TWI302922B - Flameproof thermoplastic resin compositions - Google Patents

Description

1302922 J repair (more stomach page nine, invention description r I one - one [invention of the technical field] The present invention relates to a flame resistant thermoplastic resin composition, especially by introducing a cyclic phosphonate compound A thermoplastic resin composition having a good flame resistance and heat resistance in a rubber modified polystyrene resin and a polyphenylene ether resin. [Prior Art] Polyphenylene ether resin has good heat resistance. High impact resistance and good dimensional stability, so the resin is widely used. However, due to the observation that 10 to the polyphenylene ether resin itself has excessive heat resistance, resulting in poor processing, it will be polyphenylene ether. Resin-doped rubber modified polystyrene resin or styrene resin to improve the processability of electrical products such as personal computers, fax machines, etc. To this end, it is necessary to use doped polyphenylene ether resin and Rubber modified polystyrene resin should be used as an electronic or electrical product. It must be added with flame resistance in the resin. It is known to add a flame retardant property by adding a halogen-containing compound or The elemental compound is in the rubber-modified styrene resin. However, during the molding process, the release of the hydrogen halide gas easily leads to the model of the venomous insect, and the gas released by the combustion is toxic and fatal; In particular, more than 20 bromine (iv) will produce toxic gases such as dioxin or sulphur when burned, so flame resistance is considered to be the most important consideration in the development of non-containing compounds. U.S. Patent No. 3,639,506 discloses the use of triphenyl phosphate. As a flame retardant, esters provide flame retardant properties in polyphenylene-based and styrenic resins. However, in this example, the resin group is lowered by the addition of triphenyl phosphate.

Therefore, it is necessary to additionally add a pixel-containing compound to reduce the heat resistance and heat resistance of the 1302922-resistant product. U.S. Patent No. 3,883,613, the disclosure of which is incorporated herein by reference in its entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire portion U.S. Patent No. 4,526,917 discloses the use of a <RTI ID=0.0>> However, a large amount of flame retardant is required to achieve sufficient flame retardant effect. Accordingly, the present invention utilizes a cyclic phosphonic acid-based compound fusion rubber to modify the composition of a flame-retardant thermoplastic resin having a good flame resistance but not losing its heat resistance. Things. SUMMARY OF THE INVENTION A primary object of the present invention is to provide a flame resistant thermoplastic resin composition which uses a cyclic phosphonic acid compound as a flame retardant and is stable to combustion. Another object of the present invention is to provide a flame resistant thermoplastic resin composition having good heat resistance. The remainder of the present invention will be further disclosed in the following patent application. The flame resistant thermoplastic resin composition of the present invention comprises (A) 20 to 90 20 parts by weight of a rubber modified polystyrene resin; (B) 10 to 80 parts by weight of a polyphenylene ether resin; (C) 0.1 Up to 30 parts by weight of the cyclic phosphonic acid compound per 1 part by weight of the sum of the (A) and (B) compositions; and (D) 0 to 25 parts by weight of the aromatic phosphate compound per 100 parts by weight of the sum (A) And (B) the composition. [Embodiment] 1302922 (A) Rubber modified polystyrene resin used in the present invention as a base resin for rubber modified polystyrene resin, which can be doped with a rubber. Aromatic single monomer (aromatic) Mono-alkenyl monomer) and / or alkyl ester 5 monomer, prepared by polymerization with heat or a polymerization initiator. The rubber which can be used in the present invention includes butadiene rubbers, isoprene rubbers, styrene-butadiene copolymers and alkylacrylic rubbers. The rubber amount is 0 to 30 parts by weight, preferably 0 10 to 15 parts by weight. In addition, the monomer used in the rubber modified polystyrene resin is selected from the group consisting of one or more of the following materials, including: an aromatic monoolefin monomer, an alkyl ester monomer of acrylic acid or methacrylic acid; The volume is 70-100 parts by weight, preferably 85.97 parts by weight. 15 The resin composition of the present invention may be polymerized by heat or a polymerization initiator; the polymerization initiator used in the present invention is selected from the group consisting of one or more of the following substances, including: organic peroxidation Such as benzoyl peroxide, t-butyl hydroperoxide, acetyl peroxide, and cumene hydroperoxide or azo compounds Such as azobisisobutyronitrile (ALBN). The rubber-modified polystyrene resin of the present invention can be produced by a conventional polymerization reaction, for example, a bulk polymerization, a suspension polymerization, an emulsion polymerization or a combination thereof, wherein a bulk polymerization method is preferably used.

