JPH0368663A - Flame-retardant composition - Google Patents

Flame-retardant composition

Info

Publication number
JPH0368663A
JPH0368663A JP20440289A JP20440289A JPH0368663A JP H0368663 A JPH0368663 A JP H0368663A JP 20440289 A JP20440289 A JP 20440289A JP 20440289 A JP20440289 A JP 20440289A JP H0368663 A JPH0368663 A JP H0368663A
Authority
JP
Japan
Prior art keywords
flame
phosphate
parts
polymer
retardant
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
JP20440289A
Other languages
Japanese (ja)
Other versions
JP2802780B2 (en
Inventor
Masuo Iwata
岩田 満寿夫
Koji Inoue
幸次 井上
Ryoji Takahashi
高橋 良次
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
JNC Corp
Original Assignee
Chisso Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Chisso Corp filed Critical Chisso Corp
Priority to JP20440289A priority Critical patent/JP2802780B2/en
Publication of JPH0368663A publication Critical patent/JPH0368663A/en
Application granted granted Critical
Publication of JP2802780B2 publication Critical patent/JP2802780B2/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Abstract

PURPOSE:To prevent bleeding on a resin surface from occurring even under a high-temp. and high-humidity condition by compounding a thermoplastic polymer with a specific flame-retardant phosphate polymer and condensed ammonium phosphate. CONSTITUTION:A heterocyclic diamine and a phosphate compd. having a spiro ring are polymerized to give a flame-retardant phosphate polymer having a spiro ring of formula I (wherein R1 is formula II; and R2 to R5 are each H or alkyl), being a powder pref. with a particle diameter of 100mum or lower, and having a dissolution rate at 80 deg.C of 15wt.% or lower. A thermoplastic polymer comprising an ethylene or propylene homopolymer or a copolymer of these is compounded with 15-30 pts.wt. resulting phosphate polymer and 10-40 pts.wt. condensed ammonium phosphate being a powder with pref. a particle diameter of 100mum or lower and showing a dissolution wt. of 100mg when 10g of the powder is suspended in 90g of water and stirred at room temp. for 60min (dissolution rate, 1wt.%) or lower, thus producing 100 pts.wt. flame- retardant compsn.

Description

【発明の詳細な説明】 〈産業上の利用分野〉 本発明は、耐ブリード性に優れた難燃性組成物に関する
DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a flame retardant composition with excellent bleed resistance.

〈従来の技術〉 ポリオレフィン系樹脂に難燃性を付与するのに三酸化ア
ンチモンとデカブロモフェニレンエーテルとを組み合わ
せて用いることが一般的である。
<Prior Art> Antimony trioxide and decabromophenylene ether are generally used in combination to impart flame retardancy to polyolefin resins.

しかしこれは、ハロゲン含有化合物であり燃焼時に有毒
なハロゲンガスを発生し好ましくない。
However, this is a halogen-containing compound and generates toxic halogen gas when burned, which is undesirable.

また多価アルコールとしてペンタエリスリトールあるい
はトリス(2−ヒドロキシエチル)インシアネートなど
水酸基を多数持った化合物をポリオレフィン系樹脂に添
加して難燃性樹脂としているものもある。しかし水酸基
を多く持った化合物は一般に水に溶は易く好ましくない
There are also flame-retardant resins made by adding compounds having a large number of hydroxyl groups, such as pentaerythritol or tris(2-hydroxyethyl) incyanate, to polyolefin resins as polyhydric alcohols. However, compounds having a large number of hydroxyl groups are generally easily soluble in water and are not preferred.

スピロ環を有したフォスフェート化合物とメラミンとの
低分子塩をポリオレフィン樹脂に添加し難燃性を与えて
いる。 (特公昭63−19518号公報) 〈発明が解決しようとする問題点〉 しかし、従来の難燃剤は、低分子塩であるために化学構
造的に耐水性に劣っている。確かに常温の水では不溶性
もしくは難溶性であるが、50℃以上の水に於いてはこ
の不溶性難溶性は維持されない。このことはこの難燃剤
をオレフィン樹脂に添加した場合、多価アルコールを添
加した場合と同様に、樹脂表面への粉吹きであるブリー
ド現象が現われて好ましくない。
A low-molecular salt of a phosphate compound with a spiro ring and melamine is added to polyolefin resin to impart flame retardancy. (Japanese Patent Publication No. Sho 63-19518) <Problems to be Solved by the Invention> However, conventional flame retardants are low molecular salts and therefore have poor water resistance due to their chemical structure. It is true that it is insoluble or poorly soluble in water at room temperature, but this insolubility and poorly soluble property is not maintained in water at 50°C or higher. This is undesirable because when this flame retardant is added to an olefin resin, a bleed phenomenon occurs, in which powder is blown onto the resin surface, similar to when a polyhydric alcohol is added.

