JP3115195B2 - Flame-retardant polyester resin composition and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a flame-retardant polyester resin composition having excellent flame retardancy without using a halogen-based flame retardant, and a method for producing the same. For more information,
Has excellent flame retardancy and good electrical properties, lubricity, plasticity, coloring, surface smoothness, dyeability, and good mechanical properties, heat resistance, moisture resistance, moldability, heat stability The present invention relates to a flame-retardant polyester resin composition which gives a molded article having properties and the like, and a method for producing the same.

[0002]

2. Description of the Related Art Thermoplastic polyesters typified by polyalkylene terephthalate and the like are widely used in electric and electronic equipment parts, automobile parts, and the like because of their excellent properties. In particular, in the electric and electronic device parts field, in many cases, they are used with imparting flame retardancy in order to ensure safety against fire.

In order to impart flame retardancy to a thermoplastic polyester, a halogen-based flame retardant is generally used. For this reason, at the time of kneading and molding, part of the halogen-based flame retardant is decomposed, and free halogen gas and halogen compounds are generated,
It corrodes the surfaces of cylinders and molds of compound kneaders and the like, and corrodes metal parts in the electrical and electronic equipment parts field, causing poor contact and poor conduction. Further, some of the halogen-based flame retardants include toxic ones even though the amount of decomposition generated gas is very small.

Heretofore, in order to solve such a problem, a flame retardant of a heterocyclic compound type such as melamine / cyanurate is added to a thermoplastic polyester to provide flame retardancy, electric properties, lubricity, plasticity and the like. Methods for improving characteristics such as colorability, surface smoothness, and dyeability are also known (for example, JP-A-50-105744, JP-B-60-33).
No. 850).

[0005] However, even if these flame retardants are used, their flame retardancy is insufficient, and these flame retardants have relatively poor compatibility with thermoplastic polyesters. When added in a large amount, there is a drawback that the inherent properties of the resin are impaired, such as deterioration in mechanical properties, heat resistance, moisture resistance, moldability and the like.

Various proposals have been made in the past to improve such disadvantages. For example, JP-A-54-112
No. 958 discloses thermoplastic polyester and melamine.
A method of adding flame retardancy without impairing mechanical properties by adding a carboxylic acid ester of a compound having a triazine skeleton to a composition with cyanurate as a dispersant is disclosed.

However, there is a problem that when the amount of the additive is increased in order to obtain higher flame retardancy, the mechanical properties are remarkably reduced.

[0008]

Means for Solving the Problems The present inventors have added excellent flame retardancy by adding a heterocyclic compound-based flame retardant to the above-mentioned thermoplastic polyester, and further improved electrical properties, lubricity and plasticity. Occurs when imparting properties such as coloring, surface smoothness, and dyeing properties; flame retardancy is not sufficient; mechanical properties, heat resistance, moisture resistance, moldability, heat stability, etc. decrease. As a result of intensive studies to improve the problem of the above, surprisingly, by using a heterocyclic compound containing a nitrogen atom and a compound having two or more functional groups in combination, it is Properties such as flame retardancy can be imparted, and even if a large amount of the flame retardant is added, good molded articles such as mechanical properties, heat resistance, moisture resistance, moldability, and heat stability can be obtained. Find out what can be done and complete the present invention Led was.

That is, the present invention provides (A) a thermoplastic polyester and (B) a heterocyclic compound containing a nitrogen atom in an amount of 2 to 50% (% by weight, hereinafter the same) based on the component (A).
(C) 0.1 to 50% of a compound having two or more functional groups based on the component (B) and (D) a phosphorus-based flame retardant (A)
The flame-retardant polyester resin composition containing 0 to 50% of the component (Claim 1), wherein the nitrogen-containing heterocyclic compound is represented by the general formula (I):

[0010]

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(Wherein R ¹ , R ² and R ³ represent a hydrogen atom,
The flame-retardant compound according to claim 1, wherein the compound is an amino group, an aryl group or an oxyalkyl group having 1 to 3 carbon atoms, and R ¹ , R ² and R ³ may be the same or different. The polyester resin composition (Claim 2), wherein the heterocyclic compound containing a nitrogen atom has a general formula (II):

[0012]

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(Wherein R ⁴ , R ⁵ and R ⁶ are hydrogen atoms,
The flame retardant according to claim 1, wherein the compound is an amino group, an aryl group or an oxyalkyl group having 1 to 3 carbon atoms, and R ⁴ , R ⁵ , and R ⁶ may be the same or different. The polyester resin composition (Claim 3), wherein the heterocyclic compound containing a nitrogen atom has a general formula (III):

[0014]

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(Wherein R ⁷ , R ⁸ and R ⁹ are a hydrogen atom,
Amino group, hydroxyl group, mercapto group, alkylamino group having 1 to 10 carbon atoms, anilino group, morpholino group, hydrazino group, benzylamino group, pyridylamino group, pyridylmethylamino group, thenylamino group or oxyalkyl group having 1 to 3 carbon atoms The flame-retardant polyester resin composition (Claim 4) according to claim 1, wherein the compound is a compound represented by the following formula: wherein R ⁷ , R ⁸ and R ⁹ may be the same or different. 2. The flame-retardant polyester resin composition according to claim 1, wherein the heterocyclic compound containing melamine cyanurate is a melamine cyanurate, wherein the functional group in the compound having two or more functional groups is an epoxy group or a carboxylic acid. Anhydride group, isocyanate group, oxazoline group, carbodiimide group, aldehyde group, carboxyl group, aziridinyl group (ethylene 2. The flame-retardant polyester resin composition according to claim 1, which is at least one member selected from the group consisting of a cyano group and a cyanate group, wherein at least one of the compounds having two or more functional groups is a diepoxy compound. 2. The flame-retardant polyester resin composition according to claim 1, wherein at least 80 mol% of the repeating units of the thermoplastic polyester are alkylene terephthalate units. The flame retardant according to claim 8, wherein the thermoplastic polyester comprises a polyethylene terephthalate-based copolymer containing 1 to 30% by weight of a unit derived from polyethylene terephthalate and / or a polyoxyalkylene-based compound. Polyester resin composition (Claim 9), derived from the polyoxyalkylene compound The unit is represented by the general formula (IV):

[0016]

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(Wherein, R ¹⁰ is a divalent hydrocarbon group having 2 to 4 carbon atoms, X is a direct bond or an alkylene group having 1 to 3 carbon atoms, —S—, —SO ₂ —, —O— or -CO- a divalent linking group, m and n are integers of 5 to 20, (m + n)
Number of R ¹⁰ is flame-retardant polyester resin composition according to claim 9, wherein the unit represented by the even or) not be the same (claim 10), wherein the phosphorus-based flame retardant of the general formula (V):

[0018]

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(Wherein, R ^{11 to} R ²² are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, Y is a direct bond or an alkylene group having 1 to 3 carbon atoms, —S—, —SO
_{2 -, - O -, -} CO- or -N = a N- is a divalent linking group, flame retardant polyester according to claim 1, wherein k is a condensed phosphoric acid ester represented by 0 or 1) Resin composition (Claim 11), (A) thermoplastic polyester, (B) 2-50% of melamine cyanurate based on component (A), (C) diepoxy compound, carboxylic acid 2
0.1% to 50% of at least one of anhydride, diisocyanate compound and polycarbodiimide compound with respect to component (B) and (D) condensed phosphoric ester represented by general formula (V) as component (A) 0 to 50%
A flame-retardant polyester resin composition (claim 1)
2) and (A) a thermoplastic polyester, and (B) a heterocyclic compound containing a nitrogen atom in an amount of 2 to 5 with respect to the component (A).
0%, 0.1 to 50% of a compound having two or more functional groups (C) based on the component (B), and 0 to 50% of a (D) phosphorus-based flame retardant based on the component (A). When the flame-retardant polyester resin composition is produced, the components (A) and (C) are stirred and mixed, and then the remaining components are mixed. The present invention relates to a manufacturing method (claim 13).

