JP2001187843A - Flame retarder for resin and flame retardant resin composition - Google Patents

Flame retarder for resin and flame retardant resin composition

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Publication number
JP2001187843A
JP2001187843A JP2000368515A JP2000368515A JP2001187843A JP 2001187843 A JP2001187843 A JP 2001187843A JP 2000368515 A JP2000368515 A JP 2000368515A JP 2000368515 A JP2000368515 A JP 2000368515A JP 2001187843 A JP2001187843 A JP 2001187843A
Authority
JP
Japan
Prior art keywords
resin
weight
flame
flame retardant
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
JP2000368515A
Other languages
Japanese (ja)
Other versions
JP3193029B2 (en
Inventor
Kazuhiro Matsubara
一博 松原
Kohei Kita
孝平 北
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Asahi Kasei Corp
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Asahi Kasei Corp
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Abstract

PROBLEM TO BE SOLVED: To provide a flame retardant resin composition which is excellent in flame retardancy, heat resistance and electric insulation property and doe not cause fuming at a molding process and pollution and corrosion on the dye by adding a phosphoric ester flame retardant having an excellent heat resistance. SOLUTION: The flame retarded resin composition comprises (A) a flame retardant for resins which retardant has a specific structure crosslinked with bisphenol A, contains not more than 1 wt.% of a diaryl phosphate and not more than 30 wt.ppm in total of metals and has a weight loss of not more than 15 wt.% in TGA when kept at 300 deg.C for 20 min and (B) a non-halogen synthetic resin.

Description

【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION

【0001】[0001]

【発明の属する技術分野】本発明は、ハロゲン元素を含
まない難燃剤、さらに詳しくは熱安定性に優れる燐酸エ
ステル難燃剤と、その難燃剤を添加して得られる、難燃
性樹脂組成物に関する。
BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a flame retardant containing no halogen element, and more particularly to a phosphoric ester flame retardant having excellent heat stability, and a flame retardant resin composition obtained by adding the flame retardant. .

【0002】[0002]

【従来の技術】合成樹脂は一般に軽く、耐水性、耐薬品
性、電気絶縁性、機械的諸物性などに優れ、かつ成形加
工が容易であるため、建築材料、電気・電子・家電用材
料、自動車用材料、繊維材料などとして幅広く用いられ
ている。一方で、合成樹脂は一般に可燃性であり、難燃
性を付与するための様々な提案がなされている。これら
難燃化の最も一般的な手段は、有機ハロゲン化合物、燐
化合物、無機水和物などの難燃剤を、樹脂成型品の調製
時に配合する方法である。
2. Description of the Related Art Synthetic resins are generally light, excellent in water resistance, chemical resistance, electrical insulation, mechanical properties, etc., and are easy to mold. It is widely used as a material for automobiles and a fiber material. On the other hand, synthetic resins are generally flammable, and various proposals have been made for imparting flame retardancy. The most common means of flame retardation is a method of blending a flame retardant such as an organic halogen compound, a phosphorus compound, or an inorganic hydrate at the time of preparing a resin molded product.

【0003】上記難燃剤のうち、有機ハロゲン化合物、
特に臭素化合物は、多くの合成樹脂に対して優れた難燃
効果を示すので、最も広く使用されている。しかし、こ
の難燃剤には、遊離するハロゲンのために樹脂組成物の
耐候性と電気特性、特に電気絶縁性が低下する問題や、
樹脂成型時に熱分解してハロゲン化水素を発生して作業
環境を汚染し、金型の腐食や樹脂の着色、ゲル化を引き
起こす問題がある。また、火災などによる燃焼に際し
て、腐食性で、人体に有害なハロゲン化水素ガスと共
に、多量の煙を発生するという問題もある。さらに、有
機ハロゲン化合物の難燃効果を飛躍的に増加させるため
に通常難燃助剤として添加される酸化アンチモンに対し
て発ガン性が指摘されており、ハロゲン化合物を含まな
い難燃剤が強く求められている。ハロゲンを含まない難
燃剤としては、水酸化アルミニウムや水酸化マグネシウ
ムなどの無機水和物が知られている。しかし、これらは
難燃効果が小さく、充分な難燃性を得るためには多量に
添加する必要があり、この為、樹脂本来の物性が損なわ
れる欠点があった。
[0003] Among the above flame retardants, organic halogen compounds,
In particular, bromine compounds are most widely used because they exhibit excellent flame retardant effects on many synthetic resins. However, this flame retardant has the problem that the weather resistance and the electrical properties of the resin composition, especially the electrical insulation, are reduced due to the liberated halogen,
There is a problem that thermal decomposition occurs during resin molding to generate hydrogen halide, thereby contaminating the working environment, causing mold corrosion, resin coloring, and gelling. In addition, there is also a problem that a large amount of smoke is generated together with a hydrogen halide gas which is corrosive and harmful to the human body upon burning by a fire or the like. In addition, carcinogenic properties have been pointed out for antimony oxide, which is usually added as a flame retardant aid to dramatically increase the flame retardant effect of organic halogen compounds. Have been. Inorganic hydrates such as aluminum hydroxide and magnesium hydroxide are known as halogen-free flame retardants. However, these have a small flame-retardant effect and must be added in a large amount in order to obtain sufficient flame-retardant properties. Therefore, there is a disadvantage that the physical properties of the resin are impaired.

【0004】燐化合物、特に有機燐酸エステルは、ハロ
ゲンを含まず、良好な難燃効果が得られる難燃剤として
汎用されている。代表的な有機燐酸エステルとしては、
トリフェニルホスフェート(TPP)、トリクレジルホ
スフェート(TCP)、トリキシリルホスフェート(T
XP)等のトリアリール燐酸エステルが挙げられる。し
かしこれらの化合物は比較的沸点が低く、樹脂との押し
出し、成型時に揮発して作業環境を汚染したり、金型の
汚染を引き起こしたり、成型品の表面にしみだして外観
を損なうなどの問題があった。特に金型汚染は、そのま
ま放置すると成型不良や汚染物の成型品へ転写してスト
レスクラックを引き起こすなどの深刻な問題が生じるた
め、成型作業を中断して金型をクリーニングするなどの
対策が必要で、生産性を著しく低下させる原因となって
いた。
[0004] Phosphorus compounds, especially organic phosphoric esters, do not contain halogen and are widely used as flame retardants which provide good flame retardant effects. Representative organic phosphates include:
Triphenyl phosphate (TPP), tricresyl phosphate (TCP), trixylyl phosphate (T
XP) and the like. However, these compounds have relatively low boiling points, extruding with the resin, volatilizing during molding and contaminating the working environment, causing contamination of the mold, and exuding on the surface of the molded product to impair the appearance. there were. In particular, mold contamination can cause serious problems such as improper molding and transfer of contaminants to molded products, causing stress cracks if left as it is, so it is necessary to take measures such as interrupting molding work and cleaning the mold. In this case, the productivity was significantly reduced.

【0005】これらの欠点を解決する揮発性の低い燐酸
エステルとしては、米国特許第2520090号明細書
や欧州特許公開出願明細書第129824号、同第12
9825号、同第135726号、特公昭54−328
18号公報、特公昭62−25706号広報、特公平2
−18336号公報などに記載されている燐酸エステル
オリゴマーがすでに知られている。これらの化合物の中
でも、2,2−ビス(4−ヒドロキシフェニル)プロパ
ン(以下、ビスフェノールAと略す)の残基により架橋
された、下記一般式(1)で表される燐酸エステルオリ
ゴマーは、レゾルシノールなどの単環フェノール類残基
で架橋されたものに比べ耐熱性と耐加水分解性が高いこ
とが特開平7−258539号などに記載されており、
特に好ましい。
[0005] Phosphoric esters having low volatility which solve these drawbacks include those described in US Pat. No. 252,090 and European Patent Application Publication Nos. 129824 and 12298.
No. 9825, No. 135726, Japanese Patent Publication No. 54-328
No. 18, Japanese Patent Publication No. 62-25706, Special Publication No. 2
A phosphate ester oligomer described in, for example, US Pat. Among these compounds, a phosphate ester oligomer represented by the following general formula (1) cross-linked by a residue of 2,2-bis (4-hydroxyphenyl) propane (hereinafter abbreviated as bisphenol A) is resorcinol It is described in JP-A-7-258439 and the like that the heat resistance and the hydrolysis resistance are higher than those crosslinked with a monocyclic phenol residue such as
Particularly preferred.

