JPH0848813A - Flame retardant and thermoplastic resin containing the same - Google Patents

Abstract

PURPOSE:To provide a non-halogen flame retardant and a thermoplastic resin composition containing this flame retardant and having a remarkable flame retardancy. CONSTITUTION:A flame retardant composed of (A) a water-insoluble triazine derivative synthesized by conducting reaction and/or condensation between an aldehyde represented by R1CHO or a methylol compound and a reaction product synthesized from cyanuric acid chloride and a diamine and (B) ammonium polyphosphate or polyphosphoric acid amide. The weight ratio of A/B is 0.1 to 10. Provided that R1 is selected from a group of H, CHO, a 1 to 8C alkyl group, a 2 to 6C alkenyl group, a 6 to 12C cycloalkyl group, a 6 to 12C allyl group, a 7 to 16C aralkyl group and a group expressed by a general formula, R2CHO (R2 represents a 2 to 10C alkylene group) A flame-retardant composition is prepared by blending 1 to 50wt.% this flame retardant with a thermoplastic resin.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a flame retardant comprising a water-insoluble triazine derivative obtained by reacting and / or condensing a reaction product of cyanuric chloride and a diamine with an aldehyde and a specific phosphorus compound. And a flame-retardant thermoplastic resin composition obtained by mixing the flame-retardant agent with a thermoplastic resin in a specific amount.

[0002]

2. Description of the Related Art Conventionally, thermoplastic resins have been
Taking advantage of workability, chemical resistance, weather resistance, electrical characteristics, mechanical strength, and other advantages, it can be used in a variety of fields such as construction, upholstery, and automobile parts, including the field of industrial and household electrical products. It is widely used in the field, and the applications in which thermoplastic resins are used are also expanding. With the expansion of such applications, the thermoplastic resin is beginning to be required to have flame retardancy, and the required performance is becoming severer year by year. Particularly recently, a flame-retardant resin composition in which a halogen-containing compound, which is the mainstream of conventional flame-retarding technology, is blended in a thermoplastic resin, or a flame-retardant resin in which a halogen-containing compound and antimony trioxide are blended in a thermoplastic resin It has been considered a problem that the composition generates a halogen-based gas at the time of combustion or molding. Therefore, there is a demand for flame-retardant resin compositions that do not generate these halogen-based gases during combustion or molding.

In order to meet these demands, recently, a method has been proposed in which a specific metal hydrate capable of decomposing and dehydrating by an endothermic reaction at the combustion temperature of the resin to suppress the combustion of the resin is blended as an inorganic flame retardant. Has been done. However, in this method, the effect of imparting flame retardancy of the metal hydrate used is extremely weak, and therefore it is necessary to add a large amount thereof. As a result, the flame-retardant resin composition obtained has a decrease in various properties such as a decrease in moldability and a decrease in mechanical strength of a molded product obtained from the composition. For this reason, recently, a method has been proposed in which a specific triazine derivative and a specific phosphorus compound are combined and blended with a thermoplastic resin to make them flame-retardant (for example, JP-A-3-149262 and JP-A-3-149262). No. 215564). Further, a method of flame-retarding a thermoplastic resin using a flame retardant in which a compound obtained by condensing a specific triazine derivative with an aldehyde such as formalin is combined with a specific phosphorus compound has also been proposed (for example, European Patent 0542370
No. 0542376).

However, a flame-retardant thermoplastic resin prepared by blending the flame-retardant agent described in the above-mentioned known literature with a thermoplastic resin is
Due to the poor flame retardancy of the triazine derivative, UL-
Although V-0 can be achieved at a wall thickness of 3 mm of 94 V standard (underwriters laboratories), it is V-0 at a wall thickness of 1.6 mm, which is more highly flame retardant.
Has a problem that it is difficult to achieve.

[0005]

DISCLOSURE OF THE INVENTION The present inventors have earnestly studied to obtain a non-halogen flame retardant capable of achieving a high degree of flame retardancy when blended with a thermoplastic resin. As a result, when a flame retardant obtained by combining a triazine derivative formed by reacting and / or condensing a reaction product of cyanuric chloride and a diamine with an aldehyde and a specific phosphorus compound is blended with a thermoplastic resin, it is excellent. It was found that the material exhibits flame retardancy, and the present invention was completed based on this finding. As is apparent from the above description, the object of the present invention is a non-halogen flame retardant capable of achieving a high degree of flame retardancy when blended with a thermoplastic resin, that is, a reaction product of cyanuric chloride and diamine (hereinafter referred to as CC formation). Flame retardant obtained by combining a triazine derivative obtained by reacting and / or condensing a compound) with an aldehyde with a specific phosphorus compound, and a flame retardant thermoplastic resin composition obtained by blending the flame retardant with a thermoplastic resin. It is to provide things.