[0020]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The thermoplastic polyester (A) used in the present invention refers to a divalent acid such as terephthalic acid or a derivative thereof having an ester-forming ability as an acid component, and having 2 to 10 carbon atoms as a glycol component. A saturated polyester obtained by using glycol, other dihydric alcohols or derivatives thereof having an ester-forming ability. Among these, at least 80 mol% or more of the repeating units such as polyethylene terephthalate and polybutylene terephthalate are composed of alkylene terephthalate units, for example, from the viewpoint that the workability, mechanical properties, electrical properties, heat resistance and the like are well balanced. Polyalkylene terephthalate or a polyalkylene terephthalate-based copolymer, or a polyethylene terephthalate-based copolymer containing 1 to 30% of a unit derived from a polyoxyalkylene-based compound is preferably used. These may be used alone or in combination of two or more.

Specific examples of the polyoxyalkylene compound include, for example, polyethylene glycol, polypropylene glycol, polytetramethylene glycol,
Polyoxyalkylene compounds such as ethylene oxide / propylene oxide random or block copolymers, and modified polyoxyalkylene compounds such as alkylene oxide (ethylene oxide, propylene oxide, tetramethylene oxide, etc.) adducts of bisphenol compounds, and have a number average molecular weight of 500 to There are 2,000 ones. Of these, alkylene oxides of bisphenol compounds are preferred because of good thermal stability at the time of copolymerization with polyethylene terephthalate and little decrease in heat resistance of molded articles obtained by using the resin composition of the present invention. Adducts are particularly preferred.

The alkylene oxide adduct of the bisphenol compound is represented by the following general formula (IV):

[0023]

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(Wherein R ¹⁰ is —CH ₂ CH ₂ —, —CH
2 carbon atoms such as (CH ₃ ) CH ₂ — and — (CH ₂ ) ₄ —
X is a direct bond or -CH _{2
-, - CH 2 CH 2 -} , - C (CH 3) 2 - C 1-3 alkylene group such _{as, -S -, - SO 2 -} , - O-
Or -CO- a divalent linking group, m and n are 5-2
0, preferably an integer of 7-15, those represented by (m + n) pieces of R ¹⁰ may not be the same) and the like.

The intrinsic viscosity of the thermoplastic polyester (measured at 25 ° C. in a mixed solvent of phenol / tetrachloroethane at a weight ratio of 1/1) is preferably from 0.4 to 1.2, particularly preferably from 0.6 to 1.2. It is preferably 1.0. If the intrinsic viscosity is less than 0.4, mechanical properties tend to be inferior,
If it exceeds 1.2, the moldability tends to decrease.

The nitrogen-containing heterocyclic compound (hereinafter, also referred to as nitrogen-containing heterocyclic compound) (B) makes the thermoplastic polyester (A) flame-retardant and has electrical and lubricity properties. It is a component for improving plasticity, colorability, surface smoothness and dyeability, and is a compound represented by a nitrogen-containing 5-membered heterocyclic compound, a nitrogen-containing 6-membered heterocyclic compound and the like.

The nitrogen-containing heterocyclic compound (B) includes:
Nitrogen-containing heterocyclic compounds themselves, salts of nitrogen-containing heterocyclic compounds with other compounds, salts of nitrogen-containing heterocyclic compounds, lubricants added during the preparation of these, with plasticizers and the like And mixtures.

Examples of the nitrogen-containing 5-membered heterocyclic compound include pyrroles, indoles, isoindoles,
Oxazoles, isoxazoles, thiazoles,
Imidazoles, pyrazoles, oxadiazoles,
Thiadiazoles, triazoles, tetrazoles and the like, and derivatives thereof.Examples of the nitrogen-containing heterocyclic six-membered cyclic compound include oxazines, thiazines, pyridazines, pyrimidines, pyrazines, triazines, Examples include tetrazines and derivatives thereof.

The nitrogen-containing heterocyclic compounds may be used alone or in combination of two or more.

Specific examples of the nitrogen-containing heterocyclic compound include, for example, melamine, guanamine, benzoguanamine, triphenyltriazine, diaminophenyltriazine and the like;

[0031]

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(Wherein R ¹ , R ² and R ³ are hydrogen atoms,
Amino group, aryl group (phenyl group, tolyl group, biphenyl group, naphthyl group, phenanthryl group, etc.), oxyalkyl group having 1 to 3 carbon atoms (—CH ₂ OH, —CH ₂ C
H ₂ OH, —CH (CH ₃ ) CH ₂ OH, etc.)
R ¹ , R ² and R ³ may be the same or different)
General formula (II) including compounds represented by the following formulas, for example, cyanuric acid, isocyanuric acid, triphenyl cyanurate, trisphenyl isocyanurate and the like:

[0033]

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(Wherein R ⁴ , R ⁵ and R ⁶ are a hydrogen atom,
Amino group, aryl group (phenyl group, tolyl group, biphenyl group, naphthyl group, phenanthryl group, etc.), oxyalkyl group having 1 to 3 carbon atoms (—CH ₂ OH, —CH ₂ C
H ₂ OH, —CH (CH ₃ ) CH ₂ OH, etc.)
R ⁴ , R ⁵ and R ⁶ may be the same or different)
General formula (III) including compounds represented by the following formulas, for example, purine, hypoxanthine, xanthine, uric acid, adenine, guanine, isoguanine and the like:

[0035]

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Wherein R ⁷ , R ⁸ and R ⁹ are a hydrogen atom,
Amino group, hydroxyl group, mercapto group, alkylamino group having 1 to 10 carbon atoms (methylamino group, dimethylamino group,
such as n- decylamino group), an anilino group, morpholino group, hydrazino group, benzylamino group, pyridylamino group, pyridyl methyl group, Teniruamino group, oxyalkyl group having 1 to 3 carbon atoms (-CH ₂ OH, -CH ₂ C
H ₂ OH, —CH (CH ₃ ) CH ₂ OH, etc.)
R ⁷ , R ⁸ and R ⁹ may be the same or different)
Wherein R ^{7 to} R ^{9 in the} formula (III) are hydrogen atoms, purine, and R ⁷ and R ^{9 in the} formula (III)
There hydrogen atom a is when R ⁸ is a hydroxyl group is hypoxanthine, R ⁹ of the general formula (III) is a hydrogen atom and R ⁷ and R
^{When 8} is a hydroxyl group, xanthine is represented by R ^{7 of the} general formula (III)
When R ⁹ is a hydroxyl group, uric acid; when R ⁷ and R ^{9 in} the general formula (III) are hydrogen atoms and R ⁸ is an amino group, adenine; when R ^{9 in the} general formula (III) is a hydrogen atom; When R ⁸ is a hydroxyl group and R ⁷ is an amino group, guanine is represented by the general formula (III)
In which R ⁹ is a hydrogen atom, R ⁷ is a hydroxyl group, and R ⁸ is an amino group is isoguanine, for example, pyrimidinols such as cytosine, uracil, and thymine; benzotriazoles such as benzotriazole and phenylbenzotriazole; -Benzimidazoles such as phenylbenzimidazole and 2-vinylbenzimidazole, such as melamine cyanurate (preferably equimolar adduct formed by melamine with cyanuric acid and / or its tautomer), benzoguanamine urate and the like. Salts comprising nitrogen heterocyclic compounds are exemplified.

