JP3128966B2 - Flame retardant thermoplastic resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a flame-retardant composition based on a thermoplastic polymer or an elastomer thereof.

[0002]

2. Description of the Related Art Several techniques for reducing the flammability of a polymer are already known. For example,
There are examples using hydrated alumina, magnesium hydroxide, or the like, which is a metal hydroxide compound, and as another example, a combination of a halogen-based organic flame retardant and antimony oxide is widely known. However, in the former case, it is necessary to add a large amount to the polymer, and in the latter case, there is a drawback that halogen compound gas and dust harmful to the human body are generated during combustion. In order to solve the above-mentioned problems, recent studies have revealed a method of making a polymer flame-retardant with a relatively low addition amount by a combination of an inorganic or organic phosphorus compound and a nitrogen-containing compound. For example, JP-A-59-14
Examples of combinations of a phosphorus compound with a substance obtained by providing an alkylamine to the triazine skeleton shown in No. 7050 and oligomerizing or polymerizing with a diamine,
56, JP-A-61-261334, JP-A-63-610
Examples of combinations of tris- (2-hydroxyethyl) -isocyanurate and phosphorus compounds shown in No. 55 are known. However, in the former case, sufficient flame retardancy cannot be obtained with a low addition amount, and in the latter case, since the flame retardant is water-soluble, exudation from the polymer (so-called bleed) occurs due to moisture in the air. Furthermore, Japanese Patent Application Hei 3-3
In a combination of a homopolymer material obtained by adding a hydroxyalkylamine represented by 50959 to a triazine skeleton and oligomerizing or polymerizing with a diamine and a phosphorus compound,
It cannot be said that the performance required for the flame-retardant composition such as the dripping property of the molten resin at the time of ignition of the flame-retardant composition due to the influence of the hydroxyl group is sufficiently satisfied.

[0003] As a result of intensive studies to solve the above-mentioned problems, as a result of combining with a specific phosphorus compound, a low addition amount and a weight ratio of 1/5 to the specific phosphorus compound to be combined cannot be considered conventionally. A nitrogen-containing copolymer substance having excellent flame retardancy without dripping at the time of combustion at a low blending ratio was found. Moreover, it emits less smoke and soot during combustion and has excellent water resistance. The present inventors have found that the above problems can be solved by blending a thermoplastic resin with a mixture of this and ammonium polyphosphate as a flame retardant, and arrived at the present invention. That is,
The combination is (A) a nitrogen-containing copolymer material according to the present invention. (B) Ammonium polyphosphate or polyphosphoramide. It is a combination with As apparent from the above description, an object of the present invention is to provide a novel polymerized nitrogen-containing compound and a flame retardant composition obtained by combining the compound with a phosphoric acid compound.

[0004]

The present invention has the following configurations (1) and (2). (1) For thermoplastic resin: A random copolymer material having a monomer represented by the general formula (I) and the general formula (II) as a basic unit,

Embedded image (wherein X ₁ represents —NH (R ₁ ) or —N
(R ₂₎ alkylamino group represented by group (R ₃₎ or a morpholino group, a piperidino group, R _1,
R ₂ and R _{3 each} have 1 to 6 carbon atoms. X ₂ is —NH
(R ₄₎ or a group of _{-N (R 5) (R 6} ) R 4 is a hydroxyalkyl group having 2 to 6 carbon atoms, R _5, R
₆ is a hydroxyalkyl group having one or both carbon atoms of 2 to 6, which may be the same or different. Further, in the formula (I), Y ₁ and Y ₂ are piperazine divalent groups or groups represented by —N (R ₇ ) (C _n H _2n ) N (R ₈ ) —, and Y ₁ and Y 2 ₂ may be the same group or different groups. R ₇ and R ₈ each represent H and carbon number 1 to
5 is an alkyl group, and n represents an integer of 2 to 6. Furthermore, the composition molar ratio of the general formula (I) and the general formula (II) is 0.3 ≦
(I) / (II) ≦ 3.0); A flame retardant comprising ammonium polyphosphate or polyphosphoramide, wherein the weight ratio of A / B is 0.1
C. to 10. A flame-retardant thermoplastic resin composition obtained by mixing 1 to 50% by weight of the composition. (2) The flame-retardant resin composition according to claim 1, wherein the thermoplastic resin is a polyolefin or an elastomer thereof.

