TWI314944B - Flame retardant thermoplastic resin composition - Google Patents

Description

1314944 Α7

The present invention relates to a thermoplastic composition having good flame retardancy. More particularly, the present invention relates to a tree-less/twist thermoplastic resin composition containing a tree having a good formability irrespective of the base resin, [Background of the Invention] For a long time, The main goal of improving the research and development of flame retardant resin of thermoplastic resin composition. It is known to use a functional compound to prepare a best method for retarding combustion of a thermoplastic resin composition. U.S. Patent Nos. 4,9,83,65,8 and 4,8,83,8,35 disclose the use of a halogen compound as a flame retardant for a thermoplastic resin composition. The thermoplastic resin composition using the functional compound exhibits good flame retardancy regardless of the base resin. However, it has been observed that halogen-containing compounds cause the mold itself to be corroded by the hydrogenated hydrogen gas released during molding, and release toxic gases during a fire, which is fatal and dangerous. Therefore, halogen-free flame retardants have become a major concern in this area. Today's representative flame retardant containing no _ is a flame retardant. The lining compound is superior to the halogen compound in the corrosion of the appliance and the release of toxic gases. However, the 'phosphorus compound cannot provide better flame retardancy than the dentate compound' and if a larger amount of the phosphorus compound is used to increase the flame retardancy, the heat resistance is deteriorated. In addition, when using the phosphating 4 paper size, the Chinese National Standard (CNS) A4 specification (210 X 297 publicity (please read the back note first and then fill out this page) ρί装— ί I 订· — I!— !· Ministry of Economic Affairs, Intellectual Property Office, Staff Consumer Cooperative, Printed by A7 1314944 B7_ V. Inventive Note (,) When the material is used as a flame retardant, the base resin is limited. Another method for improving the flame retardancy of the thermoplastic resin composition In order to add a material having good carbon forming ability to a base resin having poor carbon forming ability to form a carbon film during combustion, the carbon film blocks oxygen, heat, and other fuel gas transportation which accelerates resin combustion. Resin has good carbon forming ability and has been set as the target for research on retarding combustion thermoplastic resin composition. However, phenol resin has insufficient carbon film and phenol resin has poor compatibility with other resins due to resin polarity. And the disadvantage of having a color change problem due to weak weathering resistance. Therefore, the inventors of the present invention have developed a retardation combustion thermoplastic resin composition using gram. A phenol resin derivative which is disadvantageous to the above phenol resin. In the thermoplastic resin composition of the present invention, the phenol resin derivative solves the problem of color change due to the use of the phenol resin and improves compatibility with other polymer resins. The resin derivative provides a retardation combustion thermoplastic resin composition having a good carbon shape ability. [Object of the Invention] It is a feature of the present invention to provide a thermoplastic resin composition which has superior flame retardancy regardless of the base resin. Another feature is to provide a good anti-purple 5 paper size for the Chinese National Standard (CNS) A4 specification (210 X 297 mm) (please read the back note before filling this page) · ------ --Order --------- Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperatives Printed A7 1314944 __B7 _ V. Invention Description (?) External weathering resistance and good compatibility with other polymer resins A thermoplastic resin composition. A further feature of the present invention is to provide a thermoplastic resin composition which does not cause mold corrosion due to release of hydrogen halide gas during molding, and does not occur in a fire The toxic gas is released. Other objects and advantages of the present invention will be set forth in the following disclosure and the accompanying claims. [Invention Summary] The retardation combustion thermoplastic resin composition of the present invention comprises (A) 100 parts by weight of heat. The plastic resin is used as a base resin, (B) a phenol resin derivative of about 0.1 to 100 parts by weight, and (C) a mixture of a scaly compound or a compound of about 1 to 50 parts by weight. A) Thermoplastic Resin (Base Resin) Any thermoplastic resin can be used as the base resin in the present invention. If a phosphorus compound is used as the flame retardant, the base resin is limited because it is difficult to obtain sufficient flame retardancy. However, in the present invention, since both the phenol resin derivative and the polyphenylene ether resin are used, a thermoplastic resin having no or poor carbon forming ability can be used as the base resin to produce sufficient flame retardancy. . Examples of thermoplastic resins as base resin include polypropylene 6 This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) ------------_Installation Read the notes on the back and fill out this page. Order---------The Ministry of Economic Affairs, Intellectual Property Office, Staff and Consumers Cooperatives Printed 1314944 A7 _ B7_ V. Invention Description (present) Nitrile-butadiene-Benzene Ethylene copolymer (ABS resin), rubber modified polystyrene resin (HIPS), acrylonitrile-styrene-acrylic acid copolymer (AS A resin), methacrylic acid-butadiene-styrene copolymer (MBS resin) ), acrylonitrile-ethyl acrylate-styrene copolymer (AES resin), polycarbonate (PC), polyethylene (PE), polypropylene (PP), polyethylene terephthalate (PET), poly pair Butane phthalate (PBT), polyethylene (PVC), polymethyl methacrylate (PMMA), polydecylamine (PA), and copolymers thereof, and blends thereof. (B) Phenolic Resin Derivative When a phenol resin is used in the thermoplastic resin composition to improve flame retardancy, the phenol resin has the following disadvantages: the carbon film is not dense enough, and the phenol resin is compatible with other resins due to the polarity of the resin. Poor, and because of the weak anti-weathering resistance to UV, there is a problem of color change. A phenol resin derivative is used to overcome the disadvantages of the phenol resin. The phenol resin derivative has good compatibility with other polymer resins used. Use phenol resin derivative / material to provide good charcoal shape and equipment ------ (Please read the back of the note before you fill out this page) Order ---------^91 Ministry of Economic Affairs Intellectual Property Bureau Employees' consumption cooperatives print the phenolic resistance of the eucalyptus gum: increase the structure of the knot, learn the bottom of the tree (1) under the base, and have the ability to make the paper. The paper size applies to the Chinese National Standard (CNS) A4 specification. (2〗 0 X 297 mm) 1314944 A7