Examples of the salt of the nitrogen-containing heterocyclic compound and other compounds include a basic heterocyclic compound and an acid such as phosphoric acid, phosphonic acid, phosphinic acid, sulfonic acid, sulfamic acid, and silicic acid. And two or more acids such as phosphoric acid and silicic acid may be condensed. Specific compounds include melamine phosphate (phosphoric acid and melamine in a molar ratio of 3/1 to 1/3), guanamine phosphate (phosphoric acid and guanamine in a molar ratio of 2/1 to 1/1). 3), melamine metaphosphate (metaphosphoric acid and melamine in a molar ratio of 3/1 to 1/4), melamine nitrilotris (methylene) phosphonate (molar ratio of nitrilotris (methylene) phosphonic acid and melamine) 3/1 to 1/6 in ratio
).

The nitrogen-containing heterocyclic compound (B) is preferably used because it has good thermal stability, does not deteriorate the moldability and physical properties of the thermoplastic resin to be added, and the like. Solid at the processing temperature of the thermoplastic resin, and the particle size thereof is preferably 0.01 to 100 μm,
More preferably, it is a fine powder of 0.5 to 10 μm.

Such a nitrogen-containing heterocyclic compound (B)
Preferred specific examples thereof include, for example, melamine, cyanuric acid, melamine cyanurate, guanamine, guanine, and purine, which are solid at the processing temperature of the thermoplastic resin, and have an average particle size of 0.01 to 100 μm, Are fine powders of 0.5 to 10 μm. Among them, melamine, which has good thermal stability
Cyanurate is preferred.

To synthesize a salt of a nitrogen-containing heterocyclic compound (eg, melamine cyanurate, melamine phosphate, etc.), a solution of a basic compound and a solution of an acidic compound are mixed to form a salt. Alternatively, the salt may be formed while adding and dissolving the other solution to one solution, and then the separated salt may be separated, and the solvent may be removed.

The mixing ratio between the basic compound and the acidic compound is not particularly limited, but is preferably close to equimolar so as not to impair the thermal stability of the thermoplastic resin.
Preferably, it is 1.

The solvent used is preferably water, but a solvent miscible with water, for example, lower alcohol, acetone, methyl ethyl ketone, tetrahydrofuran, dimethylformamide and the like may be used.

The reaction temperature is optional, but if it is difficult to form a solution, it may be heated to preferably about 40 to 100 ° C.

The compound (C) having two or more functional groups in the present invention (hereinafter also referred to as a functional group-containing compound) is flame-retardant and has electrical properties due to the nitrogen-containing heterocyclic compound (B). It is used to prevent the mechanical properties, heat resistance, moisture resistance, etc. of the thermoplastic polyester provided with lubricity, plasticity, colorability, surface smoothness, and dyeability from being significantly reduced.

The functional group-containing compound (C) improves the affinity and compatibility between the nitrogen-containing heterocyclic compound (B) and the thermoplastic polyester (A). As a result, the thermoplastic polyester (A) It is considered that the dispersibility and adhesion of the nitrogen-containing heterocyclic compound (B) in the composition are improved.

The functional group in the functional group-containing compound (C) is preferably an epoxy group, a carboxylic anhydride group, an isocyanate group, an oxazoline group, a carbodiimide group, an aldehyde group, a carboxyl group, an aziridinyl group, or a cyanate group. Particularly preferred from the viewpoint of the bonding property between the nitrogen heterocyclic compound (B) and the thermoplastic polyester (A) include an epoxy group, an acid anhydride group, an isocyanate group and an oxazoline group. One of these groups may be contained in the molecule, or two or more thereof may be contained.

The number of the functional groups is 2 as described above.
The number is required from the viewpoint of the binding property between the nitrogen-containing heterocyclic compound (B) and the thermoplastic polyester (A), but the number is more preferably 2 to 3.

The molecular weight of the functional group-containing compound (C) is not particularly limited, but the volatility during molding and the binding between the nitrogen-containing heterocyclic compound (B) and the thermoplastic polyester (A). From the point of view, the molecular weight is 100 to 10
A liquid having a viscosity of about 1000 poise or less at room temperature or a powder at room temperature is preferable from the viewpoint of workability.

Specific examples of such compounds include compounds having an epoxy group, for example, epoxy resins such as bisphenol A type, biphenyl type, phenol novolak type, polyglycidylamine type, resorcin diglycidyl ether, and terephthalic acid. As a compound having an acid anhydride group such as a diglycidyl compound such as diglycidyl, for example, a compound having two or more acid anhydride groups such as pyromellitic anhydride and melitic anhydride, and a compound having an isocyanate group such as phenylene Compounds having an oxazoline group, such as diisocyanate compounds such as diisocyanate, tolylene diisocyanate, and naphthalene diisocyanate, include, for example, 2,2 ′-(1,3-phenylene) -bis (2-oxazoline), Examples of the compound having a carbodiimide group such as a bisoxazone compound such as 2 '-(1,4-phenylene) -bis (2-oxazoline) include an aldehyde group such as a carbodiimide compound derived from phenylene diisocyanate or toluene diisocyanate. As the compound, for example, 1,4-
Dialdehyde compounds such as dialdehyde benzene,
As the compound having a carboxyl group, terephthalic acid,
Examples of the compound having an aziridinyl group such as a dicarboxylic acid compound such as diphenic acid include compounds having two or more aziridinyl groups such as trisaziridinylphosphine oxide and trimethylolpropane-tri-β-aziridinylpropionate. Is raised.

The amount of the functional group-containing compound (C) to be used with respect to the nitrogen-containing heterocyclic compound (B) varies depending on the kind of the nitrogen-containing heterocyclic compound (B).
0.1 to 50 based on nitrogen-containing heterocyclic compound (B)
%, Preferably 0.5 to 30%. If it is less than 0.1%, it is difficult to obtain the effects of the present invention. If it exceeds 50%, the workability and the moldability of the flame-retardant polyester resin composition are significantly reduced.

