JP2001089670A - Flame retardant and flame retarded resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a flame retardant having improved hygroscopicity and foamability inherent in ammonium polyphosphate and tris-(2-hydroxyalkyl) isocyanulate and improved tackiness, coloring (grey) and the like of the surface of a molding therefrom. SOLUTION: This flame retardant comprises ammonium polyphosphate (A), tris-(2-hydroxyalkyl)isocyanulate (B), a moistureproof agent (C), and optionally an inorganic fiber (D). This flame retarded resin composition is a resin composition containing the flame retardant, and especially a polypropylene resin composition containing the flame retardant.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an improvement in a flame retardant and a flame retardant resin composition containing ammonium polyphosphate and tris- (2-hydroxyalkyl) isocyanurate as main components.

[0002]

2. Description of the Related Art Heretofore, when a resin is made flame-retardant, a combination of an organic bromine compound and antimony trioxide, which are excellent in flame-retardant effect, physical properties, price and the like, has been used in many cases. However, recently, consideration has been required for toxicity and environmental issues, and hydrated metal compounds, phosphorus-based flame retardants, N-containing compounds, silicon-based compounds, and the like have been receiving attention. APP (ammonium polyphosphate) as a phosphorus-based flame retardant,
Red phosphorus, a phosphoric acid ester, or a metal salt of a phosphinic acid are used, and a combination with a hydrated metal compound or an N-containing compound (melamine cyanurate, tris- (2-hydroxyethyl) -isocyanurate, or the like) can be given.

For example, JP-A-9-296120 and JP-A-9-235480 disclose thermoplastic resins.
A flame-retardant resin composition containing a phosphate ester-based phenol resin and melamine cyanurate is mentioned. JP-A-9-278947 discloses a flame-retardant polyolefin resin composition containing melamine phosphate and ethylenediamine phosphate. JP-A-61-3635
No. 9 discloses a flame-retardant thermosetting resin composition containing a phosphate ester-based organic phosphorus compound and tris- (2-hydroxyethyl) -isocyanurate.

A flame retardant mainly composed of an N-containing compound is often used in combination with a P compound, not with an N compound alone. The flame retardant effect of P and an inert gas generated from the N compound, and a gas generated from P and N are used. It is thought to be due to the combined effect of the above. APP
The flame retardant based on (ammonium polyphosphate) may be used in combination with a triazine compound, a phosphate and pentaerythritol. For example, JP-A-10-25379 discloses a rubber composition containing ammonium polyphosphate, melamine, and pentaerythritol.

[0005]

The flame retardant containing ammonium polyphosphate and tris- (2-hydroxyalkyl) isocyanurate as main components has a high hygroscopic property and a high foaming property as its own properties, and has a high surface roughness of a molded article. There is stickiness and coloring (gray), and a resin using a flame retardant containing only the two components has room for improvement in practical use. An object of the present invention is to provide a flame retardant which overcomes these problems and does not decrease the flame retardant effect, and a resin composition using the flame retardant.

[0006]

As a first aspect, the present invention relates to a flame retardant containing ammonium polyphosphate (A), tris- (2-hydroxyalkyl) isocyanurate (B), and a moisture-absorbing agent (C). It is.

As a second aspect, the first aspect obtained by coating the particle surfaces of ammonium polyphosphate (A) and tris- (2-hydroxyalkyl) isocyanurate (B) with a moisture absorption inhibitor (C). The flame retardant described in 1.

A third aspect is a flame retardant containing ammonium polyphosphate (A), tris- (2-hydroxyalkyl) isocyanurate (B), a moisture absorption inhibitor (C), and an inorganic fiber (D).

As a fourth aspect, the particle surfaces of ammonium polyphosphate (A) and tris- (2-hydroxyalkyl) isocyanurate (B) are coated with a moisture-absorbing agent (C), and these (A), The flame retardant according to the third aspect obtained by further adding an inorganic fiber (D) to (B) and (C).

As a fifth aspect, the particle surfaces of ammonium polyphosphate (A), tris- (2-hydroxyalkyl) isocyanurate (B), and inorganic fiber (D) are
The flame retardant according to the third aspect, which is obtained by coating with a moisture absorption inhibitor (C).

As a sixth aspect, tris- (2-hydroxyalkyl) isocyanurate (B) is a compound of tris- (2
-Hydroxyethyl) isocyanurate according to any one of the first to fifth aspects.

As a seventh aspect, the flame retardant according to any one of the first to sixth aspects, wherein the moisture absorption inhibitor (C) is liquid paraffin or silicone oil.