The configuration and effect of the present invention will be described below. The phosphoric acid compound (B) has the general formula (NH ₄ ) _{n + 2}
P _n O _{3n + 1} (wherein n is an integer of 2 or more) and ammonium polyphosphate exemplified by the molecular weight of the ammonium polyphosphate is preferably as large ones enough to become significantly water-soluble low. In order to further improve the water solubility, a substance obtained by coating particles of the substance with a thermosetting resin can also be used. An example of such an ammonium polyphosphate is Exo
lit422 (trade name, manufactured by Hoechst) or Phos-c
HeckP / 40 (trade name, manufactured by Monsanto Co., Ltd.), and Exolit 462 (trade name, manufactured by Hoechst Co., Ltd.) as an example of ammonium polyphosphate coated with a thermosetting resin.

The nitrogen-containing copolymer material represented by the above (A) is a random copolymer material having a monomer represented by the following formulas (I) and (II) as a basic unit:

[0007]

Embedded image (In the formula (I), X ₁ is —NH (R ₁ ) or —N (R ₂ )
An alkylamino group, a morpholino group or a piperidino group represented by the group (R ₃ ), wherein R ₁ , R ₂ and R ₃ have 1 to 6 carbon atoms. X ₂ is a group of —NH (R ₄ ) or —N (R ₅ ) (R ₆ ), R ₄ is a hydroxyalkyl group having 2 to 6 carbon atoms, and one or both of R ₅ and R ₆ are It is a hydroxyalkyl group having 2 to 6 carbon atoms, which may be the same or different. In addition, Y in the formula (I)
₁ , Y ₂ is a divalent group of piperazine or —N (R ₇ )
_{(C n H 2n) N (} R 8) - with a group represented, Y _1,
Y ₂ may be the same group or different groups.
R ₇ and R ₈ are each H and an alkyl group having 1 to 5 carbon atoms, and n represents an integer of 2 to 6. Furthermore, the general formula (I)
And the composition molar ratio of the general formula (II) is 0.3 ≦ (I) / (II)
≦ 3.0. ) Monomethyl amino group examples of X ₁ in the group, dimethylamino group, methylethylamino group, mono ethylamino group, diethylamino group, mono-propylamino group, dipropylamino group, methylpropylamino group, ethylpropylamino group, Methyl isopropyl amino group, ethyl isopropyl amino group, diisopropyl amino group, mono n-butyl amino group, di n-butyl amino group, methyl n-butyl amino group, ethyl n-butyl amino group, propyl n-butyl amino group, isopropyl n-
Butylamino group, monoisobutylamino group, diisobutylamino group, methylisobutylamino group, ethylisobutylamino group, propylisobutylamino group, isopropylisobutylamino group, monopentylamino group, dipentylamino group, methylpentylamino group, ethylpentylamino Group, propylpentylamino group, isopropylpentylamino group, n-butylpentylamino group, isobutylpentylamino group, monohexylamino group, dihexylamino group, methylhexylamino group, ethylhexylamino group, propylhexylamino group, isopropylhexylamino Group, n-butylhexylamino group,
Examples include an isobutylhexylamino group, a pentylhexylamino group, a morpholino group, and a piperidino group. X ₂
Examples of the group of the monohydroxyethylamino group, dihydroxyethylamino group, monohydroxypropylamino group, dihydroxypropylamino group, monohydroxyisopropylamino group, dihydroxyisopropylamino group, monohydroxy n-butylamino group, dihydroxy n- Examples include a butylamino group, a dihydroxyisobutylamino group, a monohydroxypentylamino group, a dihydroxypentylamino group, a monohydroxyhexylamino group, a dihydroxyhexylamino group, and an N-methylhydroxyethylamino group. Y _1, ethylenediamine Examples of Y ₂ groups, N, N ^'- dimethylethylenediamine, N, ^N' - diethyl ethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, piperazine, trans-2,5-dimethyl And piperazine. The weight ratio of (A) to (B) can be used in the range of 0.1 to 10, and preferably in the range of 0.15 to 1. The nitrogen-containing copolymer material according to the present invention comprises a triazine having at least one hydroxyalkyl group per triazine skeleton and at least one alkylamino group, morpholino group, or piperidino group per triazine skeleton. It is a substance characterized by being random copolymerized with triazine. Furthermore, the copolymer material according to the invention is sparingly soluble in water and does not seep out of the polymer due to moisture in the air. Moreover, surprisingly, it has been found that, when compared with the compound according to the conventional invention, a more excellent flame-retardant effect is exhibited even though the amount is low.