[0006]

The present invention has the following configurations (1) to (5). (1) Obtained by reacting and / or condensing a reaction product of (A) cyanuric chloride and a diamine with _one or more aldehydes represented by the general formula R ₁ -CHO or a methylol compound. It is composed of a water-insoluble triazine derivative and (B) ammonium polyphosphate or polyphosphoric acid amide, and has an A / B weight ratio of 0.1 to 0.1.
Flame retardant which is 10. (However, R ₁ is H, —CHO, a substituted or unsubstituted C _{1 to} C ₈ alkyl group, a substituted or unsubstituted C _{2 to} C ₆ alkenyl group, a substituted or unsubstituted C _{6 to} C ₁₂ Cycloalkyl group, substituted or unsubstituted C _{6 to} C ₁₂ allyl group, substituted or unsubstituted C _{7 to} C
₁₆ aralkyl groups and groups represented by the general formula —R ₂ —CHO (wherein R ₂ represents a substituted or unsubstituted C _{2 to} C ₁₀ alkylene group). (2) The triazine derivative as a diamine has the following (1)
The flame retardant according to claim 1, which is a triazine derivative obtained by using one or more diamines selected from the group consisting of (3) to (3). (1) General formula HNR ₃ (CH ₂ ) _n R ₄ NH (where n is 2
Is an integer of 6 to 6, and R ₃ and R ₄ are hydrogen, a methyl group, an ethyl group, an n-propyl group or an isopropyl group), (2) piperazine or a diamine containing a piperazine ring, (3) (1) and / Or a mixture of (2). (3) A triazine derivative as a methylol compound is obtained by methylating one or more compounds selected from the group consisting of melamine, guanamine, urea, thiourea, ethylene urea and ethylene thiourea. The flame retardant according to claim 1, which is a triazine derivative obtained by using the methylol compound. (4) A flame-retardant thermoplastic resin composition comprising the thermoplastic resin and the flame-retardant agent according to the above-mentioned item 1 in an amount of 1 to 50% by weight based on the composition. (5) The flame-retardant thermoplastic resin composition according to the above item 4, wherein the thermoplastic resin is an olefin resin or an olefin elastomer.

The reaction product of cyanuric acid chloride, which is a raw material of the triazine derivative used in the present invention, and a diamine (hereinafter referred to as CC product) is a method described in JP-A-6-25467, that is, 0 ° C. Cyanuric chloride and diamine at a temperature of 160 ° C., water, acetone, tetrahydrofuran, acetonitrile, 1,4-dioxane, dichloromethane, chloroform, carbon tetrachloride, benzene, toluene, xylene, chlorobenzene,
NaOH, KOH, Na in a solvent such as dichlorobenzene, trichlorobenzene or dimethylsulfoxide
An inorganic alkali such as ₂ CO ₃ or a tertiary amine such as pyridine or triethylamine, or one or more kinds of diamine as a raw material itself or a mixture thereof is used as a dehydrochlorinating agent to prepare the CC product and the diamine. It can be obtained by reacting in a molar ratio of 2: 1 to 1: 3.

Then, using the obtained CC product as a starting material, the active hydrogen residue in the CC product and the general formula R ₁ -C
Aldehyde represented by HO (provided that R ₁ is H, —CH
O, a substituted or unsubstituted C _{1 to} C ₈ alkyl group, a substituted or unsubstituted C _{2 to} C ₆ alkenyl group, a substituted or unsubstituted C _{6 to} C ₁₂ cycloalkyl group, a substituted or unsubstituted C ₆ -C ₁₂ aryl groups, aralkyl groups and the general formula -R ₂ -CHO of C ₇ -C ₁₆ substituted or unsubstituted
(Wherein R ₂ represents a substituted or unsubstituted C _{2 to} C ₁₀ alkylene group) or a methylol compound such as melamine, guanamine, urea, thiourea, ethylene urea or ethylene thiourea as well as/
Alternatively, a water-insoluble triazine derivative can be obtained by condensation. The reaction in the present invention means CC
The active hydrogen residue remaining in the product reacts with the CHO group of the aldehyde to form an OH group, and the condensation means dehydration condensation of the OH group.

The reaction and / or condensation method for obtaining the triazine derivative used in the present invention is carried out by a wet method carried out in water, alcohol or a mixed solvent thereof, a dry method without using a solvent, or a method of diluting with a small amount of solvent and adding. Any of the above semi-dry methods may be used, and any of the methods can obtain a remarkable water-insolubilized triazine derivative. In the wet method, the CC product is dispersed in water, alcohol or a mixed solvent thereof, and the aldehyde or methylol compound is used as it is or diluted with a solvent, and 10 parts by weight of the aldehyde is added to 100 parts by weight of the reaction product.
Add 0.001 parts by weight or more in terms of 0%. At this time, a catalyst may be used depending on the aldehyde used. Examples of usable catalysts are NaOH, KOH, Na ₂ CO ₃ ,
Inorganic alkaline catalysts such as K ₂ CO ₃ , acid catalysts such as HCl, H ₂ SO ₄ or metal salt catalysts such as nitrates, nitrites, sulfamate salts or commercially available methylation catalysts (Catanit A, trade name) , Manufactured by Nitto Kagaku) can also be used. In addition, the reaction of the highly reactive aldehyde proceeds even without using a catalyst. Then, the whole slurry is stirred with or without heating, filtered, and heated in an oven at 100 ° C. or higher (preferably 120 to 180 ° C.) or a heating furnace to complete condensation and dry the product. .