【0006】[0006]

【化3】 (式中、nは0〜10の整数であり、R1〜R4は各々
独立に、フェニル基、トリル基又はキシリル基である。
またnが2以上の場合、複数あるR4は各々同一でも異
なっても良い。)
Embedded image (In the formula, n is an integer of 0 to 10, and R1 to R4 are each independently a phenyl group, a tolyl group, or a xylyl group.
When n is 2 or more, a plurality of R4s may be the same or different. )

【0007】また、燐酸エステルオリゴマーの熱安定性
を支配する重要な因子の一つが、一般式(1)のn=0
の成分に相当する沸点の低いトリアリールホスフェート
の量であることは良く知られており、例えば特公昭62
−25706号公報には、この成分の割合を組成物全体
に対し40重量%以下とすべき事が記載されている。し
かし本発明者らの研究よると、燐酸エステルオリゴマー
の熱安定性は製造条件によるばらつきが大きく、例えば
連続成型で大きな問題となる金型汚染は、式(1)で示
される化合物を用いた場合においてもトリアリールホス
フェート含有量を規定したのみでは防止できず、特にポ
リフェニレンエーテル系樹脂やポリカーボネート系樹脂
などの比較的成型温度の高い、いわゆるエンジニアリン
グプラスチックに対して用いるとしばしば問題を生じる
事がある。また金型汚染の激しい難燃剤は同時に成型機
や金型の腐食を引き起こしやすく、さらに樹脂組成物の
電気絶縁性を低下させる傾向が見られた。
One of the important factors governing the thermal stability of the phosphoric acid ester oligomer is n = 0 in the general formula (1).
It is well known that the amount of triaryl phosphate having a low boiling point corresponding to the component of
Japanese Patent Publication No. 25706 discloses that the proportion of this component should be 40% by weight or less based on the whole composition. However, according to the study by the present inventors, the thermal stability of the phosphate ester oligomer greatly varies depending on the production conditions. For example, mold contamination which is a major problem in continuous molding is caused by using the compound represented by the formula (1). However, this cannot be prevented only by regulating the content of the triaryl phosphate, and a problem often arises particularly when the resin is used for a so-called engineering plastic having a relatively high molding temperature, such as a polyphenylene ether resin or a polycarbonate resin. In addition, the flame retardant with severe mold contamination tends to cause corrosion of the molding machine and the mold at the same time, and furthermore, the electric insulation of the resin composition tends to decrease.

【0008】特開平5−1079号公報には、耐熱性の
良い有機燐酸エステルとして、2位と6位にアルキル基
を持つ1価フェノール残基を置換基とする高純度の芳香
族ジホスフェートとその製造方法が示されている。しか
しこの化合物は高融点の結晶性固体であり、樹脂と相溶
性をもつ液状の燐酸エステルオリゴマー組成物に対して
成型加工性が劣る問題がある。この為、樹脂に対して相
溶性を持ち、熱安定性に優れて金型汚染などの問題を起
こすことのない、安定した品質の難燃剤の開発が熱望さ
れてきた。
Japanese Patent Application Laid-Open No. Hei 5-1079 discloses a highly heat-resistant organic phosphoric acid ester having a high-purity aromatic diphosphate having a substituent of a monohydric phenol residue having an alkyl group at the 2- and 6-positions. The manufacturing method is shown. However, this compound is a crystalline solid having a high melting point, and has a problem that molding processability is inferior to a liquid phosphate ester oligomer composition having compatibility with a resin. Therefore, development of a flame retardant of stable quality which has compatibility with resin, has excellent thermal stability and does not cause problems such as mold contamination has been eagerly desired.

【0009】[0009]

【発明が解決しようとする課題】本発明は、優れた耐熱
性を持つ燐酸エステル難燃剤と、その難燃剤を添加して
得られる、難燃性、耐熱性、電気絶縁性に優れ、成形加
工時の発煙、金型汚染、腐食を引き起こさない難燃性樹
脂組成物を提供することを目的とする。
DISCLOSURE OF THE INVENTION The present invention relates to a phosphate ester flame retardant having excellent heat resistance, and a flame-retardant, heat-resistant, and electrically insulating material obtained by adding the flame retardant. An object of the present invention is to provide a flame-retardant resin composition that does not cause smoke, mold contamination, and corrosion at the time.

【0010】[0010]

【課題を解決するための手段】本発明者らは、前記課題
を解決するため、難燃剤の熱安定性の低下がいかなる原
因によるものかを検討した。その結果、燐酸エステルオ
リゴマーそのものの分解温度及び揮発温度は十分高いも
のの、合成時に副生する下記式(2)で表されるジアリ
ール燐酸と、触媒などに由来する金属分が加熱時に燐酸
エステルオリゴマーのエステル交換反応による低分子量
化と加水分解反応を促進する作用を持ち、この結果発生
する揮発成分が金型の汚染を引き起こすことを突き止め
た。そして、難燃剤の熱安定性を大幅に改善するために
は、金属分とジアリール燐酸の含有量を共に各々特定の
値以下とすることが必要であり、これにより成形加工時
の金型の汚染や腐食、樹脂組成物の電気絶縁性低下等の
問題も解決できることを見いだし、本発明を完成するに
至った。
Means for Solving the Problems In order to solve the above problems, the present inventors have studied what causes the decrease in the thermal stability of the flame retardant. As a result, the decomposition temperature and volatilization temperature of the phosphate ester oligomer itself are sufficiently high, but the diarylphosphoric acid represented by the following formula (2) by-produced at the time of synthesis and the metal component derived from the catalyst and the like are converted into the phosphate ester oligomer by heating. It has the effect of accelerating the reduction of molecular weight and the hydrolysis reaction by transesterification, and found that the resulting volatile components cause mold contamination. In order to greatly improve the thermal stability of the flame retardant, it is necessary that both the content of the metal and the content of the diarylphosphoric acid are each equal to or less than a specific value. The inventors have found that problems such as corrosion, corrosion, and a decrease in the electrical insulation of the resin composition can be solved, and have completed the present invention.

【0011】すなわち本発明は、以下の通りである。 1.(A)下記一般式(1)で表される燐酸エステルオ
リゴマーの混合物からなり、下記一般式(2)で表され
るジアリール燐酸の含有量が1重量%以下で、金属分の
含有量合計が30重量ppm以下であり、かつ、TGA
による、不活性ガス雰囲気中100℃/分の昇温速度で
300℃まで加熱し、そのままその温度に保持した時
の、加熱開始から20分間の重量減少率が15重量%以
下である樹脂用の難燃剤と、(B)非ハロゲン合成樹脂
からなる難燃性樹脂組成物。
That is, the present invention is as follows. 1. (A) A mixture of a phosphate ester oligomer represented by the following general formula (1), the content of the diarylphosphoric acid represented by the following general formula (2) is 1% by weight or less, and the total content of the metal components is 30 ppm by weight or less and TGA
When the resin is heated to 300 ° C. at a rate of 100 ° C./min in an inert gas atmosphere and kept at that temperature, the rate of weight loss for 20 minutes from the start of heating is 15% by weight or less. A flame-retardant resin composition comprising a flame retardant and (B) a non-halogen synthetic resin.