According to an eighth aspect, the flame retardant according to any one of the third to seventh aspects, wherein the inorganic fiber (D) is a calcium silicate whisker.

According to a ninth aspect, there is provided a resin composition containing the flame retardant according to any one of the first to eighth aspects.

A tenth aspect is the resin composition according to the ninth aspect, wherein the resin is a polyolefin resin.

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION The ammonium polyphosphate (A) used in the present invention is (NH ₄ ) _{n + 2} P _n O _{3n + 1.}
(Where n is an integer of 2 or more). Examples of the product include Taien S and Taien H, trade names manufactured by Taihei Chemical Co., Ltd., and Exorit-700, trade name manufactured by Hoechst.

As the component (B) tris- (2-hydroxyalkyl) isocyanurate used in the present invention, commercially available ones can be used. For example, in JP-A-56-81571, cyanuric acid is strictly weighed in a reaction medium such as glycol or aromatic-substituted lower alcohol, ketones such as methyl ethyl ketone or n-propyl ketone, or ethers such as tetrahydrofuran or dioxane. The alkylene oxide is subjected to an addition reaction using an alkali hydroxide, an amine or a quaternary ammonium salt as a catalyst. Journal of Organic Chemistry (28, 85-89, 1963)
Year), a method of reacting cyanuric acid with an alkylene oxide in a dialkylformamide or a dialkylacetamide under pressure or normal pressure. JP-A-10-158252 discloses a production method in which cyanuric acid and an alkylene oxide are reacted in a solvent using a triarylphosphine, a trialkylphosphine or a quaternary phosphonium salt as a catalyst. These tris- (2-hydroxyalkyl) isocyanurates are:
Tris- (2-hydroxyethyl) isocyanurate,
Tris- (2-hydroxypropyl) isocyanurate, tris- (2-hydroxybutyl) isocyanurate, tris- (α-methyl-β-hydroxypropyl) isocyanurate and the like can be mentioned. Especially tris
It is preferable to use (2-hydroxyethyl) isocyanurate.

The component (C) used in the present invention is preferably a liquid paraffin or silicone oil, which can be obtained as a commercial product. Silicone oil is a polymer having a main chain formed by alternately bonding silicon and oxygen having an organic group. The organic group is a methyl group, a phenyl group, or the like, and a hydrogen atom is also used.

Ammonium polyphosphate (A) and tris- (2-hydroxyalkyl) with anti-hygroscopic agent (C)
The coating of the isocyanurate (B) on the particle surface is as described in (A)
And (B) can be performed simultaneously or separately. These coatings are achieved by putting (A) and / or (B) into a mixing device such as a supermixer and adding the component (C) with stirring.

The combination of the components (A), (B) and (C) lowers the oxygen index (OI) a little, but loses the hygroscopicity and the foaming property and improves the stickiness of the surface of the molded article. In addition, the dispersibility when the flame retardant is dispersed in the resin is also improved.

In the present invention, a flame retardant resin is obtained by adding a flame retardant containing the above-mentioned components (A), (B) and (C) to the resin. The resin to be added is a polyolefin resin, for example, polypropylene, (low density or high density)
Polyethylene, EVA, EEA, and the like, or a blend resin thereof, and the like can be mentioned, and it is particularly preferable to use polypropylene. Polypropylene is used in the form of plastics or an elastomer, and can be used alone or as an alloy to which low-density polyethylene is added.

The flame-retardant resin composition can be formed by, for example, mixing a resin and a flame retardant with a super mixer or the like, kneading and granulating the mixture using a twin-screw extruder, and then performing injection molding.

Ammonium polyphosphate (A) and tris-
The flame retardancy when added to polypropylene (PP) by changing the ratio of (2-hydroxyalkyl) isocyanurate (B) is evaluated by oxygen index (OI), as shown in Table 1 below.

[Table 1] Table 1 ＼ Ingredients＼ Test number 1 2 3 4 5 6 ──────────────────────────────────── PP 79 79 79 79 79 79 A / B = 1 A / B = 2/1-21----A / B = 3/1--21---A / B = 5/1---21--A / B = 7/1----21-A / B = 9/1-----21 ───────────────────────────酸 素 Oxygen index (OI) 26.0 28.5 30.0 29.5 28.5 26.0 ────────────────────────────── ──────

From the above Table 1, the weight ratio of ammonium polyphosphate (A) to tris- (2-hydroxyalkyl) isocyanurate (B) is (A) / (B) 3/1.
Can be used which fall within the range of 1/1 to 9/1.