[0008]

EXAMPLES In order to specifically explain the present invention, synthesis examples, examples and comparative examples are shown below, but the present invention is not limited thereto. Unless otherwise specified, parts shown in Synthesis Examples and Examples are parts by weight.

Synthesis Example 1 92.2 parts (0.5 mol) of cyanuric chloride and water 3 were placed in a 2 L reaction vessel equipped with a stirrer, a thermometer, and a dropping funnel.
00 parts were charged. A solution prepared by dissolving 21.8 parts (0.25 mol) of morpholine and 26.3 parts (0.25 mol) of diethanolamine in 100 parts of water and 20 parts of sodium hydroxide in 50 parts of water while stirring and maintaining the temperature at 0 to 5 ° C. Was simultaneously added dropwise. The time required to drop all was 2 hours. After completion of the dropwise addition, the mixture was further stirred at the same temperature for 3 hours and allowed to stand at room temperature.
mol) in 200 parts of water was added dropwise over about 30 minutes. At the same time as the dropwise addition, the temperature of the reaction solution rose to about 40 ° C. due to the heat of the reaction. After the completion of the dropping of the aqueous piperazine solution, a solution prepared by dissolving 40 parts of sodium hydroxide in 100 parts of water was dropped. After the completion of the dropping, the reaction solution was heated to 100 ° C. and maintained at the same temperature for 4 hours. After cooling, the product was filtered, washed with water and hot water and dried. The yield was 88%. The obtained product was insoluble in ordinary organic solvents, and had a solubility in water at room temperature of 0.1% or less. Further, the residual chlorine was 0.35% as a result of elemental analysis. The decomposition start temperature was 290 ° C. as measured by a differential thermal balance. The reaction product is a random copolymer having monomeric basic units of the following formulas (III) and (IV), and the composition molar ratio is (III) / (IV) = 1.

[0010]

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Synthesis Example 2 Cyanuric acid chloride 92.2 was prepared in the same apparatus as in Synthesis Example 1.
Parts (0.5 mol) and 300 parts of water. 0-5 ° C
While stirring and maintaining 10.9 parts of morpholine (0.1
25mol) and 39.4 parts (0.3
(75 mol) in 100 parts of water and a solution of 20 parts of sodium hydroxide in 50 parts of water were simultaneously added dropwise. The time required to drop all was 2 hours.
After completion of the dropwise addition, the mixture was further stirred at the same temperature for 3 hours and allowed to stand at room temperature.
A solution in which 43.1 parts (0.5 mol) of piperazine was dissolved in 200 parts of water was added dropwise over about 30 minutes. At the same time as the dropwise addition, the temperature of the reaction solution rose to about 40 ° C. due to the heat of the reaction.
After the completion of the dropping of the aqueous piperazine solution, a solution prepared by dissolving 40 parts of sodium hydroxide in 100 parts of water was dropped. After the completion of the dropping, the reaction solution was heated to 100 ° C. and maintained at the same temperature for 4 hours. After cooling, the product was filtered, washed with water and hot water and dried. The yield was 87.6%. The obtained product was insoluble in ordinary organic solvents, and had a solubility in water at room temperature of 0.1% or less. The residual chlorine was found to be 0.53% by elemental analysis. The decomposition start temperature was 284 ° C. when the decomposition temperature was measured with a differential thermobalance. The reaction product is a random copolymer having monomeric basic units of the following formulas (III) and (IV) as in Synthesis Example 1, and the composition molar ratio is (III) / (IV) = 0.33. .