【0012】[0012]

【化4】 (式中、nは0〜10の整数であり、R1〜R4は各々
独立に、フェニル基、トリル基又はキシリル基である。
またnが2以上の場合、複数あるR4は各々同一でも異
なっても良い。)
Embedded image (In the formula, n is an integer of 0 to 10, and R1 to R4 are each independently a phenyl group, a tolyl group, or a xylyl group.
When n is 2 or more, a plurality of R4s may be the same or different. )

【0013】[0013]

【化5】 (式中、R1、R2は各々独立に、フェニル基、トリル
基またはキシリル基である。)
Embedded image (In the formula, R1 and R2 are each independently a phenyl group, a tolyl group, or a xylyl group.)

【0014】2.(B)非ハロゲン合成樹脂が、ポリフ
ェニレンエーテル樹脂、ポリカーボネート樹脂、ポリス
チレン樹脂、ポリエステル樹脂、ポリアミド樹脂から選
ばれる1種またはこれらを含む複数の樹脂の組み合わせ
である、上記1記載の難燃性樹脂組成物。 3.(B)非ハロゲン合成樹脂が、ポリフェニレンエー
テル樹脂及び/又はポリスチレン樹脂である、上記1記
載の難燃性樹脂組成物。 4.(B)非ハロゲン合成樹脂が、ポリカーボネート樹
脂及びABS樹脂である、上記1記載の難燃性樹脂組成
物。
2. (B) The flame-retardant resin composition according to the above item 1, wherein the non-halogen synthetic resin is one selected from a polyphenylene ether resin, a polycarbonate resin, a polystyrene resin, a polyester resin, and a polyamide resin, or a combination of a plurality of resins containing these. object. 3. (B) The flame-retardant resin composition according to the above item 1, wherein the non-halogen synthetic resin is a polyphenylene ether resin and / or a polystyrene resin. 4. (B) The flame-retardant resin composition according to the above item 1, wherein the non-halogen synthetic resin is a polycarbonate resin and an ABS resin.

【0015】以下本発明を詳述する。まず、本発明の樹
脂用難燃剤について説明する。上記一般式(1)で表さ
れる燐酸エステルオリゴマーは、米国特許第25200
90号明細書や特公昭62−25706号公報、特開昭
63−227632号公報などに記載されている公知の
方法で製造できる。すなわち、塩化マグネシウムや塩化
アルミニウムなどのルイス酸触媒存在下に、オキシ塩化
燐とビスフェノールA及び1価フェノール類を反応させ
て合成する。1価フェノール類としてはフェノール、ク
レゾール、キシレノールを単独または混合して、または
段階的に加えて反応させることができる。合成した粗燐
酸エステルは、通常洗浄精製によって塩素分と触媒を除
いた後、脱水乾燥して製品とする。上記一般式(2)で
表されるジアリール燐酸は、触媒やフェノール類に含有
される水分と、オキシ塩化燐及び1価フェノール類の反
応、および、洗浄工程などで引き起こされる燐酸エステ
ルの加水分解によって生成し、製造条件によりその生成
量が異なる。
Hereinafter, the present invention will be described in detail. First, the flame retardant for resin of the present invention will be described. The phosphate ester oligomer represented by the general formula (1) is disclosed in US Pat.
No. 90, JP-B-62-25706, JP-A-63-227632 and the like can be used. That is, it is synthesized by reacting phosphorus oxychloride with bisphenol A and a monohydric phenol in the presence of a Lewis acid catalyst such as magnesium chloride or aluminum chloride. As the monohydric phenols, phenol, cresol, and xylenol can be reacted alone or in a mixture or in a stepwise manner. The synthesized crude phosphoric acid ester is usually dehydrated and dried after removing the chlorine content and the catalyst by washing and purification to obtain a product. The diarylphosphoric acid represented by the general formula (2) is obtained by the reaction of water contained in a catalyst or phenols with phosphorus oxychloride and monohydric phenols, and hydrolysis of a phosphoric ester caused by a washing step and the like. It is produced and its production amount varies depending on the manufacturing conditions.

【0016】ジアリール燐酸を含む燐酸エステル組成物
は、難燃作用とともに、樹脂組成物の物性を低下させる
ことなく帯電防止性を与えることが、特公昭62−25
706号公報に記載されている。しかし本発明者らの研
究によると、ジアリール燐酸は燐酸エステルオリゴマー
に比べて揮発性が高い上、加熱条件下で燐酸エステルの
不均化反応による低分子量成分とゲル状物の生成を促進
する作用があることが判明した。また、プロトンを放出
しやすく、樹脂の分解を引き起こしたり、成形加工時の
腐食の原因となるほか、水や金属との親和性が強く、洗
浄精製工程に於けるエマルジョン化の原因や電気特性を
低下させる原因となるために好ましくない。難燃剤の熱
安定性と電気絶縁性を確保するためには、ジアリール燐
酸の含有量を1重量%以下とすることが必要であり、
0.5重量%以下とすることがさらに好ましい。
The phosphoric ester composition containing a diaryl phosphoric acid can provide an antistatic property without deteriorating the physical properties of the resin composition together with the flame retardant action.
No. 706. However, according to the study of the present inventors, diarylphosphoric acid has a higher volatility than a phosphoric acid ester oligomer and has an effect of promoting the formation of a low molecular weight component and a gel-like substance by a disproportionation reaction of a phosphoric acid ester under heating conditions. It turned out that there is. In addition, it easily releases protons, causing decomposition of the resin, causing corrosion during molding, and has a strong affinity for water and metals. It is not preferable because it causes a decrease. In order to ensure the thermal stability and electrical insulation of the flame retardant, the content of diarylphosphoric acid needs to be 1% by weight or less,
More preferably, the content is 0.5% by weight or less.

【0017】難燃剤中のジアリール燐酸の量を制限する
方法としては、合成時の生成量を減らす方法と、精製工
程で粗燐酸エステルから分離する方法がある。前者は、
合成原料の含水率を抑えた上で、オキシ塩化燐に対しフ
ェノール類を過剰に仕込んで反応を完結させる方法で、
原料の総量に対して原料に含有される水分量を600p
pm以下とすることが必要であり、300ppm以下と
することがさらに好ましい。一方後者は、洗浄精製行程
においてジアリール燐酸を水相に抽出する方法であり、
例えばアルカリ性の洗浄液を用いることで達成できる。
特に前者の方法は、製品の品質管理が行いやすく、排水
への有機燐の混入が少ないので好ましい。
As methods for limiting the amount of diarylphosphoric acid in the flame retardant, there are a method of reducing the amount produced during synthesis and a method of separating from the crude phosphoric acid ester in the purification step. The former is
After suppressing the water content of the raw materials for synthesis, a method is used in which phenols are excessively charged to phosphorus oxychloride to complete the reaction.
The amount of water contained in the raw material is 600p based on the total amount of the raw material.
pm or less, and more preferably 300 ppm or less. On the other hand, the latter is a method of extracting diarylphosphoric acid into an aqueous phase in a washing and purification step,
For example, this can be achieved by using an alkaline cleaning solution.
In particular, the former method is preferable because the quality of the product can be easily controlled and the amount of organic phosphorus in the wastewater is small.