1302922 In order to achieve the desired physical properties of the doped rubber modified polystyrene resin and the polyphenylene ether resin, the average size of the rubber particles is preferably 丨·6·ηι (Ζ-average), more preferably 〇·25 to 3 · 5μηι (ζ-average). The rubber-modified polystyrene resin or rubber-free polyphenylene ether resin can be used alone or in combination of 5. (Β) Poly(phenylene ether ether) resin (pρiyphenyiene ether, ρρε) The polyphenylene ether resin is added to a rubber modified polystyrene resin to increase flame resistance and heat resistance. Examples of the poly(phenylene ether) resin include poly(2,6-bisindenyl-1,4-phenylene) ether, poly(2,6-diethyl-1,4-phenylene) ether, poly( 2,6_bispropyl·indole, 4-phenylene ether, poly(2-methyl-6-ethyl-1,4-phenylene)ether, poly(2-methyl-6-propyl) Base-1,4-phenylene ether, poly(2-ethyl-6-propyl-1,4- extended) ether, poly(2,6-diphenyl-1,4-benzene) a copolymer of poly(2,6-bismethylβ1,4-phenylene)ether 15 and poly(2,3,6-trimethyl-1,4·phenylene) ether, (2,6-Dimethylphenylene)ether and poly(2,3,5-triethyl-M-extended) ether 2 were combined. It is preferred to use a copolymer of poly(2,6-bismethyl-i,4-phenylene)ether and poly(2^,6-didecyl-1,4-phenylene)ether with poly(2). , 6_bismethyl_ι 4 phenyl)ether, more preferably poly(2,6-bismethyl·1,4-phenylene) ether. The degree of polymerization of the 20 polyphenylene ether is not particularly limited, but thermal stability or processability of the resin composition must be considered. Preferably, the viscosity of the phenyl ether is 25 于·2 to 8.8. The base resin comprises 20 to 90 parts by weight of a rubber-modified polystyrene resin (Α) and 10 to 80 parts by weight of a polystyrene resin (β). 8 25

1302922 (C) cyclic phosphonic acid_compound The cyclic phosphonate compound of the present invention is represented by the following formula ();

'(I); its center and! ^Substituted as a substituted or unsubstituted 2Ci_C2g hydrocarbyl group, a substituted 5 or unsubstituted Ci-C2g alkenyl group, a substituted or unsubstituted C^-Cm alkynyl group, a substituted or unsubstituted arylene group, a substituted or unsubstituted C6_C3 ( An aralkyl group, a substituted or unsubstituted Ci-Cso heteroalkyl group, a substituted or unsubstituted c6-c30 heteroarylene group, a substituted or unsubstituted C6_C3() heteroarylalkyl group; and the hydrazine is hydrazine or 1. Examples of cyclic phosphonate compounds containing structural formula (1) include fluorenyl-10-(5-ethyl-2-indolyl-1,3,2-dioxaphorinan-5yl)methylphosphonium phosphonate P-oxyl, decyl-bis(5-ethyl-2-methyl-l,3,2-dioxaphorinan-5-yl)phosphonate P, P-dioxy. (D) The cyclic phosphonate compound of the present invention is used in an amount of from 0.1 to 30 parts by weight per 100 parts by weight of the (A) and (B) compositions. 15 (D) Fangxiang dish ester compound The aromatic phosphate compound of the present invention is represented by the following formula (Π):