Synthesis Example 3 Cyanuric chloride 92.2 was prepared in the same apparatus as in Synthesis Example 1.
Parts (0.5 mol) and 300 parts of water. 0-5 ° C
32.7 parts of morpholine (0.3
75 mol) and 13.1 parts (0.1
(25 mol) in 100 parts of water and a solution of 20 parts of sodium hydroxide in 50 parts of water were simultaneously added dropwise. The time required to drop all was 2 hours.
After completion of the dropwise addition, the mixture was further stirred at the same temperature for 3 hours, and then allowed to stand at room temperature.
A solution in which 43.1 parts (0.5 mol) of piperazine was dissolved in 200 parts of water was added dropwise over about 30 minutes. At the same time as the dropwise addition, the temperature of the reaction solution rose to about 40 ° C. due to the heat of reaction.
After the completion of the dropping of the aqueous piperazine solution, a solution prepared by dissolving 40 parts of sodium hydroxide in 100 parts of water was dropped. After the completion of the dropping, the reaction solution was heated to 100 ° C. and maintained at the same temperature for 4 hours. After cooling, the product was filtered, washed with water and hot water and dried. The yield was 73.8%. The obtained product was insoluble in ordinary organic solvents, and had a solubility in water at room temperature of 0.1% or less. The residual chlorine was 3.8% as a result of elemental analysis. The decomposition temperature was 295 ° C. when the decomposition temperature was measured with a differential thermobalance. The reaction product is a random copolymer having monomeric basic units of the following formulas (III) and (IV) as in Synthesis Example 1, and the composition molar ratio is
(III) / (IV) = 3.0.

Synthesis Example 4 Cyanuric acid chloride 92.2 was prepared in the same apparatus as in Synthesis Example 1.
Parts (0.5 mol) and 300 parts of water. 0-5 ° C
While stirring and keeping N-methylpiperazine 24.8.
(0.25 mol) and a solution of 26.2 parts (0.25 mol) of diethanolamine in 100 parts of water and a solution of 20 parts of sodium hydroxide in 50 parts of water were simultaneously dropped. The time required to drop all was 2 hours. After completion of the dropwise addition, the mixture was further stirred at the same temperature for 3 hours, and then allowed to stand at room temperature. 43.1 parts (0.5 mol) of piperazine was added to water 20
The solution dissolved in 0 parts was added dropwise over about 30 minutes. At the same time as the dropwise addition, the temperature of the reaction solution rose to about 40 ° C. due to the heat of reaction. After the completion of the dropping of the aqueous piperazine solution, a solution prepared by dissolving 40 parts of sodium hydroxide in 100 parts of water was dropped. After the completion of the dropping, the reaction solution was heated to 100 ° C. and maintained at the same temperature for 4 hours. After cooling, the product is filtered, washed with water and hot water,
Dried. The yield was 82.2%. The obtained product was insoluble in ordinary organic solvents, and had a solubility in water at room temperature of 0.1% or less. Further, the residual chlorine was 2.5% as a result of elemental analysis. The decomposition start temperature was 292 ° C. when the decomposition temperature was measured with a differential thermobalance. The reaction product is a random copolymer having monomer basic units of the following formulas (V) and (VI), and the composition molar ratio thereof is (V) /
(VI) = 1.