V. INSTRUCTIONS (f) (I) where &丨 is (^丨.34的惊 1. 1.^;:^. Condensed, square, alkyl substituted aryl; or s• An alkyl group; a aryl group containing 〇-, N_, P-, or S- 戈 containing 0..., or S-substituted by a burnt group: C4 is a hydrogen group, a hydrogen group of Ci. 34; an aryl group; Square earth, an alkyl group containing 〇-, N·, P·, or S-; an aryl group containing, /, p_, or =; or a substitution containing 0-, N-, P-, or S- Square base; and to 10,0 if

In view of mechanical properties and handleability, it is preferred that during combustion, the phenolic resin derivative acts on the membrane to prevent the flow of combustion gases and the inflow of oxygen or air, and acts like a flame retardant additive. The anti-derivative derivative can overcome the problem that the carbon film is weak when the resin is used in the thermoplastic resin composition, the poor compatibility of the resin (4) with other tree sap, and the color change due to weak weathering resistance. The disadvantage of phenolic resin. Preferred examples of the aged resin derivative include o-cresol phenolphthalein, and phenol epoxy resin. The desired resin derivative can be used singly or in a mixture. The amount of phenolic resin derivative that can be used is 100 parts by weight. — — — — — 1^ ^ *-------^«1 —---I--. (Please read the back first Note: Please fill out this page again) Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperatives printed *'1 1314944 A7 B7 Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printing 5, invention description (b) base resin, subject to about 0.01 to 100 Parts by weight. (C) Phosphorus compound The phosphorus compound which can be used in the present invention comprises a phosphate compound, a phosphoamidate compound, an oxaphosphorane compound, a thiophosphinic acid compound, and an acid-filled acid.醢 吗 化合物 化合物 compound, and even phosphorus nitrogen compounds. The phosphorus compound can be used singly or in combination. The amount of the phosphorus compound which can be used is from about 1 to 50 parts by weight based on 1 part by weight of the base resin. The phosphorus compound is detailed as follows: Phosphate compound and amino phosphate compound The phosphate compound and the amino phosphate compound are represented by the following chemical formula (II):

Wherein R3, R4, and R5 are hydrogen or an alkyl group of Ci-4, and X is an aryl group of C6-2〇 or an aryl group of an alkyl substituted C6_2〇, which is a derivative derived from a diol such as m-phenylene Phenol, decyl alcohol, bisphenol-A, and bisphenol-S, 9 This paper scale is applicable to China National Standard (CNS) A4 specification (210 X 297 mm).--------Set---- -----Line (please read the precautions on the back and then fill out this page) 1314944 A7 B7 V. Invention Description ( ¥ is oxygen or nitrogen, and m is in the range of 〇 to 4. If, if yes, then The compound may be triphenyl squary acid vinegar, tris(dimethylphenyl) decanoic acid brewing, tris, monophenyl phenyl phosphate, tris(2,4,6_=methine_s', third (2~) Third butyl phenyl ... phenyl) linoleic acid, and its analogs, hexamethyl, bis(2,6-dimethylphenyl phenyl), bis (tertiary butyl) Phenyl)linic acid, =-methylphenyl)phosphate, decyl alcohol (2,4-di(tris-butyl citrate, and the like), either alone or in combination: "::." Chemical formula (111) represents a phosphorous compound:

m (Please read the notes on the back and fill out this page) Pack----------------- Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperatives printed in the base η alkane, 1-6 base C Fang Hydrogen-6 is CR or medium nitrogen. It is a phosphorus-oxygen-burning combination of phosphorus or chemical-independent/1 2-single-mono-homoxyl phosphatidone 2 standard scale in a country with a moderate ruler «5 paper \〇的C 3 or to R and 2 R bases of the inner circumference *·, 巳*J· and the combination of 2 to make the real good base benzeneο oxygen with PCT-9 12 X ο 21 /V grid 4 A is) - 2-1 曱 曱 匕 / / 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 , , , , , , , , , 13 13 13 13 13 13 13 13 13 13 The chemical formula (I v ) represents a carboxyphosphinic acid compound:

R

0 II . 1 P R2~~"〇〇2^ OH (IV) wherein R丨 is hydrogen, an alkyl group of CU2, an aryl group of C6-10, or an alkyl-substituted aryl group of C7_|5, R2 The alkyl group of CU2, the cyclic group of Ci-12, the alkyl group of Cm, the aryl group of Cm-12, or the aryl group substituted by C6-12. A preferred example of the carboxyphosphinic acid compound is 2-carboxy-ethyl-methyl-phospanic acid, 2-carboxyethyl-phenyl-phosphinic acid (2) -carboxy-ethyl-phenyl-phospanic acid), and 2-carboxy-methyl-phenyl-phospanic acid 0 may be used alone or in combination. Things. (Please read the precautions on the back and fill out this page.) Ministry of Economic Affairs, Intellectual Property Office, Staff and Consumer Cooperatives Printed *''" Phosphate oxime morpholine compound: Phosphate oxime morpholine compound represented by the following chemical formula (V): The paper scale applies to the Chinese National Standard (CNS) A4 specification (210 x 297 1314944 A7 B7. V. Inventions ([R"〇|

2-X

0 II P- M

0, 0 〇—r2-o-p- — II 0—R2—0—Ρ- η όJ -0-R! I R1

Ο (V) wherein Ri is C6_20 aryl or alkyl substituted C6_20 aryl, R_2 is C6-30 aryl or alkyl substituted C6-30 aryl, X is 1 or 2, and η and m are The number average degree of polymerization, and n + m is 0 to 5. In formula (V), the heart is preferably phenyl or alkyl substituted phenyl wherein alkyl is decyl, ethyl, isopropyl, tert-butyl, isobutyl, isopentyl, or a third pentyl group, preferably a methyl group, an ethyl group, an isopropyl group, or a tert-butyl group, and r2 is preferably a c6_3〇 aryl group or an alkyl substituted C6_3G aryl group derived from resorcinol, Nitrogen, or a combination of - A derivatives. The phosphate morphine compound can be used singly or in combination. The arylphosphorus compound: a linear azo-nitrogen compound represented by the following chemical formula (VI) and a cyclic azo-phosphorus compound represented by the following chemical formula (VII): 11^-------- (Please read the notes on the back and fill out this page) Line 0· Printed by the Ministry of Economic Affairs, Intellectual Property Bureau, Staff Consumer Cooperative