従来技術にあるように常温の水において不溶性であるだ
けでは、高温高湿の環境下にその難燃剤を添加した樹脂
をさらすまでもなく、加工時に樹脂上に難燃剤が浮きだ
し、外観上、好ましくない。
If the resin is insoluble in water at room temperature as in the conventional technology, there is no need to expose the resin containing the flame retardant to a high-temperature, high-humidity environment, and the flame retardant will float on the resin during processing, resulting in a poor appearance. Undesirable.

本発明は、高温高湿の環境にさらされても樹脂表面のブ
リード現象が起こらない難燃性組成物を目的とする。
The object of the present invention is to provide a flame retardant composition that does not cause bleeding on the resin surface even when exposed to a high temperature and high humidity environment.

〈問題点を解決するための手段〉 本発明は、次の一般式で示されるフォスフェート難燃性
重合体、 R1は、 (Rt Rs R* Rsは、水素原子またはアルキル
基)および縮合リン酸アンモニウムを含有することを特
徴とする難燃性組成物である。
<Means for solving the problems> The present invention provides a phosphate flame-retardant polymer represented by the following general formula, R1 is (Rt Rs R* Rs is a hydrogen atom or an alkyl group), and a condensed phosphoric acid This is a flame retardant composition characterized by containing ammonium.

本発明のフォスフェート難燃性重合体とは、複素環式ジ
アミンとスピロ環を有するフォスフェート化合物を重合
した難燃性重合体であり、次の式%式% (R* Rs R4Rsは、水素原子またはアルキル基
)本発明のフォスフェート難燃性重合体は、80℃の溶
出率が15重量%以下であることが好ましく、15重量
%を越えるとブリード性を改良することができない。ま
たフォスフェート難燃性重合体は、粒径100μm以下
の粉末を使用するのが、難燃性、加工性の点で好ましい
。フォスフェート難燃性重合体の使用量は、全難燃性組
成物100重量部に対し、15−30重量部であり、こ
の範囲外では、難燃性の効果が不十分か、ブリード性を
悪化させる。
The phosphate flame-retardant polymer of the present invention is a flame-retardant polymer obtained by polymerizing a phosphate compound having a heterocyclic diamine and a spiro ring, and has the following formula % formula % (R * Rs R4Rs is hydrogen atoms or alkyl groups) The flame-retardant phosphate polymer of the present invention preferably has a dissolution rate at 80° C. of 15% by weight or less, and if it exceeds 15% by weight, the bleedability cannot be improved. Further, it is preferable to use a powder having a particle size of 100 μm or less as the flame-retardant phosphate polymer in terms of flame retardancy and processability. The amount of the phosphate flame retardant polymer used is 15-30 parts by weight per 100 parts by weight of the total flame retardant composition; outside this range, the flame retardant effect may be insufficient or the bleed property may be reduced. make worse.

スピロ環を有するフォスフェート化合物として、3.9
−ジクロロ−2,4,8,10−テトラオキサ−3,9
−フォスフオスピロ(5,5)ウンデカン−3,9−ジ
オキサイドを例示することができる。この物質の合成方
法は、文献RATZAND  5WEETING  v
ol、28 1988 1608−1812に記載され
ている一般的な方法によればよい。また複素環式ジアミ
ンとして、ピペラジンまたはピペラジンの炭素原子に結
合した水素原子が、メチル基、エチル基、プロピル基な
どアルキル基に置換されな2−メチルビペラジン、2−
エチルピペラジン、2−プロピルピペラジンを原料とす
ることができる。
As a phosphate compound having a spiro ring, 3.9
-dichloro-2,4,8,10-tetraoxa-3,9
-Phosphospiro(5,5)undecane-3,9-dioxide can be exemplified. The method for synthesizing this substance is described in the document RATZAND 5WEETING v
The general method described in 28 1988 1608-1812 may be used. In addition, as heterocyclic diamines, 2-methylbiperazine, 2-methylbiperazine, 2-
Ethylpiperazine and 2-propylpiperazine can be used as raw materials.

