JPH07126477A - Non-halogenic flame retardant - Google Patents

Abstract

PURPOSE:To provide a non-halogenic flame retardant capable of improving the flame-retardancy of a thermoplastic resin with a non-halogenic compound while scarcely deteriorating the characteristics of the base resin. CONSTITUTION:This non-halogenic flame retardant is produced by reacting (A) a resin modified with a carboxylic acid anhydride with (B) a non-halogenic flame-retarding compound under melting. The flame retardant is produced preferably by mixing (A) a resin modified with a carboxylic acid anhydride with (B) a non-halogenic flame-retarding compound at a ratio of 80:20 to 20:80, compounding 100 pts.wt. of the obtained mixture with 0.01-5 pts.wt. of a catalyst accelerating the reaction of the components A and B, preferably further compounding (C) 5-50 pts.wt. of a phenolic resin and reacting the components under melting.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a non-halogen compound capable of imparting a high degree of flame retardancy to a thermoplastic resin such as a polyolefin resin, a polystyrene resin, or a polyphenylene oxide resin, although it is non-halogen. The present invention relates to flame retardants.

[0002]

2. Description of the Related Art Polyolefin resins, polystyrene resins, and polyphenylene oxide resins are used as a typical thermoplastic resin in a wide range of automobiles, electric parts, and other daily necessities. However, these thermoplastic resins are generally flammable, and once a fire occurs, they are easily burned and lost.
In some fields where these thermoplastic resins are used, such as automobile interior parts and textile products, it is mandatory by law to make them flame-retardant. Conventionally, halogen-based flame retardants, phosphorus-based flame retardants, nitrogen-based flame retardants, inorganic flame retardants and the like have been used to make flammable thermoplastic resins flame-retardant. However, halogen-based flame retardants have high flame-retardant effects, but they have drawbacks such as environmental problems and the generation of harmful gases during combustion.Phosphorus-based flame retardants reduce the heat resistance of resins and the deterioration of physical properties such as tensile strength. It has the drawback that the flame retardant causes bleeding. Further, in order to obtain an excellent flame retardant effect, it is necessary to add a large amount of the flame retardant to the inorganic flame retardant, which causes a drawback that the characteristics of the composition are deteriorated. From the above, it is most preferable that the thermoplastic resin can be made flame retardant by the polymer alloy of the thermoplastic resin and the halogen-free resin flame retardant.

[0003]

SUMMARY OF THE INVENTION The present invention is to provide a non-halogen flame retardant which improves the flame retardancy of a thermoplastic resin in a non-halogen manner with almost no deterioration in properties.

[0004]

The present inventors have studied a method of simply blending a thermoplastic resin and (B) a non-halogen flame-retardant compound in order to make the thermoplastic resin flame-retardant. It was found that the flame retardancy is insufficiently improved, and further, bleeding occurs, and characteristics such as cold resistance and heat resistance are deteriorated. Therefore, as a result of further diligent study, by carrying out a melt reaction of (A) a carboxylic acid anhydride-modified resin and (B) a non-halogen flame-retardant compound, bleeding, which is a conventional defect, without impairing flame retardancy, The inventors have found that cold resistance, heat resistance, etc. are improved and have completed the present invention. That is, the present invention relates to a non-halogen flame retardant characterized in that (A) a carboxylic acid anhydride-modified resin and (B) a non-halogen flame retardant compound are melt-reacted, and preferably (A) A catalyst for promoting the reaction of (A) and (B) with respect to 100 parts by weight of a mixture of a carboxylic acid anhydride-modified resin and a non-halogen flame-retardant compound (B) of 80:20 to 20:80. It is a halogen-free flame retardant obtained by blending 5 parts by weight, more preferably 5 to 50 parts by weight of (C) phenol resin, and subjecting the mixture to a melt reaction.

The carboxylic acid anhydride-modified resin which is the component (A) of the present invention has the appearance, cold resistance and mechanical properties which are deteriorated when the non-halogen flame retardant compound which is the component (B) is blended with the thermoplastic resin. It is a very important ingredient that has the function of improving. The modified polyolefin having a carboxylic acid anhydride group in the molecule used in the present invention is not particularly limited and is commercially available. For example, a copolymer of ethylene and maleic anhydride, an ethylene / acrylic acid copolymer, an ethylene / methacrylic acid copolymer, ethylene
Examples thereof include acrylate copolymers, terpolymers of ethylene / methacrylate copolymers and maleic anhydride.
The hydrogenated block copolymer containing a carboxylic acid anhydride group used in the present invention is not particularly limited and is commercially available, maleic anhydride-modified styrene-ethylene / butylene-styrene block copolymer, Examples thereof include maleic anhydride-modified styrene-ethylene / propylene-styrene block copolymers. The acid anhydride-modified block copolymer of the present invention is obtained by subjecting the block copolymer before hydrogenation to an acid anhydride having an unsaturated double bond.