, (II); 1302922; Η, ΙΙ 28 · .. - _ υΛ*... .-." where R3, 114 and 1 are respectively hydrogen or Cm alkyl; X is a C6-20 aryl group or Is an alkyl substituted C6.20 aryl group derived from a diol derivative such as resorcinol, hydroquinone and p-phenol propane; and n is 〇~4. Where η is 0, the compound represented by formula (II) is triphenyl 5 phosphate, trimethyl sulfonate, trixyrenyl phosphate, tris (2,6-dimethyl basic) acid S (2,6-di-tert-butylbenzene) filled with acid, and similar, when η is 1, the compound includes resorcinol bis(diphenyl phosphate), resorcinol double (2,6 -di-tert-butylbenzene phosphate, resorcinol bis(2,4-di-tert-butylphenyl) phosphate, hydroquinone bis(2,6-di-tert-butylphenyl) phosphate, p-benzene Diphenol bis 10 (2,4-di-tert-butylbenzene) acid ester and similar. The aromatic saccharate compounds of the present invention may be used singly or in combination. The aromatic phosphate compound of the present invention is used in an amount of from 0 to 25 parts by weight per 1 part by weight of the base resin. The flame resistant resin composition of the present invention may further comprise a conventional additive such as a heat resistant agent, an antioxidant, a light stabilizer, an organic or inorganic colorant, a dye and an inorganic filler. The additive is used in an amount of from 0 to 30 parts by weight per 100 parts by weight of the base resin. The above-described embodiments are merely examples for convenience of description, and the scope of the claims is intended to be limited to the scope of the claims. EXAMPLES The ingredients for preparing a flame resistant thermoplastic resin composition are illustrated in the examples and comparative examples: (Α) rubber modified polystyrene resin 10 1302922

(a!) Rubber-modified polystyrene resin: High-impact polystyrene (product name · HR-1380F) from Cheil Industries Inc., Korea. The butadiene rubber has a particle size of 1.5/m. And the rubber content weighs 6.5% by weight. (a2) Styrene resin: General purpose polystyrene (GPPS) (product name: HF-2680) having an average molecular weight of 210,000 by Cheil Industries Inc. was used. (B) Poly(phenylene ether) resin (PPE) (th) Powdered poly(2,6-dimethyl-phenylene ether) (product name: P-402) from Asahi Kasei Co., Japan was used. The average particle size is a few μηι.

(b2) Powdered poly(2,6-dimercapto-phenyl ether) from GE (product 1 〇: ΗΡΡ-820) was used. The average particle size is a few μπι. (C) The cyclic phosphonate compound uses a flame retardant 1045 of Rhodia Co., which contains 20.8% of phosphorus [one containing 8 weight percent of mercapto-bis(5-ethyl-2-indolyl-1,3) , 2-dioxaphorian_5-based fluorenylphosphonic acid quinone P-oxyl, with 15 weight percent 15% decyl-bis(5-ethyl-2-mercapto-l,3,2-dioxaphorinan-5-based a mixture of phosphonates P, P-dioxy).

(D) Aromatic Phosphate Compound (<1丨) was used in Japan Daihachi Chemical with a melting point of 48 ° C for triphenyl®. 2〇 (d2) Use Japan Daihachi Chemical benzodiazepine (2,6-di-tert-butylphenyl)phosphoric acid (product name · PX220). (<13) Japan Daihachi Chemical double-anti-A second acid (product name: CR-741) was used. (d4) Using Japanese Daihachi Chemical resorcinol diphosphate (product 11 1302922 ί—name: CR-733S). —..............-j (E) Additives Teflon (registered trademark) 7 illusion of Dup〇m Company. Examples 1 to 11 5 . 8 Compounds appearing in the table - and extruded in a general twin-screw: extruded into pellets at 200 to 280 ° C; resin pellets dried at 3 ° % at 8 °, and using a 6 oz injection molding machine at 18 〇~28 (processed into the test sample in rc, the temperature is 40~80. (:; the flame resistance of the test sample is tested with UL94VB, the thickness is 1/8); the heat resistance test is performed with α§τμ 10 D-1525 Tests below 5 kg; test results are presented in Table 1. Table 1 Examples Relative Examples (a〇(a2) 1 2 3 4 5 6 7 8 9 10 11 1 2 3 4 (A) 67 67 67 67 67 67 67 37 30 67 70 75 67 67 67 67 (B) (bi) (b2) 33 33 33 33 33 33 33 33 33 30 25 33 33 33 33 (C) 3 3 3 3 5 10 15 3 3 4 5 ( D〇9 - - - - (D) (d2) - 16 - 14 9 4 10 10 10 10 19 Touch • (d3) - - 17 - - 20 Howling (d4) - - - 12 - 15 (E) 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0. 3 0. 3 0. 3 0. 3 UL94 1/8” V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 V- 1 V- 1 V- 1 V- 1 VST 87 86. 5 86 86· 5 88 92 96 94 94 90 86 83 84 83 83