The amount of aldehyde used is the above-mentioned CC product 10
It may be 0.001 parts by weight or more with respect to 0 parts by weight, but depending on the type of diamine used in the process of synthesizing the CC product, the synthesis method, and the synthesis conditions, the active hydrogen residue present in the CC product may vary. There is a possibility that the amount of the group is different and the aldehydes may be excessive, but there is no problem because the unreacted aldehydes are removed by separation by filtration, decomposition by heating, evaporation, sublimation or the like. However, when it is 0.001 part by weight or less, the reaction with active hydrogen residues is poor, and a triazine derivative having remarkable water insolubility cannot be obtained.

In the dry process and the semi-dry process, the CC product and the aldehyde or methylol compound and, in some cases, the raw material such as a catalyst are placed in a stirrable apparatus such as a mixer or a kneader. And stirring with or without heating. After stirring for a certain period of time, it is taken out of the apparatus and heated in the same manner as in the wet method to complete condensation and dry.

Aldehydes that can be used include, for example, formaldehyde, paraformaldehyde, glyoxal, acetaldehyde, pyruvic aldehyde, propionaldehyde, glyceraldehyde, n-butyraldehyde, isobutyraldehyde, n-valeric aldehyde, iso-valeric aldehyde, 2-methylbutyraldehyde, trimethylacetaldehyde, 3,3-dimethylbutyraldehyde, 2-ethylbutyraldehyde, 2-
Methylvaleric acid aldehyde, 2,3-dimethylvaleric acid aldehyde, heptaldehyde, octylaldehyde, acrolein, crotonaldehyde, cyclopropane carboxaldehyde, 2-furaldehyde, 3-furaldehyde, 2-ethylacrolein, trans-2- Methyl-
Butenal, 3-methyl-2-butenal, glutaric dialdehyde, 2,2-dimethylhydroxypropionaldehyde, 2,4-hexadienal, 2-ethyl-trans-2-butenal, trans-2-hexenal,
2-methyl-2-pentenal, 3-ethoxymethacrolein, benzaldehyde, 3-hydroxybenzaldehyde, 4-hydroxybenzaldehyde, 2,3-
Dihydroxybenzaldehyde, 2,4-dihydroxybenzaldehyde, 2,5-dihydroxybenzaldehyde, 3,4-dihydroxybenzaldehyde, 2,
3,4-trihydroxybenzaldehyde, 2,4,6
-Trihydroxybenzaldehyde, 3,4,5-trihydroxybenzaldehyde, 1,2,3,6-tetrahydroxybenzaldehyde, trans, trans-2,4-
Heptadienal, 2,2-dimethyl-4-pentanal, trans-2-heptanal, isophthalaldehyde, phthalic dicarboxaldehyde, terephthaldicarboxaldehyde, 2-carboxybenzaldehyde, 4-carboxybenzaldehyde, 5-formylsalicylaldehyde, Piperonal, phenylacetaldehyde, o-tolualdehyde, m-tolualdehyde, p-
Tolualdehyde, o-anisaldehyde, m-anisaldehyde, p-anisaldehyde, 4-hydroxy-3-methylbenzaldehyde, trans-2-octenal, 2-
Ethylhexanal, phenylpropargyl aldehyde,
Cinnamic aldehyde, 4-acetoxybenzaldehyde,
2,4-dimethylbenzaldehyde, 2,5-dimethylbenzaldehyde, 4-ethylbenzaldehyde, 2,
6-dimethyl-4-hydroxybenzaldehyde, 3,
5-dimethyl-4-hydroxybenzaldehyde, 3-
Methyl-p-anisaldehyde, 2,3-dimethoxybenzaldehyde, 2,4-dimethoxybenzaldehyde,
2,5-dimethoxybenzaldehyde, 2,6-dimethoxybenzaldehyde, 3,4-dimethoxybenzaldehyde, 3,5-dimethoxybenzaldehyde, 3-ethoxy-4-hydroxybenzaldehyde, 3,4-dimethoxy-5-hydroxybenzaldehyde or 4
-Hydroxy-3,5-dimethoxy-benzaldehyde and the like can be mentioned, with preference given to formaldehyde, paraformaldehyde or glyoxal.