The non-halogen flame-retardant compound used as the component (B) of the present invention is not particularly limited and is generally commercially available. Examples of the functional group include an amino group, an isocyanate group and an oxazoline group. Those having a polar group such as a hydroxyl group are preferably used. Specific examples of the compound include polyphosphoric acid, ammonium polyphosphate, phosphorus-based compounds such as amino group-modified phosphate, or hydroxyl group-containing phosphate, boric acid, boron-based compounds such as zinc borate, melamine or melamine cyanurate. Examples thereof include compounds, melamine phosphates, melamine derivatives such as melamine borate, and guanidine or guanidine derivatives such as guanidine sulfamate and guanidine phosphate. These non-halogen flame retardant compounds may be used alone or in combination of two or more.

The phenol novolac resin used as the component (C) of the present invention is not particularly limited and is commercially available. For example, formalin and phenols are mixed at a formaldehyde / phenols molar ratio of
The mixture was charged into a reaction kettle at a compounding ratio of 0.5 to 1.0, and a catalyst such as oxalic acid, hydrochloric acid, sulfuric acid, and toluenesulfonic acid was further added, and the mixture was heated and refluxed for an appropriate time. It can be obtained by a method such as vacuum dehydration or static dehydration for removing separated water, and further removing remaining water and unreacted phenols. The catalysts for promoting the reaction of the components (A), (B) and (C) used in the present invention are not particularly limited and are commercially available. For example, imidazoles include dimethylimidazole, amines and the like. Examples of the derivative include diazabicycloundecene, dimethylbenzylamine, and organic phosphines, and examples of the derivative thereof include triphenylphosphine.

The non-halogen flame retardant of the present invention is (A)
A halogen-free flame retardant characterized by comprising a carboxylic acid anhydride-modified resin as a component and a halogen-free flame-retardant compound as a component (B), which are blended at a ratio of 80:20 to 20:80 and melt-reacted. And preferably (A)
A catalyst that accelerates the reaction of (A) and (B) with respect to 100 parts by weight of a mixture of a carboxylic acid anhydride-modified resin and a non-halogen flame-retardant compound (B) of 80:20 to 20:80.
001 to 5 parts by weight, more preferably 5 to 50 parts by weight of the (C) phenol resin, and melt-reacted with a pressure kneader or Banbury mixer at 150 to 250 ° C. for 10 to 30 minutes. In the halogen-free flame retardant of the present invention, the carboxylic acid anhydride-modified resin as the component (A) and the halogen-free flame-retardant compound as the component (B) are used.
It must be blended in a ratio of 0:20 to 20:80. When the proportion of the halogen-free flame-retardant compound as the component (B) exceeds 80 wt%, the cold resistance and mechanical properties are insufficiently improved, and when it is less than 20 wt%, the flame retardance improving effect is insufficient. The catalyst that promotes the reaction between (A) and (B) is 0.
If it is less than 01 parts by weight, the effect of promoting the reaction tends to be insufficient, and if it exceeds 5 parts by weight, the effect does not change so much. When the compounding amount of the phenolic resin as the component (C) is less than 5 parts by weight, the auxiliary effect of improving the flame retardancy tends to be insufficient, and when it exceeds 50 parts by weight, the compatibility with the thermoplastic resin tends to decrease. It is in. As described above, the non-halogen flame retardant of the present invention has an effect of improving flame retardancy without substantially deteriorating the characteristics of the thermoplastic resin. The reason therefor is the carboxylic acid anhydride of the component (A). The compound produced by the reaction of the substance-modified resin with the non-halogen flame-retardant compound of the component (B) includes a component having an affinity for the thermoplastic resin and a component having an affinity for the non-halogen flame-retardant compound in one molecule. It is considered that it is possible to micro-disperse the non-halogen flame-retardant compound of the component (B) having good flame retardancy in the thermoplastic resin because it has. The halogen-free flame retardant of the present invention, further uses, other compounding agents depending on the purpose, for example, antioxidants, light stabilizers, pigments,
Dyes, mold release agents, plasticizers, reinforcing agents and extenders can be added. The halogen-free flame retardant of the present invention is preferably used in combination with an inorganic flame retardant such as magnesium hydroxide or aluminum hydroxide.