【0018】難燃剤の熱安定性と電気絶縁性を低下させ
るもう一つの原因である金属分としては、主に触媒に由
来するマグネシウム、アルミニウムなどと、洗浄精製に
アルカリ、アルカリ土類などのイオンを含む水溶液を用
いる場合はこれに含有されるナトリウム、カリウム、カ
ルシウムなどが挙げられる。これらの金属分は、難燃剤
及びそれを含む樹脂組成物の電気抵抗を下げる上、高温
下で燐酸エステルの分解または不均化反応の触媒として
作用し、難燃剤の熱安定性を著しく低下させることが本
発明者らの研究により判明した。
The metal which is another cause of lowering the thermal stability and the electrical insulation of the flame retardant is mainly composed of magnesium and aluminum derived from the catalyst, and ions such as alkali and alkaline earth for cleaning and purification. When an aqueous solution containing is used, sodium, potassium, calcium and the like contained therein can be mentioned. These metals reduce the electric resistance of the flame retardant and the resin composition containing the same, and also act as a catalyst for the decomposition or disproportionation of the phosphate ester at a high temperature, and significantly lower the thermal stability of the flame retardant. This has been found by the present inventors' research.

【0019】燐酸エステル難燃剤に及ぼす触媒の影響に
ついては、特開平7−011121号公報にポリフェニ
レンエーテル組成物の成型品表面の変色を防止するため
に、不純物であるマグネシウムの量が50重量ppm以
下である燐酸エステルオリゴマーを難燃剤として使用す
る方法が記載されている。しかしこの発明は、6〜14
の炭素数を有する2価のアリール残基、アルキル置換ア
リール残基、及びアラルキル残基で架橋された燐酸エス
テルオリゴマーを対象としており、炭素数15のビスフ
ェノールA残基で架橋された化合物(1)は含まれてい
ない。またマグネシウム以外の金属に関する記載はな
く、金属分が難燃剤の熱安定性や電気特性に影響するこ
とも記載されておらず、金属分の総量を規制することに
より熱安定性と電気絶縁性に優れた難燃剤を提供できる
ことは類推できない。
Regarding the effect of the catalyst on the phosphoric ester flame retardant, JP-A-7-011121 discloses that the amount of magnesium as an impurity is 50 ppm by weight or less in order to prevent discoloration of the surface of a molded article of a polyphenylene ether composition. A method of using a phosphoric acid ester oligomer as a flame retardant is described. However, the present invention relates to 6-14
Compound (1), which is a phosphate ester oligomer cross-linked with a divalent aryl residue, an alkyl-substituted aryl residue, and an aralkyl residue having the following carbon number: Is not included. In addition, there is no description about metals other than magnesium, and it is not described that metals affect the thermal stability and electrical properties of the flame retardant.By regulating the total amount of metals, thermal stability and electrical insulation can be improved. There is no analogy that good flame retardants can be provided.

【0020】難燃剤の連続成型に必要な熱安定性を確保
するためには、上記の特許文献に示された、組成物に対
しマグネシウム50重量ppm以下の条件では不十分
で、金属分総量として30重量ppm以下である必要が
あり、10重量ppm以下であることがさらに好まし
い。上記の難燃剤中の金属分量は、通常温水による洗浄
のみでは達成する事が困難であるが、酸またはアルカリ
による抽出、または金属分を沈殿として除去する方法な
どにより達成できる。
In order to ensure the thermal stability required for continuous molding of the flame retardant, the condition of 50 ppm by weight or less of magnesium relative to the composition disclosed in the above-mentioned patent documents is insufficient, and the It must be 30 ppm by weight or less, and more preferably 10 ppm by weight or less. The amount of the metal in the flame retardant is usually difficult to achieve only by washing with warm water, but can be achieved by extraction with an acid or alkali, or a method of removing the metal as a precipitate.

【0021】難燃剤の熱安定性の簡便な評価法として、
熱天秤により一定の昇温速度で加熱を行い、特定温度に
達したときの重量減少量で評価する方法が知られてお
り、例えば特公昭62−25706号公報や特開昭63
−236353号公報、特開平5−186681号公報
などに開示されている。しかし、この方法は前述のトリ
アリールホスフェートなどの低沸点成分の揮発に由来す
る現象の指標としては有効であるが、不均化反応や熱分
解の促進などによる燐酸エステルの化学変化と、それに
伴う、成形加工時の発煙や金型汚染などの問題の指標と
はできない。
As a simple method for evaluating the thermal stability of a flame retardant,
A method is known in which heating is performed at a constant rate of temperature increase using a thermobalance and the amount of weight loss when a specific temperature is reached is evaluated. For example, Japanese Patent Publication No. 62-25706 and Japanese Patent Application Laid-Open No.
-236353, JP-A-5-186681 and the like. However, although this method is effective as an index of the phenomenon derived from the volatilization of low boiling components such as the above-mentioned triaryl phosphate, the chemical change of the phosphate due to the disproportionation reaction or the promotion of thermal decomposition and the accompanying change However, it cannot be used as an indicator of problems such as smoke and mold contamination during molding.

【0022】本発明者らは、熱天秤(TGA)により難
燃剤を不活性雰囲気中で特定温度まで急速に昇温した
後、その温度で一定時間保持して得られる初期重量減少
率と平衡時の重量減少速度が上記問題の指標となること
を見いだした。すなわち、20±10mgの難燃剤を、
窒素またはヘリウムの気流中100℃/分の昇温速度で
300℃まで加熱した後そのまま1時間保持した時の、
仕込量に対する加熱開始から20分間の重量減少を初期
重量減少率、加熱開始後40〜60分の20分間の重量
減少率を3倍したものを平衡時の重量減少速度と定義す
ると、前者が15重量%以下、かつ後者が4重量%/時
間以下、さらに好ましくは、前者が10重量%以下、か
つ後者が3重量%/時間以下であれば、成形加工時の発
煙や金型汚染などの問題は顕在化しない。
The present inventors have found that the temperature of a flame retardant is rapidly raised to a specific temperature in an inert atmosphere by a thermobalance (TGA) and then maintained at that temperature for a certain period of time. Was found to be an indicator of the above problem. That is, 20 ± 10 mg of the flame retardant
When heated to 300 ° C. at a rate of 100 ° C./min in a stream of nitrogen or helium and then held for 1 hour,
If the weight loss for 20 minutes from the start of heating with respect to the charged amount is defined as the initial weight reduction rate, and the weight loss rate at the equilibrium is defined as three times the weight loss rate for 40 minutes to 60 minutes after the start of heating, the former is 15%. % By weight or less, the latter being 4% by weight / hour or less, and more preferably the former being 10% by weight or less and the latter being 3% by weight / hour or less, such as problems such as smoke and mold contamination during molding. Does not appear.

【0023】初期重量減少率は主にトリアリールホスフ
ェートやジアリール燐酸などの低沸点成分の量を反映し
ており、この値を15重量%以下とするためには、難燃
剤に含まれる低沸点成分の量を概ね15重量%以下とす
ればよい。一方、平衡時の重量減少速度は主にジアリー
ル燐酸や金属によるエステルの不均化反応や熱分解促進
の作用を反映しており、難燃剤中のジアリール燐酸と金
属分の含有量が、各々本発明の範囲内であれば通常4重
量%/時間以下を達成できる。本発明の難燃性樹脂組成
物は、(A)前述の難燃剤と、(B)ハロゲン元素を含
まない非ハロゲン合成樹脂を必須成分とする組成物であ
り、難燃剤による熱安定性の低下が生じないので、成形
加工時の発煙、ゲル化、樹脂の低分子量化、金型汚染、
金型腐食などの問題を起こすことが無く、電気絶縁性の
低下もない。
The initial weight reduction rate mainly reflects the amount of low boiling components such as triaryl phosphate and diaryl phosphoric acid. To reduce this value to 15% by weight or less, the low boiling components contained in the flame retardant are used. Should be approximately 15% by weight or less. On the other hand, the rate of weight loss at equilibrium mainly reflects the disproportionation reaction of the ester by the diarylphosphoric acid and the metal and the action of promoting thermal decomposition. Normally, 4% by weight / hour or less can be achieved within the range of the invention. The flame-retardant resin composition of the present invention is a composition comprising (A) the above-described flame retardant and (B) a non-halogen synthetic resin containing no halogen element as essential components. Does not occur, causing smoke during molding, gelling, lowering the molecular weight of the resin, mold contamination,
There is no problem such as mold corrosion, and there is no decrease in electrical insulation.