The methylol compounds which can be used include dimethylolmelamine, trimethylolmelamine,
Tetramethylol melamine, pentamethylol melamine, hexamethylol melamine, methylol melamine low condensate, dimethylol benzoguanamine, trimethylol-
Lubenzoguanamine, tetramethylol benzoguanamine, dimethylolacetoguanamine, trimethylolacetoguanamine, tetramethylolacetoguanamine,
Dimethyl-acryloguanamine, trimethylol-acrylo-guanamine, tetramethyl-acrylo-guanamine, dimethylol-urea, trimethylol-urea, tetramethylol-urea, dimethylol-thiourea, trimethylol-thiourea, tetramethylol-thiourea, dimethylo- Ethylene oxide, trimethylol ethylene urea, tetramethyl ethylene urea, dimethyl ethylene thiourea,
Examples include trimethylol ethylene thiourea and tetramethyl ethylene thiourea.

The ammonium polyphosphate used in the present invention is an ammonium polyphosphate represented by the general formula (NH ₄ ) _{n + 2} P _n O _{3n + 1} (where n is an integer of 2 or more). It is preferred that the molecular weight of ammonium is large enough to significantly reduce its water solubility. Having the above formula, n
Is a sufficiently high number, metaphosphate (NH ₄ P
The compound corresponds to the formula of O ₃ ) _n . As such ammonium polyphosphate, for example, Exolit (Exoli
t) -422 (trade name, manufactured by Hoechst), Exolit-700 (trade name, manufactured by Hoechst),
Examples include Phos-chek P / 40 (trade name, manufactured by Monsanto Co., Ltd.), Sumisafe-P (trade name, manufactured by Sumitomo Chemical Co., Ltd.), and others. JP-A-4-300204 Japanese Patent Laid-Open No. 6-2471
The II type ammonium polyphosphate fine particles described in JP-A-7 can also be used. The type II ammonium polyphosphate fine particles can be obtained, for example, by the following method. That is,
Powdery diammonium phosphate and phosphorus pentoxide were mixed in an equimolar amount, heated and stirred at a temperature of 290 ° C. to 300 ° C., and then a solution containing 0.5 mol of urea with respect to the diammonium phosphate (concentration: 77). % By weight) and then heated under an atmosphere of ammonia at a temperature of 250 ° C. to 270 ° C. for several hours.

Further, in order to improve the water solubility of the ammonium polyphosphate, ammonium polyphosphate whose surface is coated with a thermosetting resin and ammonium polyphosphate to which melamine is added and / or attached are also used. You can As an example of ammonium polyphosphate whose particle surface is coated with a thermosetting resin, Exolit-462 (trade name, manufactured by Hoechst)
Is mentioned.

Further, ammonium polyphosphate having melamine added and / or attached can be obtained, for example, by the following method. That is, first, as a first step, the powdery ammonium polyphosphate particles are put into a heating and kneading device such as a preheated kneader, and the powdery ammonium polyphosphate particles are not melted, and Is heated at a temperature at which ammonia easily desorbs, that is, 300 ° C. or less, preferably 200 ° C. to 300 ° C., for 0.5 to 5 hours, and a part of ammonia which is originally present in a stoichiometric amount in ammonium polyphosphate. (5 to 10% by weight with respect to stoichiometric amount of ammonia) was desorbed, and a part of the ammonia was desorbed to form a 1% by weight suspension of ammonium polyphosphate having a pH of 4.0 to 6.0. In the known production process of ammonium polyphosphate or ammonium polyphosphate in a state of lacking ammonia, the binding amount of ammonia is less than the stoichiometric amount Form ammonium polyphosphate (hereinafter, these are referred to as ammonia-deficient ammonium polyphosphate), and then in the same apparatus as the second step at a temperature at which the ammonia-deficient ammonium polyphosphate particles do not melt and at a temperature at which melamine can sublime. Melamine is added by heating to a certain temperature of 250 ° C. to 300 ° C., and the melamine is added and / or attached to the proton of the oxygen-proton bond generated by the elimination of ammonia on the surface of the ammonium-deficient ammonium polyphosphate particles.

Here, the addition means a state in which melamine is ionically bound to a proton of an oxygen-proton bond generated by desorption of ammonia from ammonium polyphosphate, and the added melamine is stable even when heated. It will not be detached again. Adhesion means a state in which melamine is physically or chemically adsorbed on the surface of ammonium polyphosphate particles, and sublimation and adsorption are reversibly repeated depending on the temperature.

In the flame retardant of the present invention, the weight ratio (A / B weight ratio) of the water-insoluble triazine derivative as the component (A) and the ammonium polyphosphate as the component (B) is in the range of 0.1 to 10, Preferably 0.15 to 1, more preferably 0.2
Is in the range of to 0.6. If the weight ratio is less than 0.1 or more than 10, the composition obtained by blending the flame retardant with a thermoplastic resin cannot achieve sufficient flame retardancy.