[0009]

EXAMPLES The present invention will be described below with reference to examples, but these are merely examples and the present invention is not limited thereto. Tensile test is ASTM-D638, cold resistance is J
IS K6301, oxygen index is ASTM-D2863,
Combustion test is based on Underwriters Laboratories safety standard U
The results are measured by the L94 combustion test (◯: burning time within 10 seconds, Δ: burning time of 10 seconds or more, × indicates complete burning). * Production example of non-halogen flame retardant (A to N) The non-halogen flame retardant is a batch of a predetermined amount of (A) a carboxylic acid anhydride-modified resin and (B) a non-halogen flame retardant compound. It was obtained by melting reaction at 160 to 200 ° C. for 30 minutes. Further, more preferably, (A) a carboxylic acid anhydride-modified resin, (B) a halogen-free flame-retardant compound, (C) a phenol novolac resin, and a catalyst are put into a pressure kneader all at once, and the temperature is 160 to 200 ° C.
It was obtained by melting reaction for 0 minutes. (A) carboxylic acid anhydride-modified resin and (B) non-halogen flame-retardant compound,
The reaction with (C) phenol novolac resin was confirmed by the difference in the infrared absorption spectrum peak intensity of the carboxylic acid anhydride group before and after the reaction.

* Halogen-free flame retardant (A) Maleic anhydride-modified styrene-ethylene / butylene-styrene block copolymer Tuftec RM-1913 {MAH-SEBS; manufactured by Asahi Kasei Co., Ltd.} is used as the component (A). Then, as the component (B), an amino group-containing phosphate ester {AA-1000; manufactured by Nippon Soda Co., Ltd.} was used. The composition is shown in Table 1, and a non-halogen flame retardant was obtained according to the production example. * As a non-halogen flame retardant (B) (A) component, maleic anhydride modified styrene-ethylene / butylene-styrene block copolymer Tuftec RM-1913 {MAH-SEBS; manufactured by Asahi Kasei Co., Ltd.} is used. As component B), a hydroxyl group-containing phosphate ester {C
R-757; manufactured by Daihachi Chemical Co., Ltd.}, and triphenylphosphine (TPP) was used as a catalyst. The composition is shown in Table 1, and a non-halogen flame retardant was obtained according to the production example. * As a non-halogen flame retardant (C) (A) component, maleic anhydride-modified styrene-ethylene / butylene-styrene block copolymer Tuftec RM-1913 {MAH-SEBS; manufactured by Asahi Kasei Co., Ltd.} is used. As component B), a hydroxyl group-containing phosphate ester {C
R-757; Daihachi Chemical Co., Ltd.} as a (C) component, straight phenol novolac resin {PN; Sumitomo Dures Co., Ltd. Sumilite Resin R PR-5147
0} as a catalyst and triphenylphosphine (TP
P) was used. The composition is shown in Table 1, and a non-halogen flame retardant was obtained according to the production example. * As the non-halogen flame retardant (D) (A) component, maleic anhydride modified styrene-ethylene / butylene-styrene block copolymer Tuftec RM-1913 {MAH-SEBS; manufactured by Asahi Kasei Co., Ltd.} is used. As component B), melamine phosphate {MPP-A;
Manufactured by Sanwa Chemical Co., Ltd., as a component (C), straight phenol novolac resin {PN; Sumitomo Durezu Co., Ltd. Sumilite Resin R PR-51470}
And triphenylphosphine (TPP) as the catalyst. The composition is shown in Table 1, and a non-halogen flame retardant was obtained according to the production example. * As a non-halogen flame retardant (E) (A) component, maleic anhydride-modified styrene-ethylene / butylene-styrene block copolymer Tuftec RM-1913 {MAH-SEBS; manufactured by Asahi Kasei Co., Ltd.},
As the component (B), melamine phosphate {MPP-A;
Manufactured by Sanwa Chemical Co., Ltd. was used. The composition is shown in Table 1, and a non-halogen flame retardant was obtained according to the production example.