R R3 *mu N- R-

N

P

V

2 R R2 k 12 This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) 1314944 A7 B7 V. Invention description (w)

Ri

R2 (vii) Ministry of Economic Affairs, Intellectual Property Office, Staff Consumer Cooperative, which prints R!, R2, and R3 independently as alkyl, aryl, alkyl-substituted aryl, aralkyl, alkoxy, aryloxy, An amine group, or a hydroxyl group, and k are an integer of from 0 to 10. The alkoxy group and the aryloxy group may be substituted with an alkyl group, an aryl group, an amine group, a hydroxyl group, a nitrile group, a nitro group, or an aryl group having a hydroxyl group. Other additives may be used in the thermoplastic resin composition of the present invention. The additive comprises an impact modifier, a thermal stabilizer, an oxidation inhibitor, a light stabilizer, and an inorganic filler such as talc, alumina, mica, glass fibers, organic or inorganic pigments, and/or dyes. The amount of the additive used is up to about 50 parts by weight based on 1 part by weight of the base resin. The invention is to be understood as being limited by the following examples. The invention is not to be construed as limiting the scope of the invention; the scope of the invention is defined by the scope of the appended claims. In the following examples, all parts and percentages are by weight unless otherwise indicated. Example Preparation Examples 1 to 12 and Comparative Examples 1 to 6 The retarding combustion heat 13 ------------ Pack----- (Please read the back note first and then fill out this page ) 111!1 Line 0. This paper size is applicable to China National Standard (CNS) A4 specification (2〗 0 X 297 mm) 1314944 A7 V. Invention Description (丨I) The composition of the plastic resin composition is as follows: (A) Heat Plastic resin (base resin) (A丨) High impact polystyrene (H! ps) (Please read the back note and then fill out this page) Prepare high impact polystyrene by conventional methods. It has a rubber content of 9% by weight, 丨, m average rubber particle size 'and a weight average molecular weight of 220,000. (A2) SAN graft copolymer 50 parts of butyl rubber latex powder, 36 parts of styrene, i 4 parts of acrylonitrile, and 150 parts of deionized water were mixed. Add 1.0 part potassium oleate, 0.4 parts cumene hydroperoxide, 2 parts thiol-containing chain transfer agent, 0.4 parts of glucose, hydrazine hydrated iron sulphate hydroxide, and 0. 3 parts sodium pyroantimonate salt. The blend was held at 7 5 〇c for $hour to obtain ABS latex. To the ABS latex, 〇4 parts of sulfuric acid was added to coagulate and dry to obtain a powdery styrene-containing graft copolymer resin (g-ABS). (A3) SAN Copolymer Economy Ministry Intellectual Property Bureau Staff Consumer Cooperative Printed ^ 5 parts of styrene, 25 parts of propylene acrylonitrile, 12 parts of deionized water, 0.15 parts of azo-isobutyl (AIBN) ) Change. To the replacement compound, 0.4 part of tricalcium carbonate and 0.2 part of a chain transfer agent containing a mercaptan were added. The resulting solution was heated to 80 ° C for 90 minutes and held for 18 minutes. The resultant was washed, dehydrated and dried. A styrene-acrylonitrile (SAN) copolymer is obtained. (A4) Polycarbonate resin This paper scale is applicable to China National Standard (CNS) A4 specification (210 X 297 mm) 1314944 A7 B7 V. Description of invention (丨>) Using a linear shape with a weight average molecular weight of 25, 〇〇〇 The bisphenol-A type of polycarbonate is intended. (B) Phenolic resin derivative (B) A phenol resin derivative (product name: YDCN-500-7P) of Kukdo Chemical Co., Ltd. is represented by the following formula (VIII):

O-ch2-ch-ch2 \ /

^H2-CH-CH2 0-CH2-CH-^CH2 O flaC, 丄 0

Please read the note on the back S} first, then n has an average of 2.3. (Β2) 50 g has a softening point of 8 5 . C novolac resin, 200 g of base gas, and 150 g of isopropanol dissolved in 20 ml of water' and the resulting solution was heated to 7 Torr. c. 100 g of 20% N a Ο Η was added to the solution over 1 hour with stirring. After another two hours of reaction, the solution was allowed to cool to room temperature. The organic layer was separated from the aqueous layer and washed several times with deionized water. The separated organic layer was vacuum distilled to remove benzyl chloride and solvent. The resultant was dried in an oven to obtain a final product represented by the following formula (IX): I I I I I

Ministry of Economic Affairs, Intellectual Property Bureau, Staff Consumption Cooperative, Printed M

-chh〇)

15 2~0> (IX) This paper scale is applicable to China National Standard (CNS) A4 specification (210 X 297 mm) 1314944 A7 B7 V. Inventive Note (丨)) where η has an average value of 3.4. (Β3) is a novolak phenol resin having a molecular weight of about 1 Å, which is represented by the following formula (X), in comparison with a phenol resin derivative:

Where η has an average of 5.2. (C) Phosphorus compound (C,) Triphenyl phosphate (ΤΡΡ) having a melting point of 48 ° C was used. (C 2 ) Use a viscous liquid between the benzene glycol diphosphate (RDP) at room temperature. (C3) Triphenyl hydralmorphine resorcinol diphosphate (TPP) represented by the following formula (XI): (Please read the back note and fill out this page)