【0024】合成樹脂としては、例えばノボラック型・
レゾール型などのフェノール樹脂、グリシジルエーテル
型・グリシジルエステル型・グリシジルアミン型などの
エポキシ樹脂、オルトフタル酸系・イソフタル酸系・テ
レフタル酸系・ビスフェノール系・ビニルエステル系な
どの不飽和ポリエステル樹脂、ポリフェニレンエーテル
樹脂、ポリカーボネート樹脂、ポリエチレンテレフタレ
ート・ポリブチレンテレフタレートなどのポリエステル
樹脂、ポリスチレン・ゴム変性ポリスチレン・AS樹脂
・ABS樹脂などのポリスチレン系樹脂、高密度ポリエ
チレン・低密度ポリエチレン・ポリプロピレンなどのポ
リオレフィン樹脂、6−ナイロン・6,6−ナイロン・
6,10−ナイロン・12−ナイロンなどのポリアミド
樹脂、ポリエステル系・ポリエーテル系・アジペイト系
・ラクトン系などの熱可塑性ポリウレタン、スチレン−
ブタジエンブロック共重合体・エチレン−プロピレンエ
ラストマー・エチレン系アイオノマーなどの熱可塑性エ
ラストマー及びこれらの組み合わせなどを挙げる事が出
来る。これらのうち、ポリフェニレンエーテル樹脂、ポ
リカーボネート樹脂、ポリスチレン系樹脂、ポリエステ
ル樹脂、ポリアミド樹脂から選ばれる1種またはこれら
を含む複数の樹脂の組み合わせが好ましく、ポリフェニ
レンエーテル樹脂、ポリカーボネート樹脂単独またはこ
れらの樹脂を含む組み合わせが、樹脂組成物とした場合
の難燃性、耐熱性、電気特性向上の効果が顕著で、特に
好ましい。
As the synthetic resin, for example, a novolak type
Phenol resins such as resol type, epoxy resins such as glycidyl ether type, glycidyl ester type and glycidylamine type, unsaturated polyester resins such as orthophthalic acid type, isophthalic acid type, terephthalic acid type, bisphenol type and vinyl ester type, and polyphenylene ether Resin, polycarbonate resin, polyester resin such as polyethylene terephthalate / polybutylene terephthalate, polystyrene resin such as polystyrene / rubber modified polystyrene / AS resin / ABS resin, polyolefin resin such as high density polyethylene / low density polyethylene / polypropylene, 6-nylon・ 6,6-nylon ・
Polyamide resins such as 6,10-nylon and 12-nylon, thermoplastic polyurethanes such as polyester-based, polyether-based, adipate-based, and lactone-based, styrene-
Examples include thermoplastic elastomers such as butadiene block copolymers, ethylene-propylene elastomers, and ethylene ionomers, and combinations thereof. Among these, one selected from a polyphenylene ether resin, a polycarbonate resin, a polystyrene resin, a polyester resin, and a polyamide resin or a combination of a plurality of resins including these is preferable, and a polyphenylene ether resin, a polycarbonate resin alone or a resin including these resins is included. The combination is particularly preferable because the effects of improving the flame retardancy, heat resistance, and electric properties when the resin composition is used are remarkable.

【0025】難燃剤の合成樹脂への添加量は樹脂の種類
や用途により異なり、特に制限はないが、通常1〜40
重量%、好ましくは5〜25重量%である。一般に難燃
剤の添加量が1重量%未満では十分な難燃性能が得られ
ず、40重量%を越えると樹脂組成物の機械的な物性が
低下する傾向がある。本発明の難燃性樹脂組成物の製造
方法は特に規定しないが、熱可塑性樹脂に対しては、例
えば一般的に知られている押し出し機、加熱ロール、ニ
ーダー、バンバリーミキサーなどの混練機を用いて製造
することができる。また、熱硬化性樹脂に対しては、重
合前の樹脂原料に混合した後に重合反応を行う方法など
により製造することができる。
The amount of the flame retardant added to the synthetic resin depends on the type and use of the resin, and is not particularly limited.
% By weight, preferably 5 to 25% by weight. In general, if the amount of the flame retardant is less than 1% by weight, sufficient flame retardancy cannot be obtained, and if it exceeds 40% by weight, the mechanical properties of the resin composition tend to deteriorate. Although the method for producing the flame-retardant resin composition of the present invention is not particularly limited, for a thermoplastic resin, for example, a generally known extruder, a heating roll, a kneader, a kneader such as a Banbury mixer is used. Can be manufactured. Further, the thermosetting resin can be produced by a method of performing a polymerization reaction after mixing with a resin material before polymerization.

【0026】又、本発明の樹脂組成物は、本発明の効果
を損なわない範囲で他の難燃剤、例えばデカブロモジフ
ェニルエーテル、テトラブロモビスフェノールA、ヘキ
サブロモベンゼン、パークロロシクロドデカンなどの公
知の有機ハロゲン化物、赤燐、ポリ燐酸、燐酸アンモニ
ウムなどの無機燐化合物、トリス(ハロプロピル)ホス
フェート、トリス(ハロエチル)ホスフェートなどの含
ハロゲン燐化合物、メラミン、尿素、メチロールメラミ
ン、ジシアンジアミド、メラミン樹脂、尿素樹脂などの
含窒素化合物、水酸化アルミニウム、水酸化マグネシウ
ムなどの無機水酸化物、酸化アンチモン、酸化モリブデ
ン、モリブデン酸アンモニウム、酸化亜鉛、ほう酸亜
鉛、酸化錫などの無機化合物、ポリテトラフルオロエチ
レン、シロキサン化合物などの滴下防止剤などを併用し
ても良い。
The resin composition of the present invention may contain other known flame retardants such as decabromodiphenyl ether, tetrabromobisphenol A, hexabromobenzene, perchlorocyclododecane and the like as long as the effects of the present invention are not impaired. Inorganic phosphorus compounds such as halides, red phosphorus, polyphosphoric acid and ammonium phosphate, halogen-containing phosphorus compounds such as tris (halopropyl) phosphate and tris (haloethyl) phosphate, melamine, urea, methylolmelamine, dicyandiamide, melamine resin, urea resin Such as nitrogen-containing compounds, inorganic hydroxides such as aluminum hydroxide and magnesium hydroxide, inorganic compounds such as antimony oxide, molybdenum oxide, ammonium molybdate, zinc oxide, zinc borate, and tin oxide; polytetrafluoroethylene; It may be used in combination such as anti-drip agents such objects.

【0027】また、本発明の樹脂組成物に本発明の効果
を損なわない範囲で他の添加剤、例えば可塑剤、離型
剤、紫外線吸収剤、酸化防止剤、及び光安定剤などの安
定剤、あるいは染顔料を含有させることができる。さら
に、ガラス繊維、ガラスチップ、ガラスビーズ、炭素繊
維、ウォラストナイト、炭酸カルシウム、タルク、雲
母、木粉、スレート粉、繊維質アスベストなどの充填剤
を添加することもできる。
Further, other additives such as a plasticizer, a releasing agent, an ultraviolet absorber, an antioxidant, and a stabilizer such as a light stabilizer may be added to the resin composition of the present invention as long as the effects of the present invention are not impaired. Alternatively, a dye or pigment can be contained. Further, fillers such as glass fibers, glass chips, glass beads, carbon fibers, wollastonite, calcium carbonate, talc, mica, wood powder, slate powder, and fibrous asbestos can also be added.