* Halogen-free flame retardant (F) Maleic anhydride-modified polyolefin resin Bondine R AX8060 {MAH-PO; manufactured by Sumitomo CDF Co., Ltd.} is used as the component (A), and an amino group is used as the component (B). The contained phosphoric acid ester {AA-1000; manufactured by Nippon Soda Co., Ltd.} was used. The composition is shown in Table 2, and a non-halogen flame retardant was obtained according to the production example. * Halogen-free flame retardant (G) Maleic anhydride-modified polyolefin resin Bondine R AX8060 {MAH-PO; manufactured by Sumitomo CDF} is used as component (A), and hydroxyl group-containing phosphate ester is used as component (B). {CR-757; Daihachi Chemical Co., Ltd.
Manufactured by the manufacturer} and triphenylphosphine (TP
P) was used. The composition is shown in Table 2, and a non-halogen flame retardant was obtained according to the production example. * Halogen-free flame retardant (H) Maleic anhydride-modified polyolefin resin Bondine R AX8060 {MAH-PO; manufactured by Sumitomo CDF} is used as component (A), and hydroxyl group-containing phosphate ester is used as component (B). {CR-757; Daihachi Chemical Co., Ltd.
Was used as the component (C), and straight phenol novolac resin {PN; Sumirite resin R PR-51470} manufactured by Sumitomo Dures Co., Ltd., and triphenylphosphine (TPP) as the catalyst were used. The composition is shown in Table 2.
And a non-halogen flame retardant was obtained according to the production example. * Halogen-free flame retardant (I) Maleic anhydride-modified polyolefin resin Bondine R AX8060 {MAH-PO; manufactured by Sumitomo CDF} is used as the component (A), and melamine phosphate {MPP is used as the component (B). -A; Sanwa Chemical Co., Ltd.},
Straight phenol novolac resin as component (C) {PN; Sumilite Resin R manufactured by Sumitomo Dures Co., Ltd.
PR-51470} and triphenylphosphine (TPP) as catalyst. The composition is shown in Table 2, and a non-halogen flame retardant was obtained according to the production example. * Halogen-free flame retardant (J) Maleic anhydride-modified polyolefin resin Bondine R AX8060 {MAH-PO; manufactured by Sumitomo CDF} is used as the component (A), and melamine phosphate {MPP is used as the component (B). -A; manufactured by Sanwa Chemical Co., Ltd.} was used. The composition is shown in Table 2, and a non-halogen flame retardant was obtained according to the production example.

* Halogen-free flame retardant (K) As component (A), maleic anhydride-modified styrene-ethylene / butylene-styrene block copolymer Tuftec RM-1913 {MAH-SEBS; manufactured by Asahi Kasei Co., Ltd.} is used. Amino group-containing phosphate ester (AA-1000; manufactured by Nippon Soda Co., Ltd.) was used as the component (B), and triphenylphosphine (TPP) was used as the catalyst. The composition is shown in Table 3, and a halogen-free flame retardant was obtained according to the production example. * As the non-halogen flame retardant (L) (A) component, maleic anhydride-modified styrene-ethylene / butylene-styrene block copolymer Tuftec RM-1913 {MAH-SEBS; manufactured by Asahi Kasei Co., Ltd.} is used. As component B), a hydroxyl group-containing phosphate ester {C
R-757; manufactured by Daihachi Chemical Co., Ltd.}, and triphenylphosphine (TPP) was used as a catalyst. The composition is shown in Table 3, and a halogen-free flame retardant was obtained according to the production example. * Halogen-free flame retardant (M) Maleic anhydride-modified polyolefin resin Bondine R AX8060 {MAH-PO; manufactured by Sumitomo CDF} is used as the component (A), and amino group-containing phosphoric acid is used as the component (B). An ester {AA-1000; manufactured by Nippon Soda Co., Ltd.} was used, and triphenylphosphine (TPP) was used as a catalyst. The composition is shown in Table 3, and a halogen-free flame retardant was obtained according to the production example. * Non-halogen flame retardant (N) Maleic anhydride-modified polyolefin resin Bondine R AX8060 {MAH-PO; manufactured by Sumitomo CDF} is used as the component (A), and hydroxyl group-containing phosphate ester is used as the component (B). {CR-757; Daihachi Chemical Co., Ltd.
Manufactured by the manufacturer} and triphenylphosphine (TP
P) was used. The composition is shown in Table 3, and a halogen-free flame retardant was obtained according to the production example.