Ministry of Economic Affairs Intellectual Property Office Staff Consumer Cooperative Printed Examples 1 to 1 2 In Examples 1 to 5 and Comparative Examples 1 to 3, the composition of the components is shown in Table 1. The resin composition was extruded into pellets at a conventional twin screw extruder at 200 to 28 °C. 16 This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) A7 1314944 ___B7_ V. Invention description (rush) at 80. (: The resin pellets were dried for 3 hours, and a test piece was molded at 2 20 to 280 ° C using a 6 oz injection molding machine to measure a limited oxygen index (LOI). The finite oxygen index was measured according to ASTM D2863. Comparative Examples 1 to 6 In Comparative Examples 1, 3, and 5, neither a phenol resin was used, nor a phenol resin was used, and in Comparative Examples 2, 4, and 6, 'the phenol resin (B 3 ) was used. Not a phenolic resin derivative. ' Table 1

ABC Λ1 A2 A3 A4 "βΓ~ Β2 Β3 C1 C2 C3 Example 1 100 10 15 • 36 2 100 - - - 10 - - - 15 - 36 3 100 - - - 10 - - - - 15 35 4 100 - - - - 10 - 15 - - 36 5 100 - • - - 10 - - 15 - 34 6 100 - - - - 10 - - - 15 36 7 - 70 30 - 10 - - 15 - - 35 8 - 70 30 - - 10 - 15 - - 34 9 - 70 30 - 10, - - - 15 - 34 10 - 42 18 40 10 - - 15 - - 39 11 - 42 18 40 - 10 - 15 - - 36 12 - 42 18 40 - 10 - - - 15 37 Comparative example 1 100 . • 15 • 21 2 100 - - - - - 10 15 - - 27 j - 70 30 - - - - 15 - - 23 4 - 70 30 - - - 10 15 - - 29 5 - 42 IS 40 - - - 15 - 26 6 - 42 IS 40 - - 10 15 - - 30 Table 1 shows the resin groups of Examples 1 to 12 and Comparative Examples 1 to 6 4 17 This paper size applies to the Chinese National Standard (CNS) ) A4 size (2) 0 X 297 mm) (Please read the note on the back and fill out this page) | Install -------- Order --------- Line j Ministry of Economics Property Bureau employee consumption cooperative printed 1314944 A7 ___Β7_ V. Invention description (LOI of stolen goods. Higher LOI, that is, more oxygen is needed to burn resin, meaning The higher IOL showed good flame retardancy. In Examples 1 to 12, the phenol resin derivative (B!) or (B2) was used. In Comparative Examples 1, 3, and 5, neither phenol resin was used. The phenol resin was not used as the derivative, and the phenol resin (B3) was used instead of the phenol resin derivative in Comparative Examples 2, 4, and 6. The LOIs of Examples 1 to 12 were higher than those of Comparative Examples 1 to 6, It exhibits better flame retardancy. Therefore, the use of a phenol resin derivative having a good carbon forming ability in a thermoplastic resin composition can provide good flame retardancy regardless of the base resin. Even if the base resin does not have or has only Poor carbon forming ability, phenol resin derivatives can also provide good flame retardancy. The present invention can be easily implemented by those skilled in the art. Many modifications and variations are considered within the scope of the following claims. (Please read the notes on the back and fill out this page)

-Installation--------Set---------Line I Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperative Printed This paper scale applies China National Standard (CNS) A4 specification (210 X 297 mm) )

Claims (1)