[0014]

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Synthesis Example 5 Cyanuric acid chloride 92.2 was prepared in the same apparatus as in Synthesis Example 1.
Parts (0.5 mol) and 300 parts of water. 0-5 ° C
21.8 parts of morpholine (0.2
5 mol) and 26.3 parts (0.25 parts) of diethanolamine.
(mol) in 100 parts of water and a solution of 20 parts of sodium hydroxide in 50 parts of water were simultaneously dropped.
The time required to drop all was 2 hours. After completion of the dropwise addition, the mixture was further stirred at the same temperature for 3 hours and then allowed to stand at room temperature, and a solution of 30.0 parts (0.5 mol) of ethylenediamine dissolved in 200 parts of water was added dropwise over about 30 minutes. At the same time as the dropwise addition, the temperature of the reaction solution rose to about 35 ° C. due to the heat of the reaction. After completion of the dropping of the aqueous solution of ethylenediamine, a solution prepared by dissolving 40 parts of sodium hydroxide in 100 parts of water was dropped. After the completion of the dropping, the reaction solution was heated to 100 ° C. and maintained at the same temperature for 4 hours. After cooling, the product was filtered, washed with water and hot water and dried. The yield was 67.4%. The obtained product was insoluble in ordinary organic solvents, and had a solubility in water at room temperature of 0.1% or less. Further, the residual chlorine was 3.2% as a result of elemental analysis. The decomposition temperature was 280 ° C. when the decomposition temperature was measured with a differential thermobalance. The reaction product is a random copolymer having monomeric basic units of the following formulas (VII) and (VIII), and the composition molar ratio thereof is (VI
I) / (VIII) = 1.

[0016]

Embedded image

Synthesis Example 6 Cyanuric acid chloride 92.2 was prepared in the same apparatus as in Synthesis Example 1.
Parts (0.5 mol) and 300 parts of water. 0-5 ° C
A solution of 18.3 parts (0.25 mol) of diethylamine and 26.3 parts (0.25 mol) of diethanolamine in 100 parts of water and a solution of 20 parts of sodium hydroxide in 50 parts of water with stirring at a temperature of At the same time. The time required to drop all was 2 hours. After completion of the dropwise addition, the mixture was further stirred at the same temperature for 3 hours and then allowed to stand at room temperature, and a solution of 30.0 parts (0.5 mol) of ethylenediamine dissolved in 200 parts of water was added dropwise over about 30 minutes.
At the same time as the dropwise addition, the temperature of the reaction solution rose to about 35 ° C. due to the heat of the reaction. After completion of the dropping of the aqueous solution of ethylenediamine, a solution prepared by dissolving 40 parts of sodium hydroxide in 100 parts of water was dropped. After the completion of the dropping, the reaction solution was heated to 100 ° C. and maintained at the same temperature for 4 hours. After cooling, the product was filtered, washed with water and hot water and dried. The yield was 65.2%. The obtained product was insoluble in ordinary organic solvents, and had a solubility in water at room temperature of 0.1% or less. The residual chlorine was found to be 3.6% by elemental analysis. The decomposition start temperature was 282 ° C. when the decomposition temperature was measured with a differential thermobalance. The reaction product is a random copolymer having monomeric basic units of the following formulas (IX) and (X), and the composition molar ratio is (IX) / (X) = 1.

[0018]

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Comparative Synthesis Example 1 In place of 21.8 parts (0.25 mol) of morpholine and 26.3 parts (0.25 mol) of diethanolamine in Synthesis Example 1, 52.6 parts (0.5 mol) of diethanolamine.
The synthesis was carried out by the same apparatus and method as in Synthesis Example 1 except that was used. The estimated structural formula is as shown in the following formula (XI).

[0020]

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Comparative Synthesis Example 2 Except that 43.6 parts (0.5 mol) of morpholine were used instead of 21.8 parts (0.25 mol) of morpholine and 26.3 parts (0.25 mol) of diethanolamine of Synthesis Example 1. The compound was synthesized by the same apparatus and method as in Synthesis Example 1.
The estimated structural formula is as shown in the following formula (XII).

[0022]

Embedded image

Comparative Synthetic Example 3 Except that 42.6 parts (0.5 mol) of piperidine were used instead of 21.8 parts (0.25 mol) of morpholine and 26.3 parts (0.25 mol) of diethanolamine of Synthetic Example 1. The compound was synthesized by the same apparatus and method as in Synthesis Example 1.
The estimated structural formula is as shown in the following formula (XIII).