【0028】[0028]

【発明の実施の形態】以下、実施例により本発明を具体
的に説明する。まず、難燃剤の分析法を以下に示す。 1.生成物の定量 縮合度nによる組成 : 東ソー GPC カラム 東ソー TSKgel G2000HXL 2本 東ソー TSKgel G3000HXL 1本 直列 溶媒 THF flow=1ml/分 検出器 UV λ=254nm 試料 THF1000倍希釈 5μl 絶対検量線法 ジアリール燐酸の定量 : 島津 LC−10A カラム 日本分光 Finepak SIL C18S 1本 東ソー TSKgel ODS−80T 1本 直列 溶媒 メタノール/水=90/10 flow=1.0ml/分 検出器 UV λ=254nm 試料 メタノール 50倍希釈 10μl 絶対検量線法
DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described specifically with reference to examples. First, a method for analyzing a flame retardant will be described below. 1. Quantitative determination of product Composition by degree of condensation n: Tosoh GPC column Tosoh TSKgel G2000HXL 2 Tosoh TSKgel G3000HXL 1 in-line solvent THF flow = 1 ml / min Detector UV λ = 254 nm Sample THF 1000-fold dilution 5 μl absolute phosphorus analysis : Shimadzu LC-10A column JASCO Finepak SIL C18S 1 pc Tosoh TSKgel ODS-80T 1 pc. Series solvent methanol / water = 90/10 flow = 1.0 ml / min Detector UV λ = 254 nm sample methanol 50 times dilution 10 μl absolute calibration Line method

【0029】 金属分の定量 : ICP法 装置 セイコー社製 JYー38PII型 試料 MIBK 30倍希釈 絶対検量線法 水分の定量 : カールフィッシャー法 装置 三菱化成製 CA−05型微量水分測定装置 TGA熱安定性 装置 Rigaku製 TAS−300 TG−DTA 試料 20±10mg D5mm*H2.5mmアルミ試料パン 測定条件 50℃→(昇温100℃/分)→300℃1時間Determination of metal content: ICP method apparatus Seiko JY-38PII type sample MIBK 30-fold absolute calibration curve method Quantification of water content: Karl Fischer method apparatus Mitsubishi Kasei CA-05 trace water content analyzer TGA thermal stability Equipment Rigaku TAS-300 TG-DTA sample 20 ± 10mg D5mm * H2.5mm aluminum sample pan Measurement conditions 50 ° C → (temperature rise 100 ° C / min) → 300 ° C 1 hour

【0030】実施例に用いた樹脂等を以下に示す。 [ポリフェニレンエーテル樹脂(PPEと略す)]クロ
ロホルム中30℃で測定した極限粘度が0.53であ
る、ポリ2,6−ジメチル−1,4−フェニレンエーテ
ルを用いた。 [ポリスチレン樹脂(GPPSと略す)]旭化成工業
(株)製 旭化成ポリスチレン685を用いた。 [耐衝撃性ポリスチレン樹脂(HIPSと略す)]旭化
成工業(株)製 旭化成ポリスチレン9405を用い
た。 [ABS樹脂(ABSと略す)]旭化成工業(株)製
スタイラック6920(ゴム成分30重量%)を用い
た。
The resins and the like used in the examples are shown below. [Polyphenylene ether resin (abbreviated as PPE)] Poly 2,6-dimethyl-1,4-phenylene ether having an intrinsic viscosity of 0.53 measured at 30 ° C. in chloroform was used. [Polystyrene resin (abbreviated as GPPS)] Asahi Kasei Polystyrene 685 manufactured by Asahi Kasei Corporation was used. [Impact-resistant polystyrene resin (abbreviated as HIPS)] Asahi Kasei Polystyrene 9405 manufactured by Asahi Kasei Kogyo Co., Ltd. was used. [ABS resin (abbreviated as ABS)] manufactured by Asahi Kasei Corporation
Styrac 6920 (30% by weight of rubber component) was used.

【0031】[ポリカーボネート樹脂(PCと略す)]
帝人化成(株)製 パンライトL1250を用いた。 [ポリテトラフルオロエチレン(PTFEと略す)]ダ
イキン工業(株)製 ダイフロンF201Lを用いた。 [難燃剤]トリフェニルホスフェート(TPPと略す)
及びレゾルシノールビスジフェニルホスフェート(CR
733sと略す)は、大八化学工業(株)製を用いた。
又、難燃剤1〜7は、実施例1〜4及び比較例1〜3の
方法により製造した。各々の構造式を表1、組成分析値
を表2に示す。
[Polycarbonate resin (abbreviated as PC)]
Panlite L1250 manufactured by Teijin Chemicals Ltd. was used. [Polytetrafluoroethylene (abbreviated as PTFE)] Daiflon F201L manufactured by Daikin Industries, Ltd. was used. [Flame retardant] triphenyl phosphate (abbreviated as TPP)
And resorcinol bisdiphenyl phosphate (CR
733s) used by Daihachi Chemical Industry Co., Ltd.
Flame retardants 1 to 7 were produced by the methods of Examples 1 to 4 and Comparative Examples 1 to 3. Table 1 shows each structural formula, and Table 2 shows composition analysis values.

【0032】樹脂組成物の評価法を以下に示す。 1.成形加工時の揮発性 射出成型時のノズル部に於ける発煙量を、目視により観
察し判定した。 2.成形加工時の金型汚染 図1に示す金型を用いて30000ショットまで連続成
型を実施し、金型のベント部が閉塞するまでのショット
数をカウントした。閉塞が生じない物については、試験
終了後のベント部への揮発物の付着状況を観察した。ま
た、試験終了時の金型の腐食状態を目視により判定し
た。 3.電気特性 JIS−C2110に準拠して、対極、短時間法で絶縁
破壊強さを測定した。 4.難燃性能 UL94規格垂直燃焼試験(厚み1/16インチ)に準
拠して測定した。
The evaluation method of the resin composition is shown below. 1. Volatility during molding processing The amount of smoke generated at the nozzle during injection molding was visually observed and judged. 2. Mold Contamination During Molding Using the mold shown in FIG. 1, continuous molding was performed up to 30,000 shots, and the number of shots until the vent portion of the mold was closed was counted. With respect to the material that did not cause blockage, the state of attachment of volatile matter to the vent after completion of the test was observed. Further, the corrosion state of the mold at the end of the test was visually determined. 3. Electrical properties In accordance with JIS-C2110, the dielectric breakdown strength was measured by a counter electrode, short-time method. 4. Flame retardant performance Measured in accordance with the UL94 standard vertical combustion test (1/16 inch thickness).