1314944 No. 91100013, Revision 4 of 1998. 98. 4. 29 Revision Year Θ 6. Patent application scope: 1. A composition for retarding combustion of thermoplastic resin, comprising: (A) 100 parts by weight of a thermoplastic resin as a base resin; (B) about 0.1 to 100 parts by weight represented by the following formula Phenol 5 lipid derivative; Wherein R! is an alkyl group of Ci_34; an aryl group; an aryl group substituted with an alkyl group; an alkyl group containing a ruthenium, an N-, a P- or an S-; a ruthenium-, N-, P-, or S- An aryl group; or an alkyl group substituted with an alkyl group of 〇-, N-, P-, or S-, R2, R3, and R4 are a nitrogen group, a C?-34 alkyl group, an aryl group; a substituted aryl group; an alkyl group containing a fluorene-, N-, P-, or S-; an aryl group containing a fluorene-, N-, P-, or S-; or a 0-, N-, P-, Or an alkyl group-substituted aryl group of S-; and η is an integer of from 1 to 10,000; and 15 (C) of from about 1 to 50 parts by weight of the phosphorus compound. 2. The retardation combustion thermoplastic resin composition according to claim 1, wherein the base resin is selected from the group consisting of polyacrylonitrile-butadiene-styrene copolymer (AB S resin) and rubber. Polystyrene resin (HIPS), acrylonitrile-styrene-acrylic copolymer 20 (AS A resin), methacrylic acid-butadiene-styrene copolymer 19 1314944 . (MB S resin), acrylonitrile-ethyl Acrylic-styrene copolymer (AES tree), polycarbonate (PC), polyethylene (PE), polypropylene (PP), polyethylene terephthalate (PET), polybutylene terephthalate Groups of (PBT), polyethylene (PVC), polydecyl acrylate 5 (PMMA), polydecylamine (PA), and copolymers thereof, and blends thereof. 3. The composition of the retardation-fired thermoplastic resin according to claim 1, wherein the resin derivative is selected from the group consisting of o-cresol novolac epoxy resin, phenol epoxy resin 10 resins, and mixtures thereof. 4. The retardation combustion thermoplastic resin composition according to claim 1, wherein the phosphorus compound is selected from the group consisting of a phosphate compound, a phosphoamidate compound, and oxygen. Compound 15 (oxaphosphorane compound) a thiophosphoric acid compound, a phosphonium morpholine compound, an azophosphorus compound, and a mixture thereof. 5. The composition of a delayed combustion thermoplastic resin according to claim 4, wherein the phosphate compound and the aminophosphoric acid 20 salt compound are represented by the following formula: 20 (II) 1314944 Wherein R3, R4, and R5 are hydrogen or an alkyl group of C^-4, and X is an aryl group of C6_20 or an alkyl group substituted with C6.20, which is derived from resorcinol, decyl alcohol, bisphenol a derivative of -A, and a diol of bisphenol-S, 5 Y is oxygen or nitrogen, and m is in the range of 0 to 4. 6. The composition of a retardation combustion thermoplastic resin according to claim 4, wherein the oxaphosphorane compound is represented by the following formula: (Π1) 10 wherein R丨 is 'hydrogen, an alkyl group of Ch6, or an aryl group of C6_15, R2 and R3 are an aryl group of fluorene or C, _6, and η is in the range of 1 to 3. 7. The composition of the delayed combustion thermoplastic resin according to claim 4, wherein the carboxyphosphinic acid compound is represented by the following formula: 〇Ri—Ρ—R 2 —C02H (iv) OH 21 15 1314944 wherein Rl The hydrogen group, the alkyl group of Cm2, the aryl group of C6.i, or the aryl group 'R>2 substituted by C?-15 is a C!-i2 extension base, C!_!2 · A cyclic alkyl group, an aromatic group of C6.12, or an alkyl group of C6.12, substituted for an aryl group. 8. The composition for retarding combustion thermoplastic resin according to claim 4, wherein the phosphate morpholine compound is represented by the following formula: 〇 r l ii r 0, u 0 R1 0 R2 0 P 0—r2-o-p- “炎Ί Π 〇 -O-Rt I R1 (V) wherein R is a C6_20 aryl group or an alkyl substituted C6_20 aryl 10 group, and 112 is (6.3 〇 aryl or alkyl substituted C6_3 fluorene, X is 1 or 2, and η and m The number average degree of polymerization, and n + m is 0 to 5. 9. The composition of the retardation combustion thermoplastic resin according to claim 4, wherein the azo-phosphorus compound is represented by the following formula (VI) _ or ( V11) means ·· Ri γ Ri R3——P=N -P=N- -p—(r3)4 (VI) R2 R,”k 22 15 1314944 (V11) wherein Ri, R2, and R3 are each an alkyl group, an aryl group, an alkyl-substituted aryl group, an aryl aryl group, an alkoxy group, an aryloxy group, an amine group, or a hydroxyl group, and k is from 0 to 10 An integer of; alkoxy and aryloxy may be substituted by an alkyl group, an aryl group, an amine group, a benzyl group, a nitro group, or an aryl group having a hydroxyl group. The retardation combustion thermoplastic resin composition of claim 1, further comprising up to about 50 parts by weight of the additive per 100 parts by weight of the base resin, the additive A group of 10 free impact modifiers, thermal stabilizers, oxidation inhibitors, light stabilizers, and inorganic fillers such as talc, alumina, mica, glass fibers, organic or inorganic pigments, and/or dyes are selected. A molded article obtained by the composition of a delayed combustion thermoplastic resin according to any one of claims 1 to 40. twenty three