The moisture-absorbing agent (C) is used in an amount of 1 to 100 parts by weight based on the total weight of ammonium polyphosphate (A) and tris- (2-hydroxyalkyl) isocyanurate (B).
It is 10 parts by weight, preferably 3 to 5 parts by weight.

Ammonium polyphosphate (A), Tris-
(2-hydroxyalkyl) isocyanurate (B),
The relationship between the amount of the flame retardant comprising the moisture-absorbing agent (C) and the oxygen index to the resin (for example, polypropylene: PP) is as shown in Table 2 below.

[Table 2] Table 2 ＼ Ingredients＼ Test number 1 2 3 4 ──────── ──────────────────── PP 90.0 83.3 80.0 76.9 (A + B + C) 10.0 16.7 20.0 23.1 ──────────────酸 素 Oxygen index (OI) 23.0 26.0 28.0 28.5 ─────────────────────────── ─

According to Table 2, the addition of the components (A) + (B) + (C) to the resin has a remarkable effect at 15 to 16% by weight or more, and reaches a substantially constant level at about 40% by weight. Even if it is added more, the effect corresponding to the addition cannot be obtained and it is not economical. Therefore, the addition of the components (A) + (B) + (C) to the resin is preferably in the range of 10 to 30% by weight.

When polypropylene is used as the resin,
Table 3 shows the relationship between MFR (melt flow rate) and flame retardancy.

[Table 3] Table 3 ＼ Ingredients＼ Test number 1 2 3 4 5 6 ──────────────────────────────────── PP (MFR 5) 83.3 − − − 80.0 − PP (MFR 10)-83.3---80.0 PP (MFR 25)--83.3---PP (MFR 30)---83.3--(A + B + C) 16.7 16.7 16.7 16.7 20.0 20.0 ───── ─────────────────────────────── Oxygen index (OI) 26.0 25.5 27.0 27.0 28.0 29.0 ──────── ────────────────────────────

[Table 4] Continued from Table 3 ──────────────────────────────────── Ingredients ＼ Test number 7 8 9 10 11 12 ──────────────────────────────────── PP (MFR 5)--76.9-- − PP (MFR 10) − − − 76.9 − − PP (MFR 25) 80.0 − − − 76.9 − PP (MFR 30) − 80.0 − − − 76.9 (A + B + C) 20.0 20.0 23.1 23.1 23.1 23.1 ─── ───────────────────────────────── Oxygen index (OI) 29.0 31.0 28.5 31.0 30.5 31.5 ────── ──────────────────────────────

The flame retardancy as viewed from the oxygen index tends to increase as the MFR of polypropylene (PP) increases. Therefore, when polypropylene having a low MFR is used, it is necessary to increase the amount of the component (A) + (B) + (C), and when polypropylene having a high MFR is used, (A) + (B) Good flame retardancy can be imparted even when the amount of + (C) component added is low.

By further adding an inorganic fiber (D) to the components (A) + (B) + (C), a higher flame retardant effect can be obtained. As the inorganic fibers (D) used in the present invention, for example, calcium silicate whiskers, potassium titanate fiber whiskers, wollastonite, magnesium hydroxide-based needle fiber whiskers and the like can be used. In particular, calcium silicate whiskers are preferred. For example, as an example of a calcium silicate whisker used, 6CaO · 6SiO ₂
· H ₂ having a composition of O, there is a commercially available Zonohaiji (manufactured by Ube Material Industries, Ltd.).

Ammonium polyphosphate (A) and tris- (2-hydroxyalkyl) isocyanurate (B)
A first method in which the surface of the particles is coated with a moisture-absorbing agent (C) and inorganic fibers (D) are further added to (A), (B) and (C), or ammonium polyphosphate (A) , Tris- (2-hydroxyalkyl) isocyanurate (B), and inorganic fiber (D)
It is obtained by a second method of coating with a moisture absorption inhibitor (C). (A) + (B) or (A) + (B) +
When coating the component (D) with the component (C),
The components (B) and (D) can be coated simultaneously or separately. These coatings are performed by a device such as a high-speed mixer, for example, a super mixer.

In the present invention, the above (A), (B),
A flame retardant resin is obtained by adding a flame retardant containing the components (C) and (D) to the resin. Examples of the resin to be added include polypropylene, polyethylene (low density or high density), EVA resin, EEA resin and the like, and it is particularly preferable to use polypropylene. Polypropylene is used in the form of plastics and elastomers, and can be used alone or as an alloy to which low-density polyethylene is added.

The flame-retardant resin composition can be obtained by mixing the resin and the flame retardant with, for example, a super mixer, kneading and granulating using a twin-screw extruder or the like, and molding with an injection molding machine or the like. .

