Comparative Example 3 4) and poorly soluble (crosslinked) polyphosphate (B-1)
It can be seen that the use of No. 1 has a remarkable decrease in impact strength, although the effects of improving the flame retardancy and suppressing the decrease in the deflection temperature under load are recognized (Comparative Example 2).

Further, from the comparison of Example 8 and Comparative Example 4, even when glass fiber (GF) is added as a filler, flame retardancy can be imparted by addition of the polyphosphate of the present invention, and impact strength is further improved. It can be seen that there is little decrease in the deflection temperature under load and there is little bleed out of the flame retardant.

Examples 9 to 16 and Comparative Examples 5 to 12 Instead of PBT as the thermoplastic resin, PET, PCT,
PC, ABS, PC // ABS (90 // 10), Nylon 6, Nylon 66, PBT // PPO (70
/// 30) was used, and the same procedure as in the above example was performed.
A series of formulation and results are shown in Table 3.

[0097]

[Table 3]

Comparing Examples and Comparative Examples of each resin, PET, PCT, PC, PA6, PA66, AB
Similarly, in the case of S, PBT // PPO and PC // ABS, the polyphosphate of the present invention can impart flame retardancy without lowering impact strength and deflection temperature under load, and less bleed out of flame retardant. I understand. On the other hand, when a polyphosphate (B-1) having a low solubility other than that of the present invention is added, the impact resistance is remarkably lowered, and the aromatic bisphosphate (C-
1, C-2), the deflection temperature under load is remarkably lowered, and it is found that these compounds bleed out.

From the above results, by blending the polyphosphate of the present invention with a thermoplastic resin, it is possible to obtain a resin composition having excellent flame retardancy, impact resistance, heat resistance and less bleed-out of a flame retardant. I understand. The same applies when GF is added as a filler. It is also found that flame retardancy is improved by further adding a salt of a triazine compound and cyanuric acid or isocyanuric acid, a small amount of a non-halogen flame retardant, and a fluororesin as an additive.

[0100]

INDUSTRIAL APPLICABILITY A resin composition obtained by blending a novel high molecular weight polyphosphate with a thermoplastic resin is flame-retardant as compared with conventionally known resin compositions containing a phosphorus-based flame retardant such as aromatic phosphate or aromatic phosphate oligomer. Resistance, impact resistance, heat resistance, and less bleedout of flame retardant, connector, relay, switch, case member,
Electrical and electronic equipment parts such as transformer members and coil bobbins,
It can be used as a flame-retardant resin composition suitable for automobile parts, machine parts, and building materials.

Claims (12)

[Claims] (1) 100 parts by weight of a thermoplastic resin (A) is composed of (B) a repeating unit represented by the following general formula (1), measured by gel permeation chromatography, and converted by standard polystyrene. Acetone having a number average molecular weight of 10,000 or more and 20 ° C.,
A flame-retardant resin composition containing 1 to 100 parts by weight of a polyphosphate having a solubility of 90 wt% or more in at least one organic solvent selected from chloroform, dimethylformamide, dimethylsulfoxide, and tetrahydrofuran. Embedded image (However, R ¹ represents the same or different hydrogen atom or an alkyl group having 1 to 5 carbon atoms. Ar represents a phenyl group or a phenyl group substituted with a halogen-free organic residue.) 2. The flame-retardant resin composition according to claim 1, wherein Ar has a structure represented by any one of formulas (2) to (7). Embedded image (X represents a direct bond, O, S, SO ₂ , CH ₂ and CHPh, and Ph represents a phenyl group.) 3. The flame-retardant resin composition according to claim 1, wherein R ¹ is an alkyl group having 1 to 5 carbon atoms. 4. The flame-retardant resin composition according to claim 1, further comprising 1 to 100 parts by weight of a salt of a triazine compound and cyanuric acid or isocyanuric acid, based on 100 parts by weight of the thermoplastic resin. . 5. The flame-retardant resin composition according to claim 4, wherein the triazine compound is melamine. 6. The flame-retardant resin composition according to claim 1, further comprising 1 to 50 parts by weight of a non-halogen flame retardant with respect to 100 parts by weight of the thermoplastic resin. 7. The flame-retardant resin composition according to claim 6, wherein the halogen-free flame retardant is a flame retardant containing phosphorus. 8. The flame-retardant resin composition according to claim 1, wherein 0.01 to 10 parts by weight of a fluororesin is further added to 100 parts by weight of the thermoplastic resin. 9. The flame-retardant resin composition according to claim 1, which further comprises 0.01 to 3 parts by weight of a hindered phenolic stabilizer based on 100 parts by weight of the thermoplastic resin. 10. The flame-retardant resin composition according to claim 1, further comprising 5 to 140 parts by weight of a filler with respect to 100 parts by weight of the thermoplastic resin. 11. The flame retardant according to claim 1, wherein the thermoplastic resin is one kind or a mixture of two or more kinds selected from polyester, polyethylene, polypropylene, ABS, polyamide, polycarbonate, phenoxy resin, polyphenylene sulfide and phenol resin. Resin composition. 12. A molded article comprising the flame-retardant resin composition according to claim 1.