As described above, the use of the cyclic phosphonate compound and the aromatic phosphate compound as a flame retardant exhibits good flame resistance and heat resistance as compared with the resin composition using the aromatic phosphate compound alone. 12 1302922

I view! i 2# repair (more) is replacing page I The present invention can be completed by iiTii llFli [Arts Department 1]. Many modifications and variations are obvious to the point of the invention and are disclosed in the scope of the disclosure. [Simple description of the diagram] 5 None

[Main component symbol description] None

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Claims (1)

1302922 No. 93139337, revised page of September 1995.......-df * ; X. Patent application scope: -1. A fuel-burning thermoplastic resin composition, including: (A) 20 to 90 parts by weight of rubber Modified polystyrene resin; (B) 10 to 80 parts by weight of one poly(phenylene ether) resin; 5 10 15 (C) 0.1 to 30 parts by weight per 100 parts by weight of the total of the (A) and (B) compositions a cyclic phosphonate compound which is represented by the following formula (I) 〇I ch2 , II h3c—-ρ- x I Ri 2-x R| , (1); wherein 1 and 112 are respectively a substituted or unsubstituted alkylene group, a substituted or unsubstituted heart-fluorene (9) alkenyl group ( Alkenylene group), substituted or unsubstituted 匕/(9) alkynylene group, substituted or Unsubstituted 2C6-C3 arylene group, substituted or unsubstituted C6-C3 () arylakylene group, substituted or unsubstituted Ci-C2 heteroalkylene group, a substituted or unsubstituted C6-C3 heteroarylene group, a substituted or unsubstituted C6_C3 heteroaryl arylakylene group; and X is 0 or 1; and (D) per 100 parts by weight 4 to 25 parts by weight of the aromatic phosphate compound of the sum of the (A) and the (B) composition, which is represented by the following formula (II): 14 1302922 5 10 15 〇〇Rs % ? 0 ή %ψ%Β3Χ , 5 3 ^ X , formula (II); wherein R 3 , R 4 and R 5 are each hydrogen or hydrazine: "alkyl; hydrazine is aryl or county substituted C6.2g aryl, which is derived from diol The materials are, for example, 雠rcinol, hydr〇qum〇i and phenol bus-propane-A (busphenol_A); and η is 〇~4. 2·If Shenkouyue patent scope is the first! The flame-resistant thermoplastic resin composition according to the item, wherein the polyphenylene resin is selected from the group consisting of: poly(2,6-diindenyl), stilbene (tetra), poly( 2,6-Diethyl_μ_phenylene)ether, poly(2,6-dipropyldecylphenyl)ether, poly(2-methyl-ethylethyl-1,4-phenylene) Ether, poly(2-methyl-6-propyl.anthracene)phenyl, poly(2-ethylidene-anthracene-phenyl), poly(organic phenyl_μ_phenyl) Ether, poly(2,6-dimercapto-1,4-phenylene) and poly(2,3,6-trimethyl^,phenylphenyl) bond total H?{(2,6· Copolymerization of dimercaptopurine, 4-phenylene ether and poly(2,3,5-triethyl-1,4-phenylene) ether. 3. Flame resistance as described in the scope of the Shenqing patent scope a thermoplastic resin composition wherein the cyclic phosphonate compound is methyl-bis(5-ethyl_2-mercapto-1,3,2-di〇Xaph〇rinan-5-yl)methylmethylphosphine Acid ester p-oxyl or methyl-yl-(5-ethyl-2-methyl-l,3,2-dioxaphorinan-5-)phosphonate p,p-dioxy 0 4. The composition of the flame resistant thermoplastic resin as described in the scope of the patent application, which further comprises an anti-stress agent, an impact-resistant modification, a plasticizer, an inorganic filler 15 1302922 filling, a combustion stabilizer, an antioxidant, Compatibilizer, light stabilizer, pigment and/or dye. 16