本発明の難燃性組成物は、縮合リン酸アンモニウムは、
一般式(NHa)−4*P−Os、+ (式中のnは2
あるいはそれ以上の整数で表わされる)を使用でき、好
ましくは水中での溶解度が著しく低いものである。好ま
しくは、綜合リン酸アンモニウム粉末10gを水90g
に懸濁し室温にて60分攪拌した時の溶解溶出量が10
0mg(溶出率1重量%)以下である縮合リン酸アンモ
ニウムである。また縮合リン酸アンモニウムは、粒径1
00μm以下の粉末を使用するのが、難燃性、加工性の
点で好ましい。縮合リン酸アンモニウムの使用量は、全
難燃性組成物100重量部に対し、10−40重量部で
あり、この範囲外では、難燃性の効果が不十分か、ブリ
ード性を悪化させる。
In the flame retardant composition of the present invention, the condensed ammonium phosphate is
General formula (NHa)-4*P-Os, + (n in the formula is 2
or a larger integer) can be used, preferably those having extremely low solubility in water. Preferably, 10 g of combined ammonium phosphate powder is mixed with 90 g of water.
When suspended in water and stirred at room temperature for 60 minutes, the amount dissolved and eluted was 10
It is condensed ammonium phosphate with a concentration of 0 mg (elution rate 1% by weight) or less. In addition, condensed ammonium phosphate has a particle size of 1
It is preferable to use powder with a diameter of 00 μm or less in terms of flame retardancy and processability. The amount of condensed ammonium phosphate used is 10 to 40 parts by weight per 100 parts by weight of the total flame retardant composition; outside this range, the flame retardant effect is insufficient or the bleed property is deteriorated.

本発明の難燃性組成物は、ポリプロピレンまたはポリエ
チレンの単独重合体、これらの共重合体などの熱可塑性
重合体を含むものである。
The flame retardant composition of the present invention contains a thermoplastic polymer such as a homopolymer of polypropylene or polyethylene, or a copolymer thereof.

本発明の難燃性組成物は、熱可塑性重合体と縮合リン酸
アンモニウム、およびスピロ環を有するフォスフェート
難燃性重合体以外に、−膜内に使用される安定剤、充填
剤、顔料などを本発明の目的を損なわない範囲で添加す
ることができる。また本発明の難燃性組成物は、混合機
、造粒機を限定するものではない。
The flame retardant composition of the present invention includes, in addition to the thermoplastic polymer, condensed ammonium phosphate, and the phosphate flame retardant polymer having a spiro ring, - stabilizers, fillers, pigments, etc. used in the membrane. can be added within a range that does not impair the purpose of the present invention. Furthermore, the flame retardant composition of the present invention is not limited to mixers or granulators.

〈実施例〉 実施例1 撹拌機還流装置温度計及び滴下漏斗を備えた2部反応容
器に溶剤としてジクロロメタン600部及び3.9−ジ
クロロ−2,4,8,10−テトラオキサ−3,9−ホ
スフォスピロ(5,5)ウンデカン−3,9−ジオキサ
イドを118.8部トリエチルアミン81.0部を投入
し充分攪拌する。
Examples Example 1 600 parts of dichloromethane and 3,9-dichloro-2,4,8,10-tetraoxa-3,9- as solvent were added to a two-part reaction vessel equipped with a stirrer, reflux device, thermometer and addition funnel. 118.8 parts of phosphospiro(5,5)undecane-3,9-dioxide and 81.0 parts of triethylamine were added and stirred thoroughly.

ジクロロメタン400部に溶解させた無水ピペラジン3
4.4部をゆっくり滴下する。還流温度に保ち5−10
時間反応をおこなう。冷却後濾過し熱水で2回洗浄した
のち乾燥する。得られたフォスフェート難燃性重合体1
.は白色ないしわずかに黄色であり熱水及びアセトン、
アルコールなどの有機溶剤には溶解しない。
Anhydrous piperazine 3 dissolved in 400 parts dichloromethane
4. Slowly drop 4 parts. Keep at reflux temperature 5-10
Perform a time reaction. After cooling, it is filtered, washed twice with hot water, and then dried. Obtained phosphate flame-retardant polymer 1
.. is white to slightly yellow; hot water and acetone;
It does not dissolve in organic solvents such as alcohol.