[0024]

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Table 1 shows the decomposition start temperatures of the compounds synthesized in Synthesis Examples 1 to 6 and Comparative Examples 1 to 3, and the solubility in 100 g of water at room temperature.

[0026]

[Table 1]

Example 1 As a polypropylene resin, an ethylene content of 8.5% by weight, a melt flow rate (temperature of 230 ° C., load 2.16)
(discharge rate of molten resin for 10 minutes when kg is added) 20
g / 10 minutes of a crystalline ethylene-propylene block copolymer (49.5% by weight) and a polyethylene resin (component A) having a melt index (at a temperature of 190 ° C. under a load of 2.16 k)
g of molten resin for 10 minutes when g is added) 6.5
g / 10 minutes of ethylene homopolymer (Nissopolyethylene (trademark) M680, manufactured by Chisso Corporation) 10% by weight, ethylene-propylene rubber (JSR EP (trademark) 02P, ethylene-based synthetic rubber or elastomer (component B))
10% by weight of Nippon Synthetic Rubber Co., Ltd., 24.2% by weight of Exolit-422 (trade name, manufactured by Hoechst) as ammonium polyphosphate (Component C), Synthesis Example 1 (Component D)
4.8% by weight of the compound synthesized in 1), which is pulverized by a commonly known pulverizer, 1% by weight of vinyltrimethoxysilane as a silane coupling agent (component E), and 2,6- 0.2% by weight of di-t-butyl-p-cresol, 0.2% by weight of di-myristyl-β, β′-thiodipropionate and 0.1% by weight of calcium stearate are put into a Henschel mixer (trade name). ,
Stir and mix for 3 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, and pelletized. After drying the obtained pellets at a temperature of 100 ° C. for 3 hours, the temperature was adjusted to 20
A predetermined test piece for flame retardancy evaluation was prepared by a hot press set at 0 ° C. Flame retardancy was evaluated using the test piece. Flame retardancy was performed by ASTM and measuring the compliant oxygen index in D-2863, UL-94 ( Underweriters Laboratories) thick vertical combustion test according to the 1.2 mm ^t. Regarding the cotton ignition rate, it was confirmed whether the melt dropped on the surgical absorbent cotton placed 30 cm below the test piece and the surgical absorbent cotton ignited. Table 2 shows the evaluation results of the flame retardancy.

[0028]

[Table 2]

Component A Polyethylene resin: Chissopoly M6
80 (manufactured by Chisso Corporation) Component B Ethylene-propylene rubber: JSR EP
02P (Nippon Synthetic Rubber Co., Ltd.) Component C Ammonium polyphosphate: Exolit-
422 (trade name, manufactured by Hoechst) Component D1 Compound of Synthesis Example 1 Component D2 Compound of Synthesis Example 2 Component D3 Compound of Synthesis Example 3 Component D4 Compound of Synthesis Example 4 Component D5 Compound of Synthesis Example 5 Component D6 Synthesis Example 6 Compound Component D7 Compound of Comparative Synthesis Example 1 Component D8 Compound of Comparative Synthesis Example 2 Component D9 Compound of Comparative Synthesis Example 3 Component D10 Tris (2-hydroxyethyl) isocyanurate Component E Silane coupling agent: vinyltrimethoxysilane stabilizer 2 , 6-Di-t-butyl-p-cresol di-myristyl-β, β′-thiodipropionate calcium stearate