The following are preferred examples of the thermoplastic resin used in the present invention. That is, a polyolefin resin, for example, a crystalline ethylene homopolymer, ethylene as a main component, the ethylene and propylene, butene-
1, a crystalline copolymer with an α-olefin having 3 or more carbon atoms such as hexene-1, octene-1, a crystalline propylene homopolymer, propylene as a main component, and the propylene and ethylene or a carbon number of 4 or more Crystalline copolymer with α-olefin, butene-1 homopolymer, butene-1 as main component, copolymer of butene-1 with ethylene, propylene or α-olefin having 5 or more carbon atoms, 4 -Methyl-1-pentene homopolymer, 4-methyl-1-pentene as a main component, and a copolymer of 4-methyl-1-pentene with ethylene, propylene, butene-1 or an α-olefin having 6 or more carbon atoms. It is a polymer or a mixture of two or more thereof, a blend of these with a polymer or a copolymer other than these, a modified product thereof, or a thermoplastic elastomer.

As a method for producing the flame-retardant thermoplastic resin composition of the present invention, the above-mentioned thermoplastic resin is used as a base resin, and a predetermined amount of the flame-retardant agent of the present invention and, if necessary, various types are used. Synthetic rubber, silane-based, titanium-based, aluminum-based coupling agents, inorganic fillers, antioxidants, antistatic agents, anti-UV agents, copper anti-aging agents, antioxidants, lubricants, pigments and other additives A predetermined amount of a mixing device such as a Henschel mixer
(Trade name), super mixer, tumbler mixer,
After putting in a cooking mixer or the like and mixing for 1 to 10 minutes, the obtained mixture is melt-kneaded at a melt-kneading temperature of 170 ° C. to 300 ° C. by a roll, an extruder or the like, and pelletized. it can.

The amount of the flame retardant used in the present invention is 1 to 50% by weight, preferably 15 to 50% by weight, based on the composition.
35% by weight. If the blending amount is less than 1% by weight, a composition having excellent flame retardancy cannot be obtained, and if the blending amount exceeds 50% by weight, it is difficult to obtain a further effect of improving flame retardancy.

[0022]

EXAMPLES In order to specifically explain the present invention, the following examples are shown, but the present invention is not limited thereto. Unless otherwise specified, the parts shown in the examples are parts by weight. The flame retardance was evaluated by the following method. 1) UL-94V test: Based on the vertical combustion test method specified in "Combustion test of plastic material for parts of equipment" of UL Subject 94 (Underwriter-Laboratories Co-porated). 2) Oxygen index (O.I.): Japanese Industrial Standard JIS K7
201 (combustion test method for polymer materials by oxygen index method)
Complies with.

Example 1 (Synthesis of water-insoluble triazine derivative (A1 component)) 100 parts of CC product produced by the following production method and 5% by weight in a reaction vessel having an internal volume of 1 liter equipped with a stirrer and a thermometer.
600 parts of formalin aqueous solution are mixed and stirred at room temperature for 2 hours. Then, the solution is filtered, and the filtration residue is placed in an oven for 6 minutes.
The mixture is reacted at 0 ° C. for 1 hour, dried and then heated and condensed at 150 ° C. for 5 hours. PH 1.2 of the obtained reaction product (A1 component),
The water solubility at pH 9.0 was 0% by weight and 0.9% by weight, respectively. (Production of flame-retardant thermoplastic resin composition) As a thermoplastic resin, ethylene content of 8.5% by weight, melt flow rate (temperature of 230 ° C., load of 2.16 kg, 10)
Discharge amount of molten resin per minute) 20 g / 10 minutes of crystalline ethylene-propylene block copolymer (C1 component) 70.
7% by weight, 8% by weight of the above-mentioned A1 component as a triazine derivative pulverized by a commonly known pulverizer, Exolit-4 as ammonium polyphosphate
22 (trade name, manufactured by Hoechst) (B1 component) 21% by weight, and 2,6-di-t-butyl-p- as other additives
Cresol 0.1% by weight, di-myristyl-β, β'-
Henschel mixer (trade name) containing 0.1% by weight of thiodipropionate and 0.1% by weight of calcium stearate.
And mixed for 3 minutes with stirring. The mixture obtained is calibrated to 3
The mixture was melt-kneaded at a melt-kneading temperature of 200 ° C. and extruded into pellets with a 0 mm extruder. After drying the obtained pellets at a temperature of 100 ° C. for 3 hours, the pellets were used to make an UL having a thickness of 1.6 mm with an injection molding machine in which the temperature was set to 200 ° C.
A −94 V test piece and an oxygen index test piece were prepared. Flame retardancy was measured using the test piece. As a result, the oxygen index was 38.3, and it was V-0 in the UL-94V test.