Judging from the viewpoint of suitably exhibiting the effects of the present invention as a whole, the combination of the nitrogen-containing heterocyclic compound (B) and the functional group-containing compound (C) may be a combination of melamine cyanurate and a diepoxy compound. A combination, a combination of melamine cyanurate and carboxylic dianhydride, a combination of melamine cyanurate and a bisoxazoline compound, a combination of melamine cyanurate and polycarbodiimide, a combination of melamine cyanurate and a diisocyanate compound, and the like are preferable.

In the present invention, in order to impart more excellent flame retardancy and obtain a molded article having good mechanical properties, heat resistance, moisture resistance, etc., or when the desired flame retardancy is obtained. In order to reduce the decrease in mechanical properties other than flame retardancy, heat resistance, moisture resistance, etc. due to the use of a flame retardant while maintaining it, a phosphorus-based compound is used together with the nitrogen-containing heterocyclic compound (B). You may use together a flame retardant (D).
In addition, when the nitrogen-containing heterocyclic compound (B) and the functional group-containing compound (C) are used in combination with the phosphorus-based flame retardant (D), an advanced halogen-based flame retardant can be used without using a halogen-based flame retardant. The effect is that flame retardancy can be imparted and the mechanical properties can be reduced without deteriorating the mechanical properties.

The phosphorus-based flame retardant (D) is not particularly limited as long as it contains a phosphorus atom in the molecule and does not decompose or volatilize during molding of the thermoplastic polyester. Organic phosphorus compounds such as phosphate compounds of alcohols or phenols having a linear or branched aliphatic group, aromatic group or alicyclic group of 1 to 8, preferably 1 to 8, phosphonate compounds, and nitrogen-containing organic phosphorus compounds And inorganic phosphorus compounds.

Specific examples of the phosphorus-based flame retardant (D) include, for example, monophosphate esters such as triphenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, octyl diphenyl phosphate, octyl diphenyl phosphate, ammonium polyphosphate, and polyphosphoric acid. Acid amide, red phosphorus, guanidine phosphate, dialkylhydroxymethyl phosphonate, such as a condensed phosphate ester represented by the following general formula (V), and the like.

Among the above-mentioned phosphorus-based flame retardants, the reason is that they are low in volatility and good in thermal stability at the time of molding, and the thermal stability and physical properties of the thermoplastic polyester (A) are hardly impaired. From the general formula (V):

[0056]

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(Wherein, R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ ,
R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ and R ²² each independently represent a hydrogen atom or —CH ₃ , —C ₂ H ₅ , —C
_{3 H 7, -CH (CH 3} ) 2, -C alkyl group having 1 to 4 carbon atoms such as (CH _{3) 3;} Y is a direct bond or -CH
_{2 -, - CH 2 CH 2} -, - CH (CH 3) CH 2 -,
-C (CH _{3) 2} - C 1-3 alkylene group such _{as, -S -, - SO 2 -} , - O -, - CO- or -
A divalent linking group wherein N = N-; k represents an integer of 0 or 1).

In the above general formula (V), when the position to which R ¹¹ , R ¹⁵ , R ¹⁶ and R ²⁰ are bonded is blocked by an alkyl group having 1 to 4 carbon atoms, the heat stability is further improved. It is particularly preferable because of its excellent properties. It is also preferable from the viewpoint that the molecular weight is increased so that the volatility can be further reduced.

Specific examples of the above-mentioned condensed phosphate ester include, for example, those represented by the formula (VI):

[0060]

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Examples thereof include hydroquinone bis (diphenyl) phosphate, resorcinol bis (diphenyl) phosphate, bisphenol A bis (dicresyl) phosphate (hereinafter referred to as BBCP), and bisphenol A bis (diphenyl) phosphate. Among these, the compounds represented by the formulas (VI) to (VIII) and BBCP are particularly low in volatility and excellent in thermal stability, and when used in combination with the nitrogen-containing heterocyclic compound (B), When the flame retardant alone is used to impart the desired flame retardancy, it is possible to reduce the reductions in mechanical properties, heat resistance, moisture resistance, and the like, which are disadvantages that occur when the flame retardant alone is used. Particularly in terms of imparting flame retardancy and reducing the amount of each flame retardant additive, it is possible to obtain a molded article having excellent mechanical properties, heat resistance such as heat distortion temperature, etc. preferable.

When sufficient flame retardancy is to be obtained only with the nitrogen-containing heterocyclic compound (B) and the functional group-containing compound (C), the functional group-containing compound (C) is not used. Although it is possible to obtain much better mechanical properties and the like as compared with the above, it is preferable to use it in combination with a phosphorus-based flame retardant (D).

The amount of the nitrogen-containing heterocyclic compound (B) added to the thermoplastic polyester (A) depends on the level of flame retardancy, the type of the nitrogen-containing heterocyclic compound (B) (the nitrogen-containing heterocyclic compound). Although it depends on the nitrogen atom content in the formula compound (B) and the average particle size, the thermoplastic polyester (A)
2 to 50%, preferably 5 to 40%, more preferably 10 to 30%. If it is less than 2%, the level of improvement in flame retardancy is insufficient, and if it exceeds 50%, the intrinsic properties of the thermoplastic polyester (A) such as mechanical properties deteriorate.

The amount of the phosphorus-based flame retardant (D) added to the thermoplastic polyester (A) depends on the level of imparting flame retardancy,
Depending on the phosphorus atom content in the phosphorus-based flame retardant (D), it is 0 to 50 with respect to the thermoplastic polyester (A).
%, Preferably 2 to 30%, more preferably 5 to 30%.
20%. When the addition amount of the phosphorus-based flame retardant (D) is less than 2%, the effect produced by the combined use with the nitrogen-containing heterocyclic compound (B), ie, high flame retardancy and moldability. In addition, effects such as improvement in thermal stability tend to be hardly exhibited, and if it is more than 50%, mechanical properties and heat resistance are significantly reduced.

The combination ratio of the phosphorus-based flame retardant (D) with the nitrogen-containing heterocyclic compound (B) and the functional group-containing compound (C) depends on the type of the thermoplastic polyester (A) and the thermoplastic polyester (A). )), The nitrogen-containing heterocyclic compound (B) and Phosphorus-based flame retardant (D) is preferably 5-600 relative to 100 parts of functional group-containing compound (C).
Parts, more preferably 20 to 200 parts. When the content of the phosphorus-based flame retardant (D) is less than the above range, the phosphorus-based flame retardant (D) is used in combination with the nitrogen-containing heterocyclic compound (B) and the functional group-containing compound (C). In this case, the effects of high flame retardancy and molding processability, which are the effects of the above, tend to be difficult to obtain sufficient effects such as improvement in thermal stability, and when the amount is more than the above range, the mechanical properties and heat resistance are poor. Tends to decrease.

As a method of using the nitrogen-containing heterocyclic compound (B) and the functional group-containing compound (C) in combination with the phosphorus-based flame retardant (D), for example, the nitrogen-containing heterocyclic compound (B)
And a method in which a premix of the functional group-containing compound (C) and the phosphorus-based flame retardant (D) is mixed with the thermoplastic polyester (A), a nitrogen-containing heterocyclic compound (B), a functional group-containing compound ( C), phosphorus-based flame retardant (D)
And the method of mixing the thermoplastic polyester (A) all at once. When the phosphorus-based flame retardant (D) is liquid at room temperature, the former method is preferred because it is easy to mix uniformly.