Example 2 As an APP, 21.0% by weight of Exolit-422 (trade name, manufactured by Hoechst), and the compound synthesized in Synthesis Example 1 (component D1) was pulverized with a commonly known pulverizer.
The flame retardancy was evaluated using the same method and apparatus as in Example 1 except that the weight was 0% by weight. Table 2 shows the evaluation results of the flame retardancy. Example 3 24.2% by weight of Exolit-422 (trade name, manufactured by Hoechst) as an APP, and the compound synthesized in Synthesis Example 2 (component D2) was pulverized by a commonly known pulverizer.
The flame retardancy was evaluated using the same method and apparatus as in Example 1 except that the content was 8% by weight. Table 2 shows the evaluation results of the flame retardancy. Example 4 As an APP, 21.0% by weight of Exolit-422 (trade name, manufactured by Hoechst) and the compound synthesized in Synthesis Example 2 (component D2) pulverized with a commonly known pulverizer.
The flame retardancy was evaluated using the same method and apparatus as in Example 1 except that the weight was 0% by weight. Table 2 shows the evaluation results of the flame retardancy. Example 5 As an APP, Exolit-422 (trade name, manufactured by Hoechst) was 24.2% by weight, and the compound synthesized in Synthesis Example 3 (component D3) was pulverized with a commonly known pulverizer.
The flame retardancy was evaluated using the same method and apparatus as in Example 1 except that the content was 8% by weight. Table 2 shows the evaluation results of the flame retardancy. Example 6 APP was Exolit-422 (trade name, manufactured by Hoechst) 21.0% by weight, and the compound synthesized in Synthesis Example 3 (component D3) was pulverized by a commonly known pulverizer.
The flame retardancy was evaluated using the same method and apparatus as in Example 1 except that the weight was 0% by weight. Table 2 shows the evaluation results of the flame retardancy. Example 7 As an APP, Exolit-422 (trade name, manufactured by Hoechst) was 24.2% by weight, and the compound synthesized in Synthesis Example 4 (component D4) was pulverized with a commonly known pulverizer.
The flame retardancy was evaluated using the same method and apparatus as in Example 1 except that the content was 8% by weight. Table 2 shows the evaluation results of the flame retardancy. Example 8 APP was 21.0% by weight of Exolit-422 (trade name, manufactured by Hoechst), and the compound synthesized in Synthesis Example 4 (component D4) was pulverized by a commonly known pulverizer.
The flame retardancy was evaluated using the same method and apparatus as in Example 1 except that the weight was 0% by weight. Table 2 shows the evaluation results of the flame retardancy. Example 9 As an APP, 24.2% by weight of Exolit-422 (trade name, manufactured by Hoechst) and the compound synthesized in Synthesis Example 5 (component D5) pulverized with a generally known pulverizer are used.
The flame retardancy was evaluated using the same method and apparatus as in Example 1 except that the content was 8% by weight. Table 2 shows the evaluation results of the flame retardancy. Example 10 APP was Exolit-422 (trade name, manufactured by Hoechst) 21.0% by weight, and the compound synthesized in Synthesis Example 5 (component D5) was pulverized with a commonly known pulverizer.
The flame retardancy was evaluated using the same method and apparatus as in Example 1 except that the weight was 0% by weight. Table 2 shows the evaluation results of the flame retardancy. Example 11 As an APP, Exolit-422 (trade name, manufactured by Hoechst) was 24.2% by weight, and the compound synthesized in Synthesis Example 6 (component D6) was pulverized by a commonly known pulverizer.
The flame retardancy was evaluated using the same method and apparatus as in Example 1 except that the content was 8% by weight. Table 3 shows the evaluation results of the flame retardancy. Example 12 APP was Exolit-422 (trade name, manufactured by Hoechst) 21.0% by weight, and the compound synthesized in Synthesis Example 6 (component D6) was pulverized with a commonly known pulverizer.
The flame retardancy was evaluated using the same method and apparatus as in Example 1 except that the weight was 0% by weight. Table 3 shows the evaluation results of the flame retardancy.