The amount of the inorganic fiber (D) added and the flame retardancy and impact resistance of the resin are as shown in Table 4 below.

[Table 5] Table 4 {Component} Test No. 1 2 3 4 5 6 7 ＰＰ PP (MFR30) 80.0 80.0 79.4---- PP (MFR25)---80.0 80.0 80.0 80.0 (A + B) 20.0------(A + B + C)-20.0 19.8 20.0 20.0 20.0 20.0 (D)--0.8-0.5 1.0 1.5 ─── ───────────────────────────────── Oxygen index (OI) 29.0 31.0 32.0 29.0 30.5 32.5 31.5 IZOD 2.20-3.22- ---────────────────────────────────────

In Table 4, PP represents polypropylene, and I
ZOD indicates an impact resistance test value. The addition amount of the inorganic fiber (D), particularly the addition amount of the calcium silicate whisker,
It is 1 to 10 parts by weight, preferably 3 to 5 parts by weight based on 100 parts by weight as the total weight of the components (A) + (B) + (C). If the amount of the inorganic fiber (D) is too large, the oxygen index decreases.

The flame retardant of the present invention includes fillers such as magnesium hydroxide, zinc borate, and talc, as well as various modifiers such as silane-based, titanium-based, and aluminum-based coupling agents, as long as the physical properties are not impaired. Fillers, antioxidants, antistatic agents, ultraviolet inhibitors, deterioration inhibitors, lubricants and pigments can be added.

[0037]

Examples: As the component (A), ammonium polyphosphate (trade name: Taien H, manufactured by Taihei Chemical Co., Ltd.), and as the component (B), tris- (2-hydroxyethyl) isocyanurate [produced by Nissan Chemical Industries, Ltd .; Product name NF-SE],
(C) Liquid paraffin as a component [Mobile Oil Co., Ltd.
(Trade name: HW-350), calcium silicate whisker (trade name: Zonoheidi, manufactured by Ube Materials Co., Ltd.) as component (D), polypropylene elastomer (commercially available) as resin, polypropylene resin (Nippon Polychem Co., Ltd.)
Manufactured by Novatec BC3, MFR10].

Example 1 72 parts by weight of ammonium polyphosphate and 24 parts by weight of tris- (2-hydroxyethyl) isocyanurate were charged into a Henschel mixer and premixed, and then 4 parts by weight of liquid paraffin was added with stirring. Then, the surfaces of ammonium polyphosphate and tris- (2-hydroxyethyl) isocyanurate were coated with liquid paraffin to obtain a flame retardant 1.

Example 2 69 parts by weight of ammonium polyphosphate and 23 parts by weight of tris- (2-hydroxyethyl) isocyanurate were charged into a Henschel mixer, and 4 parts by weight of liquid paraffin was added with stirring, and ammonium polyphosphate was added. And the surface of tris- (2-hydroxyethyl) isocyanurate were coated with liquid paraffin, and 4 parts by weight of calcium silicate whiskers were further added and mixed to obtain a flame retardant 2.

Example 3 Resins (A) and (A) + (D) were added to the resin at the ratios shown in Table 5.
After the components, (A) + (B) + (D) components, the flame retardant 1 or the flame retardant 2 were mixed by a Henschel mixer or the like, kneading, granulation and injection molding were performed using a twin screw extruder.

[Table 6] Table 5 {Component} Test number 1 2 3 4 5 6 7 ＰＰ PP elastomer--------PP resin 83.3 80.0 76.9 80.0 75.0 73.0 70.0 (A) − − − − − − − (B) − − − − − − − − (C) − − − − − − − − (D) − − − − − − − Black pigment − ----2.0-Flame retardant 1 16.7 20.0 23.1----Flame retardant 2---20.0 25.0 25.0 30.0 ──────────────────────── ────────────

[Table 7] Continuation of Table 5 {Component} Test No. 8 9 Comparative Test No. 1 2 3 ────────────────────────────── PP elastomer 75.0 75.0 75.0 75.0 75.0 PP resin − − − − − (A) − − 25.0 24.0 20.0 (B) − − − − 4.0 (C) − − − − (D) − − − 1.0 1.0 Flame retardant 1 25.0 − − − − Flame retardant 2 − 25.0 − − − ─────────中 で In Table 5, PP elastomer is polypropylene elastomer,
PP resin refers to polypropylene resin.