The CC product used here was prepared by the following method. That is, 752.2 parts of cyanuric acid chloride, 2000 parts of water and 300 parts of ice are placed in a 4-neck reaction container having an internal volume of 10 liters equipped with a stirrer, a thermometer, and a dropping funnel.
The department was set up. A solution prepared by dissolving 490.5 parts of ethylenediamine in 1600 parts of water was added dropwise while stirring at a temperature of 0 to 5 ° C. After the completion of dropping, the mixture was stirred at the same temperature for 3 hours, and then the reaction vessel was heated from the outside to make the reaction slurry 75
The temperature is raised to 48 ° C., and 489.5 parts of sodium hydroxide is added to water 1
After adding 000 parts of the solution dropwise, the reaction solution was kept under reflux for 5 hours. After cooling the obtained reaction slurry, the reaction product was filtered, the filtration residue was washed with boiling water several times, and then dried at 100 ° C. to obtain a CC product.

Example 2 (Synthesis of water-insoluble triazine derivative (component A2)) 100 parts of CC product produced according to Example 1 and 300 parts of water
Parts, 52 parts of 35% by weight aqueous formalin solution, and 2.42 parts of Cattanit A (trade name, manufactured by Nitto Kagaku Co., Ltd.) as a catalyst are charged in the same reaction vessel as in Example 1 and stirred. The mixture was heated at 80 ° C. for 3 hours and then held at reflux temperature for a further 2 hours. After completion of the reaction, the reaction product was filtered, the filtration residue was washed with water, and condensed in an oven at 160 ° C. for 5 hours. The water solubility of the obtained reaction product (A2 component) at pH 1.2 and pH 9.0 is 0.17% by weight and 0.73% by weight, respectively.
Met. (Production of flame-retardant thermoplastic resin composition) A obtained above
A flame-retardant thermoplastic resin composition is produced according to the method for producing a flame-retardant thermoplastic resin composition of Example 1 except that two components are used, and a predetermined test piece is prepared from the obtained composition. Then
Flame retardance was measured. The result is an oxygen index of 38.0, UL
It was V-0 in the -94V test.

Example 3 (Synthesis of water-insoluble triazine derivative (A3 component)) 100 parts of CC product was put into a tabletop universal mixer, 20 parts of 35% by weight formalin aqueous solution was sprayed with vigorous stirring, and the mixture was kept for 3 hours. Mix with stirring. The mixture was taken out and condensed in an oven at 160 ° C. for 5 hours. The water solubility of the obtained compound (A3 component) at pH 1.2 and pH 9.0 was 0% by weight and 0.95% by weight, respectively. (Production of flame-retardant thermoplastic resin composition) A obtained above
A flame-retardant thermoplastic resin composition is produced according to the method for producing a flame-retardant thermoplastic resin composition of Example 1 except that three components are used, and a predetermined test piece is prepared from the obtained composition. Then
Flame retardance was measured. The result is an oxygen index of 36.3, UL
It was V-0 in the -94V test.

Example 4 (Production of Flame Retardant Thermoplastic Resin Composition) As the thermoplastic resin which is the C component, melt flow rate (temperature 230 ° C.,
Discharge amount of molten resin for 10 minutes when a load of 2.16 kg is applied) 10 g / 10 minutes of crystalline propylene homopolymer (C2 component) 75.7% by weight, as a triazine derivative, A1 component 6% by weight, poly Exolit-462, which is ammonium polyphosphate coated with melamine resin as ammonium phosphate (trade name,
A flame-retardant thermoplastic resin composition was produced in accordance with Example 1 except that 18% by weight of Hoechst (component B2) was used, and a predetermined test piece was prepared from the obtained composition, The flame retardancy was measured. The result is an oxygen index of 35.4, UL
It was V-0 in the -94V test.

Example 5 (Synthesis of water-insoluble triazine derivative (A4 component)) A water-insoluble triazine derivative was synthesized according to the method for synthesizing A1 component of Example 1 except that 600 parts of a 5 wt% glyoxal aqueous solution was used. did. The water solubility of the obtained compound (A4 component) at pH 1.2 and pH 9.0 was 0.0, respectively.
It was 1% by weight and 0.35% by weight. (Production of flame-retardant thermoplastic resin composition) As a thermoplastic resin, ethylene content of 8.5% by weight, melt flow rate (temperature of 230 ° C., load of 2.16 kg, 10)
Discharge amount of molten resin per minute) 20 g / 10 min of crystalline ethylene-propylene block copolymer (C1 component) 54.
2% by weight and melt index (amount of molten resin discharged at a temperature of 190 ° C. and a load of 2.16 kg for 10 minutes) 6.5 g / 10 min ethylene homopolymer 10% by weight, ethylene-based synthetic rubber or elastomer Ethylene-Propylene Rubber (JSR EP (trademark))
02P, made by Japan Synthetic Rubber Co., Ltd.) 10% by weight, 6% by weight of A4 component pulverized by a commonly known pulverizer, 18% by weight of II type ammonium polyphosphate fine particles (B3 component) as ammonium polyphosphate, silane Vinyltrimethoxysilane 0.8% by weight as a coupling agent, hydrotalcite 0.7% by weight as other additives, 2,6-di-t-butyl-p-cresol 0.1% by weight, di- 0.1% by weight of myristyl-β, β'-thiodipropionate
And 0.1% by weight of calcium stearate were put in a Henschel mixer (trade name) and mixed by stirring for 5 minutes. The obtained mixture is melted and kneaded at a temperature of 20 with an extruder having a diameter of 30 mm.
The mixture was melt-kneaded at 0 ° C. and extruded into pellets. After drying the obtained pellets at a temperature of 100 ° C. for 3 hours, a 1.6 mm-thick test piece for UL-94V and a test piece for oxygen index were prepared by using the pellets and an injection molding machine at a temperature of 200 ° C. Were produced respectively. Flame retardancy was measured using the test piece. As a result, the oxygen index was 37.6, and it was V-0 in the UL-94V test.