【0033】[0033]

【実施例1】(難燃剤1の製造)真空乾燥により脱水し
たビスフェノールA100重量部(モル比1.0、水分
120重量ppm)、オキシ塩化燐168重量部(モル
比2.5)、及び無水塩化マグネシウム0.62重量部
(モル比0.015、水分0.83重量%)を、攪拌機
・還流管及び減圧蒸留設備の付属する反応器に仕込み、
窒素気流下70〜120℃にて5時間反応させた。反応
終了後、反応温度を維持しつつ、反応器を50mmHgまで
減圧し、未反応のオキシ塩化燐を回収した。ついで反応
器を70℃まで冷却し、脱水乾燥したフェノール165
重量部(モル比4.0、水分30重量ppm)を加え、
100〜150℃に加熱して7時間反応させた。そのま
まの温度で10mmHgまで減圧し、未反応のフェノー
ル類を溜去して粗燐酸エステル284重量部を得た。
Example 1 (Production of flame retardant 1) 100 parts by weight of bisphenol A dehydrated by vacuum drying (molar ratio 1.0, water 120 ppm by weight), 168 parts by weight of phosphorus oxychloride (molar ratio 2.5), and anhydrous 0.62 parts by weight of magnesium chloride (a molar ratio of 0.015, and a water content of 0.83% by weight) were charged into a stirrer, a reflux tube, and a reactor attached to a vacuum distillation facility,
The reaction was carried out at 70 to 120 ° C. for 5 hours under a nitrogen stream. After the completion of the reaction, the pressure in the reactor was reduced to 50 mmHg while maintaining the reaction temperature, and unreacted phosphorus oxychloride was recovered. The reactor was then cooled to 70 ° C. and dehydrated and dried phenol 165.
Parts by weight (molar ratio 4.0, water 30 ppm by weight)
The mixture was heated to 100 to 150 ° C. and reacted for 7 hours. The pressure was reduced to 10 mmHg at the same temperature, and unreacted phenols were distilled off to obtain 284 parts by weight of a crude phosphoric ester.

【0034】粗燐酸エステル100重量をジャケット、
サイトグラス付きの攪拌槽に移し、0.1規定塩酸10
0重量部を加えて80℃で1時間攪拌した後30分静置
して水相を分離、除去した。次に純水100重量部を加
えて80℃で1時間攪拌した後30分静置して水相を分
離、除去した。同様の方法で純水による濯ぎをさらに3
回行った後、薄膜蒸発機により水分と残留フェノールを
留去して、“難燃剤1”96.4重量部を得た。組成分
析結果と、TGAによる評価結果を表2に示す。又、T
GAの重量減少曲線を図2に示す。
100 weight parts of the crude phosphoric acid ester is jacketed,
Transfer to a stirring tank with a sight glass and add 0.1N hydrochloric acid 10
After adding 0 weight part and stirring at 80 degreeC for 1 hour, it left still for 30 minutes, and separated and removed the aqueous phase. Next, 100 parts by weight of pure water was added, and the mixture was stirred at 80 ° C. for 1 hour and left standing for 30 minutes to separate and remove an aqueous phase. 3 additional rinses with pure water in the same manner
After repeating the process, water and residual phenol were distilled off by a thin film evaporator to obtain 96.4 parts by weight of "flame retardant 1". Table 2 shows the results of composition analysis and the results of evaluation by TGA. Also, T
The GA weight loss curve is shown in FIG.

【0035】[0035]

【実施例2】(難燃剤2の製造)実施例1の方法で合成
した粗燐酸エステル100重量部を用い、0.1規定塩
酸の代わりに1規定の水酸化ナトリウム水溶液100重
量部を用いる以外は実施例1と同じ方法により洗浄精製
を行って、“難燃剤2”89.2重量部を得た。組成分
析結果と、TGAによる評価結果を表2に示す。又、T
GAの重量減少曲線を図2に示す。
Example 2 (Production of Flame Retardant 2) Except that 100 parts by weight of the crude phosphoric ester synthesized by the method of Example 1 was used, and 100 parts by weight of a 1 N aqueous solution of sodium hydroxide was used instead of 0.1 N hydrochloric acid. Was subjected to washing and purification in the same manner as in Example 1 to obtain 89.2 parts by weight of "flame retardant 2". Table 2 shows the results of composition analysis and the results of evaluation by TGA. Also, T
The GA weight loss curve is shown in FIG.

【0036】[0036]

【実施例3】(難燃剤3の製造)ビスフェノールA10
0重量部(モル比1.0、水分123重量ppm)、オ
キシ塩化燐269重量部(モル比4.0)、及び無水塩
化マグネシウム0.64重量部(モル比0.015、水
分1.7重量%)を、攪拌機・還流管及び減圧蒸留設備
の付属するGL反応器に仕込み、窒素気流下70〜12
0℃にて6時間反応させた。反応終了後、反応温度を維
持しつつ、反応器を50mmHgまで減圧し、未反応のオキ
シ塩化燐を回収した。ついで反応器を70℃まで冷却
し、2,6−キシレノール57重量部(モル比1.1、
水分82重量ppm)及び塩化アルミニウム1.1重量
部(モル比0.02、水分2.3重量%)を加え、11
0〜150℃で6時間反応させた。
Example 3 (Production of Flame Retardant 3) Bisphenol A10
0 parts by weight (molar ratio 1.0, water 123 ppm by weight), phosphorus oxychloride 269 parts by weight (molar ratio 4.0), and anhydrous magnesium chloride 0.64 parts by weight (molar ratio 0.015, water 1.7) % By weight) into a GL reactor equipped with a stirrer / reflux tube and a vacuum distillation facility, and the GL reactor is placed under a nitrogen stream at 70 to 12%.
The reaction was performed at 0 ° C. for 6 hours. After the completion of the reaction, the pressure in the reactor was reduced to 50 mmHg while maintaining the reaction temperature, and unreacted phosphorus oxychloride was recovered. The reactor was then cooled to 70 ° C and 57 parts by weight of 2,6-xylenol (molar ratio 1.1,
Water (82 ppm by weight) and 1.1 parts by weight of aluminum chloride (molar ratio: 0.02, moisture: 2.3% by weight).
The reaction was performed at 0 to 150 ° C. for 6 hours.

【0037】再び反応器を70℃まで冷却し、フェノー
ル125重量部(モル比3.1、水分35重量ppm)
を加え、100〜150℃に加熱して7時間反応させ
た。そのままの温度で10mmHgまで減圧し、未反応
のフェノール類を溜去して粗燐酸エステル310重量部
を得た。この粗燐酸エステル100重量部を用いて、実
施例1と同様の方法で洗浄、濯ぎ、蒸留を行い、“難燃
剤3”95.8重量部を得た。組成分析結果と、TGA
による評価結果を表2に示す。
The reactor was cooled to 70 ° C. again, and 125 parts by weight of phenol (a molar ratio of 3.1 and a water content of 35 ppm by weight) were used.
And heated to 100 to 150 ° C. to react for 7 hours. The pressure was reduced to 10 mmHg at the same temperature, and unreacted phenols were distilled off to obtain 310 parts by weight of a crude phosphoric ester. Using 100 parts by weight of the crude phosphate, washing, rinsing and distillation were carried out in the same manner as in Example 1 to obtain 95.8 parts by weight of "flame retardant 3". Composition analysis results and TGA
Table 2 shows the evaluation results.

【0038】[0038]

【実施例4】(難燃剤4の製造)フェノール164重量
部の代わりにクレゾール190重量部(モル比4.0、
水分320重量ppm)を用いる以外は実施例1と同様
の方法により、粗燐酸エステル310重量部を得た。こ
の粗燐酸エステル100重量部を用いて、実施例1と同
様の方法で洗浄、濯ぎ、蒸留を行い、“難燃剤4”9
6.2重量部を得た。組成分析結果と、TGAによる評
価結果を表2に示す。
Example 4 (Production of Flame Retardant 4) 190 parts by weight of cresol instead of 164 parts by weight of phenol (molar ratio 4.0,
310 parts by weight of a crude phosphoric ester were obtained in the same manner as in Example 1, except that water (320 ppm by weight) was used. Using 100 parts by weight of the crude phosphate, washing, rinsing and distillation were carried out in the same manner as in Example 1, and "flame retardant 4" 9
6.2 parts by weight were obtained. Table 2 shows the results of composition analysis and the results of evaluation by TGA.