Example 4 The resin compositions of Test Nos. 1 to 9 and Comparative Test Nos. 1 to 3 shown in Table 5 were subjected to an oxygen index and a UL94 combustion test to obtain flame retardancy and impact strength (IZOD). ) Was evaluated.
Table 6 shows the evaluation results.

[Table 8] Table 6 ──────────────────────────────────── Results ＼ Test number 1 2 3 4 5 6 7 ──────────────────────────────────── Oxygen index (OI) 25.5 29.0 31.0 30.5 33.0 32.0 34.5 ──────────────────────────────────── IZOD 2.97 2.79 2.99 3.24 2.98 2.96 1.99 ─────────────────────────────── Combustion test (UL94) <Judgment> V-2 V-2 V-2 NG V -2 V-2 V-0 ────────────────────────────────────

[Table 9] Continued from Table 6 ──────────────────────────────────── Results ＼ Test number 8 9 Comparative test number 1 2 3 Oxygen index (OI) 29.0 32.0 20.0 22.5 30.0 燃 焼 Combustion test (UL94) <Judgment> NG V-0 NG NG V-0 ────────────────────────────────────

[0042]

According to the present invention, the flame-retardant comprising ammonium polyphosphate (A) and tris- (2-hydroxyalkyl) isocyanurate (B) has a hygroscopic property, a foaming property and a resin molding containing the flame retardant. In order to improve the stickiness and colorability (gray) of the surface of the product, the particle surfaces of ammonium polyphosphate (A) and tris- (2-hydroxyalkyl) isocyanurate (B) are treated with a moisture-absorbing agent (C). It was coated using As a result, the defects of the raw material could be improved by surface treatment, and as a result, the fluidity and dispersibility of the resin composition were improved. However, the flame retardant effect of the component (A) + (B) + (C) is equal to or lower than that of the component (A) + (B). In the present invention, by adding an inorganic fiber (D) to the components (A) + (B) + (C), a resin molded article containing the flame retardant and the hygroscopicity and foaming properties of the flame retardant It was found that the surface was improved in stickiness and coloring (gray), and at the same time, had a higher flame retardant effect. The present invention exhibits excellent performance by adding these flame retardants to a resin, particularly a polypropylene resin.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat ゛ (Reference) C08L 23/02 C08L 23/02 C09K 21/02 C09K 21/02 21/04 21/04 21/10 21 / 10 21/14 21/14 (72) Inventor Genichiro Ochiai 9-6-19 Togasa, Toride-shi, Ibaraki Prefecture (72) Inventor Susumu Suda 3-7-1, Kandanishikicho, Chiyoda-ku, Tokyo Nissan Chemical Industry Co., Ltd. F-term (Reference) 4H028 AA07 AA30 BA06 4J002 AE052 BB031 BB061 BB081 BB121 CP032 CP042 DE078 DE188 DH056 DJ008 EU197 FA048 FB266 FB267 FD010 FD030 FD050 FD068 FD070 FD090 FD100 FD136 FD137 FD170

Claims (10)

[Claims] 1. A flame retardant comprising ammonium polyphosphate (A), tris- (2-hydroxyalkyl) isocyanurate (B), and a moisture-absorbing agent (C). 2. The method according to claim 1, which is obtained by coating the particle surfaces of ammonium polyphosphate (A) and tris- (2-hydroxyalkyl) isocyanurate (B) with a moisture absorption inhibitor (C). Fire retardant. 3. A flame retardant containing ammonium polyphosphate (A), tris- (2-hydroxyalkyl) isocyanurate (B), a moisture-absorbing agent (C), and an inorganic fiber (D). 4. A particle surface of ammonium polyphosphate (A) and tris- (2-hydroxyalkyl) isocyanurate (B) is coated with a moisture-absorbing agent (C),
The flame retardant according to claim 3, which is obtained by further adding an inorganic fiber (D) to (A), (B) and (C). 5. A method in which ammonium polyphosphate (A), tris- (2-hydroxyalkyl) isocyanurate (B), and inorganic fiber (D) are coated on their particle surfaces with a moisture-absorbing agent (C). The flame retardant according to claim 3, which is used. 6. The flame retardant according to claim 1, wherein the tris- (2-hydroxyalkyl) isocyanurate (B) is tris- (2-hydroxyethyl) isocyanurate. 7. The flame retardant according to claim 1, wherein the moisture absorption inhibitor (C) is liquid paraffin or silicone oil. 8. The flame retardant according to claim 3, wherein the inorganic fibers (D) are calcium silicate whiskers. 9. A resin composition containing the flame retardant according to any one of claims 1 to 8. 10. The resin composition according to claim 9, wherein the resin is a polyolefin resin.