Example 6 (Synthesis of water-insoluble triazine derivative (A5 component)) 100 parts of CC product produced according to Example 1 and 300 parts of water
Parts, 40 parts by weight of a 40% by weight aqueous glyoxal solution and 2 parts of concentrated hydrochloric acid as a catalyst are charged in a reaction vessel similar to that in Example 1 and stirred. After reacting the mixture at 60 ° C. for 1 hour,
Neutralize the reaction solution with a 5% by weight aqueous sodium hydroxide solution,
The reaction product was filtered, washed with water, and heated in an oven at 160 ° C for 5
Allowed to condense for time. PH of the obtained compound (A5 component)
Water solubility at 1.2 and pH 9.0 is 0% by weight, respectively.
It was 0.02% by weight. (Production of flame-retardant thermoplastic resin composition) A flame-retardant thermoplastic resin composition was produced according to the production of the flame-retardant thermoplastic resin composition of Example 5 except that the above A5 component was used. .
A predetermined test piece was prepared from the obtained composition, and flame retardancy was measured. As a result, the oxygen index was 36.3, and it was V-0 in the UL-94V test.

Example 7 (Synthesis of water-insoluble triazine derivative (A6 component)) A water-insoluble triazine derivative was produced according to the method for synthesizing A3 component of Example 3 except that 10 parts of a 40 wt% glyoxal aqueous solution was used. did. PH of the obtained compound (A6 component)
The water solubility at 1.2 and pH 9.0 was 0.5% by weight and 0.98% by weight, respectively. (Production of flame-retardant thermoplastic resin composition) As a thermoplastic resin, ethylene content of 8.5% by weight, melt flow rate (temperature of 230 ° C., load of 2.16 kg, 10)
Amount of molten resin discharged per minute) 20 g / 10 min of crystalline ethylene-propylene block copolymer (C1 component)] 55
% By weight, melt index (temperature 190 ° C., load 2.
(Discharge amount of molten resin for 10 minutes when 16 kg is added)
10% by weight of ethylene homopolymer at 6.5 g / 10 min, ethylene-propylene rubber as an ethylene-based synthetic rubber or elastomeric rubber (JSR EP (trademark) 02
P, manufactured by Japan Synthetic Rubber Co., Ltd.) 10% by weight, 6% by weight of A6 component crushed by a commonly known crusher, ammonium polyphosphate (B4 component) added and / or attached with melamine as ammonium polyphosphate 18% by weight, and 0.7% by weight of hydrotalcite as another additive,
2,6-di-t-butyl-p-cresol 0.1% by weight, di-myristyl-β, β'-thiodipropionate 0.1% by weight and calcium stearate 0.1% by weight.
Was placed in a Henschel mixer (trade name) and mixed with stirring for 5 minutes. The obtained mixture was melt-kneaded and extruded at a melt-kneading temperature of 200 ° C. with an extruder having a diameter of 30 mm to form pellets. After drying the obtained pellets at a temperature of 100 ° C. for 3 hours, a 1.6 mm-thick test piece for UL-94V and a test piece for oxygen index were prepared by using the pellets and an injection molding machine at a temperature of 200 ° C. Were produced respectively. Flame retardancy was measured using the test piece. The result is an oxygen index of 36.5,
It was V-0 in the UL-94V test.

Example 8 (Synthesis of water-insoluble triazine derivative (A7 component)) 100 parts of CC product produced according to Example 1 and 300 parts of water
Parts were placed in a reaction vessel similar to that of Example 1, and then a solution prepared by diluting 10 parts by weight of hexamethylolmelamine with 150 parts of water was added. The entire reaction solution is heated to 80 ° C. for 2
Held for hours. After 2 hours, 2N hydrochloric acid was added as a catalyst so that the pH of the solution became 3 to 4. After adding hydrochloric acid,
After reacting for 2 hours at the reflux temperature, the reaction solution was filtered, the filtration residue was washed several times with water, and condensed in an oven at 160 ° C. for 5 hours. The obtained compound (A7 component) had a pH of 1.
2, and the water solubility at pH 9.0 was 0.33% by weight and 0.8% by weight, respectively. (Production of flame-retardant thermoplastic resin composition) A obtained above
A flame-retardant thermoplastic resin composition was produced according to the production of the flame-retardant thermoplastic resin composition of Example 5 except that 7 components were used, and a predetermined test piece was prepared from the obtained composition. , Flame retardancy was measured. The result is an oxygen index of 34.8, UL-9.
It was V-0 in the 4V test.