Comparative Example 1 24.2% by weight of Exolit-422 (trade name, manufactured by Hoechst) as an APP, and the compound synthesized in Comparative Synthesis Example 1 (component D7) was pulverized by a commonly known pulverizer. The flame retardancy was evaluated using the same method and apparatus as in Example 1 except that the content was set to 0.8% by weight. Table 3 shows the evaluation results of flame retardancy.
Shown in Comparative Example 2 24.2% by weight of Exolit-422 (trade name, manufactured by Hoechst) as APP, and 4.8% by weight of a compound synthesized in Comparative Synthesis Example 2 (component D8) crushed by a commonly known crusher. %, The flame retardancy was evaluated using the same method and apparatus as in Example 1. Table 3 shows the evaluation results of flame retardancy.
Shown in Comparative Example 3 Exolit-422 (trade name, manufactured by Hoechst) as an APP was 21.0% by weight, and the compound synthesized in Comparative Synthesis Example 2 (Component D8) was pulverized with a commonly known pulverizer to 8.0% by weight. %, The flame retardancy was evaluated using the same method and apparatus as in Example 1. Table 3 shows the evaluation results of flame retardancy.
Shown in Comparative Example 4 24.2% by weight of Exolit-422 (trade name, manufactured by Hoechst) as APP, and 4.8% by weight of a compound synthesized in Comparative Synthesis Example 3 (component D9) crushed by a commonly known crusher. %, The flame retardancy was evaluated using the same method and apparatus as in Example 1. Table 3 shows the evaluation results of flame retardancy.
Shown in Comparative Example 5 Exolit-422 (trade name, manufactured by Hoechst) as an APP was 21.0% by weight, and the compound synthesized in Comparative Synthesis Example 3 (Component D9) was pulverized with a commonly known pulverizer to 8.0% by weight. %, The flame retardancy was evaluated using the same method and apparatus as in Example 1. Table 3 shows the evaluation results of flame retardancy.
Shown in Comparative Example 6 Example 1 was the same as Example 1 except that Exolit-422 (trade name, manufactured by Hoechst) was 21.0% by weight and tris (2-hydroxyethyl) isocyanurate (component D8) was 8.0% by weight as APP. Flame retardancy was evaluated using the same method and apparatus. Table 3 shows the evaluation results of the flame retardancy.

[0032]

[Table 3]

[0033]

The nitrogen-containing copolymer material of the present invention exhibits excellent flame retardancy at a low addition amount. In addition, it has been clarified that the flame retardancy at a low content is improved by including the hydroxyalkyl group in the functional group. Further, although the functional group contains a hydroxyalkyl group, it also contains an alkylamino group, a morpholino group, and a piperidino group, so that the drip property during combustion is extremely low. Further, since it is poorly water-soluble, it does not exude from the compounded polymer due to moisture in the air.

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Continuation of the front page (58) Field surveyed (Int. Cl. ⁷ , DB name) C08L 79/00-79/08 C08G 73/00-73/26 C08K 3/22 CA (STN) REGISTRY (STN)

Claims (2)

(57) [Claims] 1. A thermoplastic resin comprising: A random copolymer material having a monomer represented by the general formula (I) or (II) as a basic unit; (In the formula (I), X ₁ is —NH (R ₁ ) or —N (R ₂ )
An alkylamino group, a morpholino group or a piperidino group represented by the group (R ₃ ), wherein R ₁ , R ₂ and R ₃ have 1 to 6 carbon atoms. X ₂ is a group of —NH (R ₄ ) or —N (R ₅ ) (R ₆ ), R ₄ is a hydroxyalkyl group having 2 to 6 carbon atoms, and one or both of R ₅ and R ₆ are It is a hydroxyalkyl group having 2 to 6 carbon atoms, which may be the same or different. In addition, Y in the formula (I)
₁ , Y ₂ is a divalent group of piperazine or —N (R ₇ )
_{(C n H 2n) N (} R 8) - with a group represented, Y _1,
Y ₂ may be the same group or different groups.
R ₇ and R ₈ are each H and an alkyl group having 1 to 5 carbon atoms, and n represents an integer of 2 to 6. Furthermore, the general formula (I)
And the composition molar ratio of the general formula (II) is 0.3 ≦ (I) / (II)
≦ 3.0); A flame retardant comprising ammonium polyphosphate or polyphosphoramide, wherein the weight ratio of A / B is 0.1
C. to 10. A flame-retardant thermoplastic resin composition obtained by mixing 1 to 50% by weight of the composition. 2. The flame-retardant resin composition according to claim 1, wherein the thermoplastic resin is a polyolefin or an elastomer thereof.