When the nitrogen-containing heterocyclic compound (B) and the functional group-containing compound (C) are used in combination with the phosphorus-based flame retardant (D), the total amount of the flame retardant added to the thermoplastic polyester (A) is as follows: Although it depends on the type of the nitrogen-containing heterocyclic compound (B), the type of the thermoplastic polyester (A), the type of the property to be imparted to the thermoplastic polyester (A), such as the flame retardancy, and the level of the property, The total addition amount of the nitrogen-containing heterocyclic compound (B) and the functional group-containing compound (C) and the phosphorus-based flame retardant (D) is preferably 7 to 70%, more preferably to the thermoplastic polyester (A). Is 15 to 50%. This amount is equal to or less than the addition amount of only the nitrogen-containing heterocyclic compound (B) or the addition amount of only the phosphorus-based flame retardant (D) necessary to obtain the same flame retardant effect. . If the preferred addition amount of the nitrogen-containing heterocyclic compound (B), the functional group-containing compound (C) and the phosphorus-based flame retardant (D) is less than the above range, the properties such as flame retardancy are sufficiently improved to a desirable level. When the ratio exceeds the above range, the effect of using these together, that is, the effect of not deteriorating the original properties of the thermoplastic resin such as mechanical properties so much while realizing good flame retardancy is sufficient. It tends to be impossible to obtain.

The thermoplastic polyester (A), the nitrogen-containing heterocyclic compound (B), the functional group-containing compound (C) and the phosphorus-based flame retardant (D) have been described above. Comprehensively judging from the viewpoint of suitably expressing, the combination of the thermoplastic polyester (A) with the nitrogen-containing heterocyclic compound (B) and the functional group-containing compound (C) includes polyethylene terephthalate, melamine cyanurate and Combination with epoxy resin, combination of polyethylene terephthalate with a compound having melamine cyanurate and acid anhydride, unit 1 derived from polyoxyalkylene compound (particularly bisphenol-modified polyoxyalkylene)
Unit 1 derived from a polyoxyalkylene compound (particularly bisphenol-modified polyoxyalkylene) in combination with a polyethylene terephthalate copolymer containing -30% by weight, melamine cyanurate and epoxy resin
Combination of polyethylene terephthalate-based copolymer containing up to 30% with a compound having melamine cyanurate and acid anhydride, combination of polybutylene terephthalate with melamine cyanurate and epoxy resin, 70 / of polybutylene terephthalate and polyethylene terephthalate A combination of a 30 (weight ratio) blend with melamine cyanurate and an epoxy resin is preferred.

When the phosphorus-based flame retardant (D) is used in combination, the above various combinations are further used in combination with the above-mentioned condensed phosphoric ester (especially a compound represented by the general formula (V)); (Eg, a combination of monophosphoric acid triesters such as triphenyl phosphate), a combination of the above phosphonate compounds, and a combination of red phosphorus and the like.

If necessary, the composition of the present invention may further contain other flame retardants, particularly Mg-based compounds, Zn-based compounds, and Sn-based compounds.
Inorganic flame retardants containing flame retardants, flame retardant aids, strengthening agents, heat stabilizers, antioxidants, UV absorbers, release agents,
Various inorganic or organic compounds such as a coloring agent, a crystal nucleating agent, an antistatic agent, a filler, a lubricant, a plasticizer, and other polymers can be added to the extent that the object of the present invention is not impaired.

The flame-retardant resin composition of the present invention can be produced by mixing by various methods. For example, it can be obtained by a method in which each component and additive are put into a usual stirring mixer and mixed by stirring, and further melt-kneaded by an extruder. As a method of stirring and mixing these components, the thermoplastic polyester (for the reason of simplicity of the operation and hardly impairing the binding property between the nitrogen-containing heterocyclic compound (B) and the functional group-containing compound (C)) is used. It is preferred that after A) and the functional group-containing compound (C) are stirred and mixed, the remaining components are mixed. When the phosphorus-based flame retardant (D) is a liquid, it is preferable to add it from the middle of the extruder.

After the surface treatment of the nitrogen-containing heterocyclic compound (B) with the functional group-containing compound (C),
Thermoplastic polyester (A) and phosphorus-based flame retardant (D)
May be mixed. When the nitrogen-containing heterocyclic compound (B) is surface-treated in advance with the functional group-containing compound (C), the nitrogen-containing heterocyclic compound (B) and the thermoplastic polyester (A) are obtained by using the functional group-containing compound (C). ), And the reliability of the dispersibility and adhesion of the nitrogen-containing heterocyclic compound (B) in the thermoplastic polyester (A) is improved.

The amount of the functional group-containing compound (C) after the surface treatment of the nitrogen-containing heterocyclic compound (B) is usually 2 to 50% based on the thermoplastic polyester (A). , More preferably 5-40%, especially 10-3
0% is adopted.

The method of the surface treatment is not particularly limited as long as the nitrogen-containing heterocyclic compound (B) and the functional group-containing compound (C) are used, and the surface treatment is performed by a usual surface treatment with an inorganic filler or the like. A method or the like can be used. For example, a nitrogen-containing heterocyclic compound (B) and a functional group-containing compound are mixed in a mixer such as a high-speed stirring mixer, a flash mixer, an air blender, a ribbon blender, a double cone mixer, a V-shaped mixer, a pug mixer, and a rotary mixer. (C) or its solvent diluent,
After mixing for about 20 minutes, drying is performed as necessary to obtain a nitrogen-containing heterocyclic compound (B) surface-treated with the functional group-containing compound (C). Further, the nitrogen-containing heterocyclic compound (B) is dispersed in a solvent to form a slurry, the functional group-containing compound (C) is added with stirring, the mixture is stirred by the mixer, separated, and dried. In addition, it can also be obtained, for example, by adding a solvent diluent of the functional group-containing compound (C) to the nitrogen-containing heterocyclic compound (B) in a high temperature state by spraying.

Among the above-mentioned methods, a high-speed stirring mixer is used because of the simplicity of the operation and the difficulty in deteriorating the binding property between the nitrogen-containing heterocyclic compound (B) and the functional group-containing compound (C). A method of mixing and mixing the nitrogen heterocyclic compound (B) and the functional group-containing compound (C) is preferable.

The nitrogen-containing heterocyclic compound (B) surface-treated with the functional group-containing compound (C) thus obtained
Has an average particle diameter of 0.01 to 100 μm, preferably 0.1 to 100 μm.
It is in the form of a fine powder of 5 to 10 μm.

The composition of the present invention can be formed into various forms by various molding methods, for example, various molded articles, sheets, pipes, bottles and the like. In addition, it has excellent flame retardancy despite being non-halogen and has good balance with other properties, so it is suitable for injection molded products such as electronic and electric parts such as home appliances and OA equipment. Used for In particular, excellent dielectric strength, arc resistance,
As applications utilizing electric characteristics such as tracking resistance, it is suitably used for breaker parts, switch parts, motor parts, ignition coil cases, power plugs, power outlets, coil bobbins, connector terminals, relay terminals, fuse cases, and the like.