[0013]

[0014]

[0015]

(Examples 1 to 10) Polyethylene (PE; Ultzex 2022L manufactured by Mitsui Petrochemical Co., Ltd.) and polypropylene (PP; Sumitomo Noblen RH501 manufactured by Sumitomo Chemical Co., Ltd.) were used as thermoplastic resins, Using non-halogen flame retardant, magnesium hydroxide (M
gOH; Kyowa Chemical Co., Ltd. Kisuma 5B) was used together.
The blending and evaluation results are shown in Tables 4 and 5. (Examples 11 to 20) Polyphenylene ether (PPE; Asahi Kasei Corporation Zylon X0061) and polystyrene (PS; Sumitomo Chemical Co., Ltd. Sumibright E1) were used as thermoplastic resins.
63), a non-halogen flame retardant, and magnesium hydroxide (MgOH; Kyowa Chemical Co., Ltd. Kisuma 5
B) was used in combination. The blending and evaluation results are shown in Tables 6 and 7. (Comparative Examples 1 to 8) Polyethylene (PE;
Mitsui Petrochemical Co., Ltd. Ultzex 2022L), polypropylene (PP; Sumitomo Chemical Co., Ltd. Sumitomo Noblen RH501), non-halogen flame retardant, magnesium hydroxide (MgOH; Kyowa Chemical Co., Ltd.) Manufactured by Kisuma 5B) was also used. The formulations and the evaluation results are shown in Tables 8 and 9. (Comparative Examples 9 to 12) Polyphenylene ether (PPE; Zylon X0061 manufactured by Asahi Kasei Co., Ltd.) was added to the thermoplastic resin,
Polystyrene (PS; Sumitomo Chemical Co., Ltd. Sumibrite E163) is used, non-halogen flame retardant is used, and magnesium hydroxide (MgOH; Kyowa Chemical Co., Ltd.)
Kisuma 5B) was also used. The composition and the evaluation results are shown in Table 1.
It shows in 0.

[0017]

[0018]

[0019]

[0020]

[0021]

[0022]

[0023]

[0013]

As is apparent from the table, the non-halogen flame retardant of the present invention is a novel flame retardant which imparts a high degree of flame retardancy while maintaining the characteristics of the thermoplastic resin.

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Claims (7)

[Claims] 1. A modified polyolefin resin having (A) a carboxylic acid anhydride group in the molecule, a terminal polymer block containing at least two vinyl aromatic compounds as a main component, and at least one conjugated diene compound as a main component. One or more resins selected from the carboxylic anhydride modified products of the hydrogenated block copolymer obtained by hydrogenating a block copolymer comprising an intermediate polymer block and (B) a carboxylic anhydride A halogen-free flame-retardant compounded with at least one non-halogen flame-retardant compound selected from the group consisting of phosphorus, nitrogen and boron compounds having a functional group capable of reacting with groups Fuel. 2. The ratio of (A) carboxylic acid anhydride-modified resin to (B) halogen-free flame-retardant compound is 80:20.
The non-halogen flame retardant according to claim 1, which is ˜20: 80. 3. An imidazole or an amine which accelerates the reaction of (A) and (B) with respect to 100 parts by weight of a mixture of (A) a carboxylic anhydride modified resin and (B) a non-halogen flame retardant compound. And at least one catalyst selected from organic phosphines and organic phosphines and their derivatives, and 0.01 to 5 parts by weight of the catalyst are added, and the mixture is melt-reacted. Non-halogen flame retardant. 4. A compound comprising 5 to 50 parts by weight of the (C) phenolic resin and 100 parts by weight of the halogen-free flame retardant according to claim 1, 2 or 3, and melt-kneading. The halogen-free flame retardant according to 1, 2 or 3. 5. The halogen-free flame-retardant compound (B) is a phosphoric acid ester and / or polyphosphate having a functional group selected from an amino group, an isocyanate group, an oxazoline group, and a hydroxyl group. The halogen-free flame retardant according to 2, 3 or 4. 6. The non-halogen flame retardant according to claim 1, 2, 3 or 4, wherein the non-halogen flame retardant compound (B) is boric acid and / or zinc borate. 7. The non-halogen flame-retardant compound (B) is at least one compound selected from melamine, melamine derivatives, guanidine, and guanidine derivatives, 1, 2, 3 or 4. Non-halogen flame retardant.