Comparative Example 1 According to the method for producing a flame-retardant thermoplastic resin composition of Example 1, except that the reaction product A8 component produced by the following production method was used as the triazine derivative as the component A, A test piece of a flame-retardant thermoplastic resin composition was prepared and the flame retardancy was measured. The result was an oxygen index of 33.0 and a failure in the UL-94V test (no applicable rank).

The reaction product A8 component used here is the method disclosed in EP 0542370, namely a stirrer,
In a reaction vessel having an internal volume of 3 liter equipped with a thermometer, a dropping funnel, a condenser and a cooling bath, 0.6 liter of xylene, 2-chloro-4-morpholino-6-amino-1,
After charging 107.8 g of 3,5-triazine and stirring, the temperature of the mixture was raised to 100 ° C. and kept at the same temperature for 2 hours, and then 10 g of sodium hydroxide was added to 160 ° C.
The temperature is raised to ℃ to react. Then the reaction product is heated to 140 ° C.
After being kept at room temperature for 16 hours, it was cooled to room temperature, filtered, and the filtration residue was washed with pure water to obtain 106.1 g of an intermediate. Then, in a reaction vessel having an internal volume of 1 liter, methanol 150c
c, 100 cc of water, 37% by weight aqueous formaldehyde solution, 66.6 g of the intermediate obtained above and melamine 3
1.5 g was charged, the temperature was raised to 60 ° C., and the same temperature was maintained for 4 hours with stirring. Then 2.9% of 85% by weight phosphoric acid solution
An aqueous solution prepared by diluting g with 10 cc of water is added, and the mixture is maintained at the boiling temperature for about 10 hours. Thereafter, 300 cc of water is added and the temperature is lowered to 50 ° C. to neutralize by adding 4.3 g of potassium hydroxide. After holding at 50 ° C. for 1 hour, the mixture was filtered, and the filtration residue was washed with hot water to obtain A8 component.

Comparative Example 2 In the method for producing a flame-retardant thermoplastic resin composition of Example 5, except that the reaction product (A8 component) produced according to Comparative Example 1 was used as the triazine derivative which is Component A. A flame-retardant thermoplastic composition was produced in conformity with the flame-retardant property. As a result, the oxygen index was 32.4, and it was V-2 in the UL-94V test.

[0035]

EFFECTS OF THE INVENTION The flame retardant of the present invention exhibits superior flame retardancy to conventionally known flame retardants by only adding a small amount to a thermoplastic resin.

Claims (5)

[Claims] 1. A reaction product of (A) cyanuric chloride and a diamine is reacted and / or condensed with one or more aldehydes represented by the general formula R ₁ -CHO or a methylol compound. The resulting water-insoluble triazine derivative is composed of (B) ammonium polyphosphate or polyphosphoric acid amide, and the weight ratio of A / B is 0.
Flame retardant which is 1-10. (However, R ₁ is H, —CHO,
A substituted or unsubstituted alkyl group of C ₁ -C _8, a substituted or unsubstituted alkenyl group having C ₂ -C _6, substituted or unsubstituted C ₆ -C ₁₂ cycloalkyl groups, substituted or unsubstituted C ₆ To C ₁₂ allyl groups, substituted or unsubstituted C ₇
To C ₁₆ aralkyl group and a group represented by the general formula —R ₂ —CHO (provided that R ₂ represents a substituted or unsubstituted C _{2 to} C ₁₀ alkylene group). 2. The flame retardant according to claim 1, wherein the triazine derivative is a triazine derivative obtained by using, as the diamine, one or more diamines selected from the group consisting of the following (1) to (3). (1) General formula HNR ₃ (CH ₂ ) _n R ₄ NH (where n is 2
Is an integer of 6 to 6, and R ₃ and R ₄ are hydrogen, a methyl group, an ethyl group, an n-propyl group or an isopropyl group), (2) piperazine or a diamine containing a piperazine ring, (3) (1) and / Or a mixture of (2). 3. A triazine derivative as a methylol compound selected from the group consisting of melamine, guanamine, urea, thiourea, ethylene urea and ethylene thiourea.
The flame retardant according to claim 1, which is a triazine derivative obtained by using a methylol compound obtained by methylating one kind or two or more kinds of compounds. 4. A flame-retardant thermoplastic resin composition comprising a thermoplastic resin and the flame-retardant agent according to claim 1 in an amount of 1 to 50% by weight based on the composition. 5. The flame-retardant thermoplastic resin composition according to claim 4, wherein the thermoplastic resin is an olefin resin or an olefin elastomer.