Next, the composition and the production method of the present invention will be specifically described with reference to examples, but the present invention is not limited to these.

Examples 1 to 7 Polyethylene terephthalate (PET) having intrinsic viscosity (measured at 25 ° C. in a mixed solvent of phenol / tetrachloroethane at a weight ratio of 1/1, the same applies hereinafter) of 0.65 and sufficiently dried The amount of bisphenol A type epoxy resin (Eicoat 828, manufactured by Yuka Shell Epoxy Co., Ltd.) as the functional group-containing compound (C) is not the amount shown in Table 1 (the amount is not based on the nitrogen-containing heterocyclic compound (B)). )
The mixture was stirred and mixed in a ribbon blender for 3 minutes, and then as a nitrogen-containing heterocyclic compound (B), melamine cyanurate (average particle size: 1 μm, molecular weight: 255, nitrogen content: 49.4)
%, Decomposition temperature 450 ° C.), the amount shown in Table 1, talc 1%,
Antioxidants (tetrakis methylene-3,5-di-t-
Butyl-4-hydroxyhydrocinnamate / methane (0.5%) was added and mixed with stirring for 3 minutes. Further, 30% of glass fiber (fiber length 3 mm, diameter 11 μm, aminosilane treatment) was added, and the mixture was melt-kneaded at 280 ° C. by a vented 45 mmφ extruder to be pelletized. After drying these pellets at 140 ° C. for 4 hours, an injection molding machine (mold clamping pressure 5
0 tons), cylinder temperature 280 ° C, mold temperature 1
Test specimens were formed at 00 ° C.

Using the obtained test pieces, a flame retardant (UL-9)
4 standard, 1/16 "thickness), tensile strength (ASTM D-
638), Izod value (ASTM D-256, with notch), HDT (ASTM D-648, 18.6 kg)
/ Cm ² load) and moisture resistance (the tensile strength retention after treatment at 90 ° C. and a relative humidity of 100% for 72 hours). Table 1 shows the results.

Not-V of the evaluation result of flame retardancy is UL.
Indicates non-compliance with the -94 standard.

Example 8 Example 8 was repeated except that 0.5% of an acid anhydride (pyromellitic anhydride) was used as the functional group-containing compound (C) and 10% of RBXP was used as the phosphorus-based flame retardant (D). Evaluation was performed in the same manner as in Example 2. Table 1 shows the results.

Example 9 In Example 2, 0.5% of tolylene diisocyanate (Coronate, manufactured by Nippon Polyurethane Co., Ltd.) was used as the functional group-containing compound (C), and tricresyl phosphate was used as the phosphorus-based flame retardant (D). Daihachi Chemical Industry Co., Ltd., TCP)
Evaluation was performed in the same manner as in Example 2 except that 8% was used.
Table 1 shows the results.

Example 10 In Example 2, a polycarbodiimide (Stavaxol P, manufactured by Hiraizumi Yoko Co., Ltd.) was used as the functional group-containing compound (C).
CD) was evaluated in the same manner as in Example 2, except that 0.5% of red phosphorus-containing flame retardant (D) and 0.3% of red phosphorus (Novared 120, manufactured by Rin Kagaku Kogyo Co., Ltd.) were used. Table 1 shows the results.

Example 11 In Example 2, 0.5% of diglycidyl terephthalate (Denacol EX-711, manufactured by Nagase Kasei Kogyo Co., Ltd.) as the functional group-containing compound (C) and BBCP as the phosphorus-based flame retardant (D) Evaluation was performed in the same manner as in Example 2 except that 25% was used. Table 1 shows the results.

Example 12 In Example 2, PET / bisphenol A ethylene oxide adduct (molecular weight: 1,000, molar ratio of bisphenol A to ethylene oxide unit: 0.06), 30% block copolymer P as thermoplastic polyester (A)
ET (copolymer (1)) mixture (weight ratio 85/15)
Was evaluated in the same manner as in Example 2 except that BBCP 10% was used as the phosphorus-based flame retardant (D). Table 1 shows the results.

Example 13 In Example 2, bisphenol A ethylene oxide adduct (molecular weight: 10) was used as the thermoplastic polyester (A).
The molar ratio of bisphenol A to ethylene oxide units is 0.06) 10% block copolymerized PET (copolymer (2)), and bisoxazoline (2,2 '-(1,3 -Phenylene) -bis (2-oxazoline)) 0.5%, phosphorus-based flame retardant (D)
Was evaluated in the same manner as in Example 2 except that RBXP 10% was used. Table 1 shows the results.

Comparative Example 1 Evaluation was made in the same manner as in Example 1 except that the nitrogen-containing heterocyclic compound (B) and the functional group-containing compound (C) were not used. Table 1 shows the results.

Comparative Example 2 Evaluation was made in the same manner as in Example 5 except that the functional group-containing compound (C) was not used. Table 1 shows the results.

Comparative Example 3 Evaluation was made in the same manner as in Example 5 except that the nitrogen-containing heterocyclic compound (B) was not used. Table 1 shows the results.

Comparative Example 4 Evaluation was made in the same manner as in Example 13 except that the functional group-containing compound (C) was not used. Table 1 shows the results.

[0092]

[Table 1]

Example 14 A polybutylene terephthalate (PBT) having an intrinsic viscosity of 0.85 and sufficiently dried was added to a functional group-containing compound (C).
1.0% of bisphenol A type epoxy resin (Eicoat 828, manufactured by Yuka Shell Epoxy Co., Ltd.)
The mixture was stirred and mixed for 3 minutes in a ribbon blender. Then, as a nitrogen-containing heterocyclic compound (B), 20% of melamine cyanurate (average particle size: 1 μm) and an antioxidant (tetrakis.
0.5% of methylene-3,5-di-t-butyl-4-hydroxyhydrocinnamate / methane) was added, and the mixture was further stirred and mixed for 3 minutes. This mixture is vented 30 mmφ
The mixture was melt-kneaded at 250 ° C. in an extruder and pelletized. After drying the pellets at 140 ° C. for 4 hours, the cylinder temperature was set to 250 using an injection molding machine (mold clamping pressure: 50 tons).
A test piece was molded at a temperature of 80 ° C. and a mold temperature of 80 ° C.

Using the obtained test pieces, the flame retardancy (LO
I; ASTM D2863), tensile strength (ASTM D
-638) and Izod value (ASTM D-256, with notch). Table 2 shows the results.

Example 15 In Example 14, a mixture of PBT / PET (weight ratio 70/30) was used as the thermoplastic polyester (A), and 10% of melamine cyanurate was used as the nitrogen-containing heterocyclic compound (B). Example 1 except that 0.5% of acid anhydride (pyromellitic anhydride) was used as the functional group-containing compound (C) and 10% of RBXP was used as the phosphorus-based flame retardant (D).
Evaluation was performed in the same manner as in Example 4. Table 2 shows the results.

Comparative Example 5 Evaluation was made in the same manner as in Example 14 except that the nitrogen-containing heterocyclic compound (B) and the functional group-containing compound (C) were not used. Table 2 shows the results.

Comparative Example 6 Evaluation was made in the same manner as in Example 14 except that the functional group-containing compound (C) was not used. Table 2 shows the results.