この得られたフォスフェート難燃性重合体1.を粉砕機
によって粒径を40μm以下に粉砕した。
This obtained phosphate flame retardant polymer 1. was pulverized to a particle size of 40 μm or less using a pulverizer.

次に安定剤を含んだ ポリプロピレンパウダー(ネモMFR8)     7
0部縮合リン酸アンモニウム        20部フ
ォスフェート難燃性重合体1.    10部をヘンシ
ェルミキサーを使ってブレンドし、通常の単軸押出機を
使い溶融混練温度180−230℃でペレタイズし、難
燃性組成物を得た。この難燃性組成物を210℃、30
 kg / cm 2の条件で熱プレスをおこない3−
mのプレートを得た。このプレートを評価し、第1表に
示す。
Next, polypropylene powder containing stabilizer (Nemo MFR8) 7
0 parts condensed ammonium phosphate 20 parts phosphate flame retardant polymer 1. 10 parts were blended using a Henschel mixer and pelletized using a conventional single-screw extruder at a melt-kneading temperature of 180-230°C to obtain a flame-retardant composition. This flame retardant composition was heated at 210℃ for 30 minutes.
Heat press under the conditions of kg/cm2 3-
m plates were obtained. This plate was evaluated and is shown in Table 1.

実施例2 実施例1のフォスフェート難燃性重合体l。Example 2 Phosphate flame retardant polymer l of Example 1.

15部 縮合リン酸アンモニウム        15部ポリプ
ロピレンパウダー         70部とする以外
は実施例1と同様に行なう。
15 parts condensed ammonium phosphate 15 parts polypropylene powder The same procedure as Example 1 was carried out except that the amount was 70 parts.

実施例3 実施例1のフォスフェート難燃性重合体1゜10部 縮合リン酸アンモニウム        15部ポリプ
ロピレンパウダー        75部とする以外は
実施例1と同様に行なう。
Example 3 The same procedure as in Example 1 was repeated, except that the phosphate flame-retardant polymer of Example 1 was 1°, 10 parts, condensed ammonium phosphate, 15 parts, and polypropylene powder, 75 parts.

比較例1 実施例1のフォスフェート難燃性重合体1゜30部 ポリプロピレンパウダー        70部とする
以外実施例1と同様に行なう。
Comparative Example 1 The same procedure as in Example 1 was carried out except that the phosphate flame-retardant polymer of Example 1 was 1.30 parts and the polypropylene powder was 70 parts.

比較例2 ジクロロペンテイト1モルに対し79772モルを15
分100℃で反応したスピロ環を有したホスフェート化
合物とメラ主ンの塩(低分子塩2.)10部 縮合リン酸アンモニウム        20部ポリプ
ロピレンパウダー        70部とする以外は
実施例1と同様に行なう。
Comparative Example 2 79772 mol per 1 mol of dichloropentate at 15
The same procedure as in Example 1 was carried out, except that the salt consisting of a phosphate compound having a spiro ring and a mela-based salt (low molecular salt 2.) reacted at 100° C., 10 parts, condensed ammonium phosphate, 20 parts, and 70 parts polypropylene powder.

評価はつぎの方法で行う。Evaluation is performed in the following manner.

難燃性の評価はUL−94(Unde rwr 1te
rsLaboratories)、及び酸素指数法(A
STM  D−2863)に準じておこなう。UL−9
4では、垂直燃焼試験を採用しこれは、難燃性によりV
−2V−IV−0に区分する。また、綿着火率として、
UL−94の垂直燃焼試験をおこなう際に、試験片の下
方12インチに置いた外科用脱脂綿に溶融物が落下し外
科用脱脂綿が着火したか否かを確認する。
Flame retardant evaluation is UL-94 (Unde rwr 1te
rsLaboratories), and the oxygen index method (A
STM D-2863). UL-9
4, a vertical combustion test was adopted, which was determined by the flame retardancy.
Classified into -2V-IV-0. In addition, as the cotton ignition rate,
When performing the UL-94 vertical combustion test, it is determined whether the molten material falls onto surgical cotton wool placed 12 inches below the test piece and the surgical cotton ignites.