[0098]

[Table 2]

Example 16 The procedure of Example 1 was repeated, except that the amount of melamine cyanurate was changed to 15% and the amount of bisphenol A type epoxy resin was changed to 1.5%. The breaking strength (ASTM D-149, specimen thickness 2 mm), arc resistance (ASTM D-495), and tracking resistance (IEC-112) were additionally evaluated.
Table 3 shows the results.

Example 17 Evaluation was made in the same manner as in Example 16 except that 10% of RBXP was further added as a phosphorus-based flame retardant (D). Table 3 shows the results.

Comparative Example 7 In Example 16, brominated polystyrene (FERRO Co., Ltd., PYRO-CHEK68P) was used in place of melamine cyanurate and bisphenol A type epoxy resin.
B) 10% and antimony trioxide (Nippon Seimitsu Co., Ltd .;
Evaluation was carried out in the same manner as in Example 16 except that 3% of Patox-H) was used. Table 3 shows the results.

Comparative Example 8 A melamine / phenol resin powder (National Light Melamine, Matsushita Electric Works, Ltd.) was compression-molded at a mold temperature of 160 ° C., a molding pressure of 150 kg / cm ² and a curing time of 80 seconds to produce a test piece. Evaluation was performed in the same manner as in Example 16. Table 3 shows the results.

[0103]

[Table 3]

Production Example 1 Melamine cyanurate (average particle size 1 μm, molecular weight 25
5, nitrogen content 49.4%, decomposition temperature 450 ° C) 300
0 g and Epicoat 828 (bisphenol A type epoxy resin manufactured by Yuka Shell Epoxy Co., Ltd.)
2%, and high-speed stirring and mixing were performed for 5 minutes with a “Supermixer” manufactured by Kawata Corporation, and a nitrogen-containing heterocyclic compound (hereinafter, referred to as “surface-treated”) was surface-treated with a functional group-containing compound (C) as a white powder.
Flame retardant (BC)).

Production Example 2 Melamine cyanurate was added to melamine phosphate (“MPP-A” manufactured by Sanwa Chemical Co., Ltd., average particle size: 2 μm), and 2% of Epicoat 828 was acid anhydride (pyromellitic anhydride). The treatment was carried out in the same manner as in Production Example 1 except that the content was changed to 2% to obtain a white powdery flame retardant (BC).

Production Example 3 Melamine cyanurate was converted to melamine phosphate (“MPP-A” manufactured by Sanwa Chemical Co., Ltd., average particle size: 2 μm), and 2% of Epicoat 828 was changed to 2,2 ′-(1 , 3-phenylene) -bis (2-oxazoline) in the same manner as in Production Example 1 except that the flame retardant was in the form of a white powder (B
C).

Production Example 4 Production Example 1 except that 2% of Epicoat 828 was changed to 5%.
A flame retardant (BC) in the form of a white powder was obtained in the same manner as described above. An equal weight of condensed phosphoric acid ester (compound represented by formula (VI), phosphorus content 9%, acid value 0.1%) was added to the obtained flame retardant (BC).
2, a melting point of 169 ° C., in the form of a white powder), followed by stirring and mixing to obtain a mixed flame retardant comprising a flame retardant (BC) and a phosphorus-based flame retardant (D).

Production Example 5 A white powdery flame retardant (BC) was obtained in the same manner as in Production Example 1, except that 2% of Epicoat 828 was changed to 2% of acid anhydride (pyromellitic anhydride).

Production Example 6 Melamine cyanurate was converted to cyanuric acid (average particle size: 5 μm).
m), a flame retardant (BC) was obtained in the same manner as in Production Example 1 except that the epicoat 828 was changed to 2% of an acid anhydride (pyromellitic anhydride).

Production Example 7 Melamine cyanurate was added to melamine phosphate (same as that used in Production Example 2), and 2% of Epicoat 828 was added to 2%.
A flame retardant (BC) was obtained in the same manner as in Production Example 1, except that 2% of 2 '-(1,3-phenylene) -bis (2-oxazoline) was used.

Production Example 8 Melamine cyanurate was converted to melamine (average particle size: 5 μm)
A white powdery flame retardant (BC) was obtained in the same manner as in Production Example 1 except for changing the composition.

Comparative Production Example 1 Melamine cyanurate not treated with functional group-containing compound (C) was used in place of melamine cyanurate treated with functional group-containing compound (C), and an equal weight of condensed phosphoric acid Esters (compound of formula (VI), phosphorus content 9%,
(Acid value 0.2, melting point 169 ° C, white powder) was added to obtain a mixed flame retardant comprising melamine cyanurate and a phosphorus-based flame retardant in the same manner as in Production Example 4.

Examples 18 to 20 The flame retardant (BC) obtained in Production Example 1 was added to 10% (Example 18) and 20% of polyethylene terephthalate (PET) having an intrinsic viscosity of 0.65 and sufficiently dried. (Example 19), 30% (Example 20), and glass fiber (ECS-03, manufactured by Nippon Electric Glass Co., Ltd.)
T-195H) 30%, talc 1%, antioxidant (tetrakis methylene-3,5-di-t-butyl-4-hydroxyhydrocinnamate methane) 0.5% with a vented 45 mmφ extruder for 280. The mixture was melted and kneaded at ℃ to form pellets. After the obtained pellets were dried at 140 ° C. for 4 hours, a test piece was prepared at a cylinder temperature of 280 ° C. and a mold temperature of 100 ° C. using an injection molding machine (mold clamping pressure of 50 tons).

Using the obtained test pieces, a flame retardant (UL-
94 standard, 1/16 "thickness), tensile strength (ASTM D)
-638), Izod value (ASTM D-256, with notch), HDT (ASTM D-648, 18.6k)
g / cm ² load), moisture resistance (90 ° C, relative humidity 100%)
For 72 hours after the treatment). Table 4 shows the results.

Example 21 A test piece was prepared and measured in the same manner as in Example 18 except that 20% of the flame retardant (BC) obtained in Production Example 2 was added. Table 4 shows the results.

Example 22 The flame retardant (BC) obtained in Production Example 3 was replaced with a PET copolymer (terephthalic acid and bisphenol A ethylene oxide adduct (molecular weight: 1,000, molar ratio of bisphenol A to ethylene oxide unit: 0.06)) Block copolymer obtained by copolymerizing 10% of a polyester consisting of
A test piece was prepared and measured in the same manner as in Example 18 except that it was added. Table 4 shows the results.

Example 23 A test piece was prepared in the same manner as in Example 18 except that the mixed flame retardant obtained in Production Example 4 was added to a PET copolymer (the same as that used in Example 22) in an amount of 20%. Was prepared and measured. Table 4 shows the results.

Comparative Example 9 A test piece was prepared in the same manner as in Example 18 except that the flame retardant (BC) of Production Example 1 used in Example 18 was not used.
A measurement was made. Table 4 shows the results.

Comparative Example 10 In place of melamine cyanurate treated with functional group-containing compound (C) (Production Example 1), melamine cyanurate not treated with functional group-containing compound (C) was added to PET.
A test piece was prepared and measured in the same manner as in Example 18 except for adding%. Table 4 shows the results.

Comparative Example 11 Comparative Production Example 1 was replaced with the mixed flame retardant obtained in Production Example 4.
A test piece was prepared and measured in the same manner as in Example 23, except that the same amount (20%) of the mixed flame retardant obtained above was used. Table 4 shows the results.

[0121]

[Table 4]

Example 24 To the sufficiently dried polybutylene terephthalate (PBT) having an intrinsic viscosity of 0.85, the flame retardant (BC) obtained in Production Example 4 (but no condensed phosphate ester was added) %, An antioxidant (tetrakis / methylene-3,
0.5% of 5-di-t-butyl-4-hydroxyhydrocinnamate / methane) was melt-kneaded at 250 ° C. with a vented 30 mmφ extruder, and pelletized. After drying the pellets at 140 ° C. for 4 hours, test pieces were prepared at 250 ° C. cylinder temperature and 80 ° C. mold temperature using an injection molding machine (mold clamping pressure of 50 tons), and the flame retardancy (LOI; ASTM) was obtained.
D2863), tensile strength (ASTM D-638), and Izod value (ASTM D-256, with notch). Table 5 shows the results.

Example 25 A test was conducted in the same manner as in Example 24, except that PBT was replaced with a PBT / PET (70/30 by weight) blend and the flame retardant (BC) was replaced with that obtained in Production Example 5. Pieces were made and measured. Table 5 shows the results.

Comparative Example 12 The flame retardant (BC) obtained in Production Example 4 used in Example 24
A test piece was prepared and measured in the same manner as in Example 24 except that was not used. Table 5 shows the results.

Comparative Example 13 Example 24 was repeated except that 20% of melamine cyanurate not treated with the functional group-containing compound was added instead of melamine cyanurate treated with the functional group-containing compound (C).
A test piece was prepared and measured in the same manner as described above. Table 5 shows the results.

[0126]

[Table 5]

[0127]

Industrial Applicability The flame-retardant polyester resin composition according to the present invention has excellent flame retardancy and has good electrical properties, lubricity, plasticity, coloring, surface smoothness, and dyeability. Moldings with excellent mechanical properties, heat resistance, moisture resistance, etc. In addition, it is used for various applications by taking advantage of its excellent characteristics, and is particularly preferably used as a non-halogen flame-retardant polyester resin composition for electronic and electric parts.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-54-112958 (JP, A) JP-A-53-88854 (JP, A) JP-A-50-105744 (JP, A) (58) Field (Int.Cl. ⁷ , DB name) C08L 67/00-67/04

Claims (13)

(57) [Claims] 1. A thermoplastic polyester (A), a heterocyclic compound containing a nitrogen atom (B),
(C) 0.1 to 50% by weight based on the component (B), and (D) 0 to 50% by weight of the (A) component based on the component (A). A flame-retardant polyester resin composition, which contains about 10% by weight. 2. The method according to claim 1, wherein the heterocyclic compound containing a nitrogen atom has the general formula (I): (Wherein R ¹ , R ² , and R ³ are a hydrogen atom, an amino group, an aryl group, or an oxyalkyl group having 1 to 3 carbon atoms, and R ¹ , R ² , and R ³ may be the same or different. The flame-retardant polyester resin composition according to claim 1, which is a compound represented by the following formula: 3. The heterocyclic compound containing a nitrogen atom has a general formula (II): (Wherein R ⁴ , R ⁵ , and R ⁶ are a hydrogen atom, an amino group, an aryl group, or an oxyalkyl group having 1 to 3 carbon atoms, and R ⁴ , R ⁵ , and R ⁶ may be the same or different. The flame-retardant polyester resin composition according to claim 1, which is a compound represented by the following formula: 4. The heterocyclic compound containing a nitrogen atom has a general formula (III): (Wherein R ⁷ , R ⁸ , and R ⁹ represent a hydrogen atom, an amino group, a hydroxyl group, a mercapto group, an alkylamino group having 1 to 10 carbon atoms, an anilino group, a morpholino group, a hydrazino group, a benzylamino group, a pyridylamino group , A pyridylmethylamino group, a thenylamino group or an oxyalkyl group having 1 to 3 carbon atoms, and R ⁷ , R ⁸ and R ⁹ may be the same or different.) Flame retardant polyester resin composition. 5. The flame-retardant polyester resin composition according to claim 1, wherein the nitrogen-containing heterocyclic compound is melamine cyanurate. 6. The functional group in the compound having two or more functional groups is an epoxy group, a carboxylic acid anhydride group, an isocyanate group, an oxazoline group, a carbodiimide group, an aldehyde group, a carboxyl group, an aziridinyl group (ethyleneimino group). The flame-retardant polyester resin composition according to claim 1, which is at least one member selected from the group consisting of a cyanate group and a cyanate group. 7. The flame-retardant polyester resin composition according to claim 1, wherein at least one of the compounds having two or more functional groups is a diepoxy compound. 8. The flame-retardant polyester resin composition according to claim 1, wherein at least 80 mol% or more of the repeating units of the thermoplastic polyester are alkylene terephthalate units. 9. The flame-retardant polyester according to claim 8, wherein the thermoplastic polyester comprises a polyethylene terephthalate copolymer containing 1 to 30% by weight of a unit derived from polyethylene terephthalate and / or a polyoxyalkylene compound. Resin composition. 10. The unit derived from the polyoxyalkylene compound has a general formula (IV): (Wherein, R ¹⁰ is a divalent hydrocarbon group having 2 to 4 carbon atoms, X is a direct bond or an alkylene group having 1 to 3 carbon atoms, -S-,
A divalent linking group of —SO ₂ —, —O— or —CO—, m and n are integers of 5 to 20, and (m + n) R ¹⁰ may be different. The flame-retardant polyester resin composition according to claim 9. 11. The phosphorus-based flame retardant represented by the general formula (V): (Wherein, R ^{11 to} R ²² are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, Y is a direct bond or an alkylene group having 1 to 3 carbon atoms, —S—, —SO ₂ —, -O
-, -CO- or a divalent linking group wherein -N = N-,
2. The flame-retardant polyester resin composition according to claim 1, wherein k is 0 or 1. (A) a thermoplastic polyester, (B)
Melamine cyanurate is used in an amount of 2 to 50 with respect to the component (A).
% By weight, at least one of (C) a diepoxy compound, a carboxylic dianhydride, a diisocyanate compound and a polycarbodiimide compound, in an amount of 0.1 to 50% by weight based on the component (B); )) Is added to the component (A) in an amount of 0 to 50.
A flame-retardant polyester resin composition, which contains about 10% by weight. 13. (A) a thermoplastic polyester, (B)
2 to 50% by weight of the heterocyclic compound containing a nitrogen atom with respect to the component (A), 0.1 to 50% by weight of the compound having two or more functional groups (C) with respect to the component (B), (D)
When producing a flame-retardant polyester resin composition containing a phosphorus-based flame retardant in an amount of 0 to 50% by weight based on the component (A), the components (A) and (C) are mixed after stirring. A method for producing a flame-retardant polyester resin composition, comprising mixing the remaining components.