ブリート性に対する評価は、温度80°C湿度80%に
調節した恒温恒湿器に各試験片を3日、7日放置した後
、目視により試験片のブリード性を評価する。
For evaluation of bleedability, each test piece was left in a constant temperature and humidity chamber adjusted to a temperature of 80° C. and a humidity of 80% for 3 or 7 days, and then the bleedability of the test piece was visually evaluated.

耐水性の評価は、重合体1.及び低分子塩2゜をそれぞ
れ10gを所定の温度の水90gに懸濁させ1時間その
温度で攪拌し仕込の10gに対する溶出量を溶出率とし
て表わす。
The evaluation of water resistance was as follows: Polymer 1. 10 g of each of 2° and a low molecular salt were suspended in 90 g of water at a predetermined temperature, stirred at that temperature for 1 hour, and the amount eluted per 10 g of charge was expressed as the elution rate.

耐熱性の評価は、SEI’KO熱分析装置 5SC−5
000を使って測定する。
Heat resistance evaluation was performed using SEI'KO thermal analyzer 5SC-5.
Measure using 000.

難燃性及び耐水性 耐熱性に関する評価結果を、次の第
1表、第2表に示する。
Flame retardancy and water resistance Evaluation results regarding heat resistance are shown in Tables 1 and 2 below.

〈発明の効果〉 複素環状ジアミンとスピロ環を有したフォスフェート難
燃性重合体、および縮合燐酸アンモニウムとを併用する
ことにより本発明の難燃性組成物は、従来技術のスピロ
環を有したフォスフェート化合物とメラミンとの低分子
の塩を添加した場合では避けることができなかったブリ
ードの発生を抑えることができた。さらに難燃性重合体
組成物としての難燃性のU L −94、酸素指数共に
すぐれていた。
<Effects of the Invention> By using a heterocyclic diamine, a phosphate flame-retardant polymer having a spiro ring, and condensed ammonium phosphate in combination, the flame-retardant composition of the present invention can be used in combination with a flame-retardant composition having a spiro ring than that of the prior art. It was possible to suppress the occurrence of bleed, which could not be avoided when a low-molecular salt of a phosphate compound and melamine was added. Furthermore, the flame retardant U L-94 and oxygen index as a flame retardant polymer composition were excellent.

Claims (1)

【特許請求の範囲】 1)次の一般式で示されるフォスフェート難燃性重合体
、▲数式、化学式、表等があります▼ R1は、 ▲数式、化学式、表等があります▼ (R_2R_3R_4R_5は、水素原子またはアルキ
ル基)および縮合リン酸アンモニウムを含有することを
特徴とする難燃性組成物。 2)全難燃性組成物100重量部に対し、ポリプロピレ
ンまたはポリエチレンと、縮合リン酸アンモニウム10
−40重量部、および80℃の溶出率が15重量%以下
のフォスフェート難燃性重合体を15−30重量部含有
することを特徴とする第1請項記載の難燃性組成物。
[Claims] 1) A phosphate flame-retardant polymer represented by the following general formula, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ R1 is ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (R_2R_3R_4R_5 is 1. A flame-retardant composition containing a hydrogen atom or an alkyl group) and condensed ammonium phosphate. 2) Polypropylene or polyethylene and 10 parts by weight of condensed ammonium phosphate per 100 parts by weight of the total flame retardant composition.
-40 parts by weight, and 15-30 parts by weight of a phosphate flame-retardant polymer having an elution rate of 15% by weight or less at 80°C.
JP20440289A 1989-08-07 1989-08-07 Flame retardant composition Expired - Lifetime JP2802780B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP20440289A JP2802780B2 (en) 1989-08-07 1989-08-07 Flame retardant composition

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP20440289A JP2802780B2 (en) 1989-08-07 1989-08-07 Flame retardant composition

Publications (2)

Publication Number Publication Date
JPH0368663A true JPH0368663A (en) 1991-03-25
JP2802780B2 JP2802780B2 (en) 1998-09-24

Family

ID=16489953

Family Applications (1)

Application Number Title Priority Date Filing Date
JP20440289A Expired - Lifetime JP2802780B2 (en) 1989-08-07 1989-08-07 Flame retardant composition

Country Status (1)

Country Link
JP (1) JP2802780B2 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007177861A (en) * 2005-12-27 2007-07-12 Enplas Corp Gear

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007177861A (en) * 2005-12-27 2007-07-12 Enplas Corp Gear

Also Published As

Publication number Publication date
JP2802780B2 (en) 1998-09-24

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