【0039】[0039]

【比較例1】(難燃剤5の製造)実施例1の方法で合成
した粗燐酸エステル100重量部を攪拌槽に移し、洗浄
水として0.1規定塩酸の代わりに純水100重量部を
用いる以外は実施例1と同様の操作条件により、洗浄水
のpHが5以上となるまで洗浄を行った後、蒸留乾燥し
て、“難燃剤5”93.6重量部を得た。組成分析結果
と、TGAによる評価結果を表2に示す。又、TGAの
重量変化曲線を図2に示す。
Comparative Example 1 (Production of Flame Retardant 5) 100 parts by weight of a crude phosphoric ester synthesized by the method of Example 1 was transferred to a stirring tank, and 100 parts by weight of pure water was used instead of 0.1 N hydrochloric acid as washing water. After washing under the same operating conditions as in Example 1 until the pH of the washing water became 5 or more, the residue was distilled and dried to obtain 93.6 parts by weight of "flame retardant 5". Table 2 shows the results of composition analysis and the results of evaluation by TGA. FIG. 2 shows a weight change curve of TGA.

【0040】[0040]

【比較例2】(難燃剤6の製造)ビスフェノールA10
0重量部(モル比1.0、水分1100重量ppm)、
オキシ塩化燐176重量部(モル比2.6)、無水塩化
マグネシウム1.0重量部(モル比0.025、水分
7.2重量%)、及びクレゾール191重量部(モル比
4.0、水分930重量ppm)を用い、実施例1と同
様の装置、操作条件にて粗燐酸エステル307重量部を
得た。この粗燐酸エステル100重量部を用いて、比較
例1と同じ方法で洗浄精製を行って、“難燃剤6”9
5.1重量部を得た。組成分析結果と、TGAによる評
価結果を表2に示す。
Comparative Example 2 (Production of Flame Retardant 6) Bisphenol A10
0 parts by weight (molar ratio 1.0, water 1100 weight ppm),
176 parts by weight of phosphorus oxychloride (molar ratio 2.6), 1.0 part by weight of anhydrous magnesium chloride (molar ratio 0.025, water content 7.2% by weight), and 191 parts by weight of cresol (molar ratio 4.0, water content) 930 parts by weight), and 307 parts by weight of a crude phosphoric ester was obtained in the same apparatus and operating conditions as in Example 1. Using 100 parts by weight of this crude phosphate, washing and purification were carried out in the same manner as in Comparative Example 1 to obtain "flame retardant 6" 9
5.1 parts by weight were obtained. Table 2 shows the results of composition analysis and the results of evaluation by TGA.

【0041】[0041]

【比較例3】(組成物7の製造)フェノール149重量
部(モル比3.6、水分30重量ppm)を用いる以外
は実施例1と同様の装置、操作条件にて粗燐酸エステル
282重量部を得た。この粗燐酸エステル100重量部
を攪拌槽に移し、実施例1と同じ方法で洗浄精製を行っ
て、“難燃剤7”94.8重量部を得た。組成分析結果
と、TGAによる熱安定性の測定結果を表2に示す。
又、TGAの重量変化曲線を図2に示す。
Comparative Example 3 (Production of Composition 7) 282 parts by weight of crude phosphoric acid ester in the same apparatus and under the same operating conditions as in Example 1 except that 149 parts by weight of phenol (molar ratio 3.6, water 30 ppm by weight) were used. I got 100 parts by weight of the crude phosphoric acid ester was transferred to a stirring tank and subjected to washing and purification in the same manner as in Example 1 to obtain 94.8 parts by weight of "flame retardant 7". Table 2 shows the results of composition analysis and the results of measurement of thermal stability by TGA.
FIG. 2 shows a weight change curve of TGA.

【0042】[0042]

【実施例5〜8及び比較例4〜8】PPE60重量部、
HIPS21重量部、GPPS9重量部、及び難燃剤1
0重量部を、シリンダー温度300℃に設定した2軸押
出機にて溶融混練してペレットとした後、射出成型機に
て物性測定用試験片の作成と、連続ショット試験を実施
した。前述の方法により行った評価結果を表3に示す。
Examples 5 to 8 and Comparative Examples 4 to 8 60 parts by weight of PPE,
21 parts by weight of HIPS, 9 parts by weight of GPPS, and flame retardant 1
After 0 parts by weight were melt-kneaded with a twin-screw extruder set at a cylinder temperature of 300 ° C. to form pellets, a test piece for measuring physical properties was prepared using an injection molding machine, and a continuous shot test was performed. Table 3 shows the results of the evaluation performed by the above-described method.

【0043】[0043]

【実施例9〜12及び比較例9〜12】PC75重量
部、ABS25重量部、難燃剤15重量部、及びPTF
E0.3重量部を、シリンダー温度240℃に設定した
2軸押出機にて溶融混練してペレットとした後、射出成
型機にて難燃性測定用の試験片の作成と、連続ショット
試験を実施した。前述の方法により行った評価結果を表
4に示す。
Examples 9-12 and Comparative Examples 9-12 PC 75 parts by weight, ABS 25 parts by weight, flame retardant 15 parts by weight, and PTF
E0.3 parts by weight was melt-kneaded with a twin-screw extruder set at a cylinder temperature of 240 ° C. to form pellets. Then, a test piece for measuring the flame retardancy was measured using an injection molding machine, and a continuous shot test was performed. Carried out. Table 4 shows the results of the evaluation performed by the above-described method.

【0044】[0044]

【表1】 [Table 1]

【0045】[0045]

【表2】 [Table 2]

【0046】[0046]

【表3】 [Table 3]

【0047】[0047]

【表4】 [Table 4]

【0048】[0048]

【発明の効果】本発明の難燃剤は、優れた熱安定性と電
気絶縁性を持ち、これを用いる本発明の難燃性樹脂組成
物は、優れた難燃性能と耐熱性、電気絶縁性を併せ持
ち、押出し、成形加工時の発煙、金型汚染、腐食などの
諸問題を起こすこともないことから、産業上大いに有用
である。
The flame retardant of the present invention has excellent thermal stability and electrical insulation, and the flame retardant resin composition of the present invention using the flame retardant has excellent flame retardancy, heat resistance and electrical insulation. It is very useful in industry because it does not cause problems such as smoke during extrusion and molding, mold contamination and corrosion.

【図面の簡単な説明】[Brief description of the drawings]

【図1】連続成型試験に用いた金型の略図である。FIG. 1 is a schematic view of a mold used for a continuous molding test.

【図2】実施例1、2と比較例1、3で得られた難燃
剤、及びTPPのTGA加熱減量曲線である。
FIG. 2 is a TGA weight loss curve of the flame retardants and TPP obtained in Examples 1 and 2 and Comparative Examples 1 and 3.

【符号の説明】[Explanation of symbols]

1:難燃剤1のTGA加熱減量曲線 2:難燃剤2のTGA加熱減量曲線 3:難燃剤5のTGA加熱減量曲線 4:難燃剤7のTGA加熱減量曲線 5:CR733sのTGA加熱減量曲線 6:温度を示す曲線 1: TGA weight loss curve of flame retardant 1 2: TGA weight loss curve of flame retardant 2: 3: TGA weight loss curve of flame retardant 5 4: TGA weight loss curve of flame retardant 7 5: TGA weight loss curve of CR733s 6: Curve showing temperature

─────────────────────────────────────────────────────
────────────────────────────────────────────────── ───

【手続補正書】[Procedure amendment]

【提出日】平成13年4月9日(2001.4.9)[Submission date] April 9, 2001 (2001.4.9)

【手続補正1】[Procedure amendment 1]

【補正対象書類名】明細書[Document name to be amended] Statement

【補正対象項目名】請求項1[Correction target item name] Claim 1

【補正方法】変更[Correction method] Change

【補正内容】[Correction contents]

【化1】 (式中、nは0〜10の整数であり、R1〜R4は各々
独立に、フェニル基、トリル基又はキシリル基である。
またnが2以上の場合、複数あるR4は各々同一でも異
なっても良い。)
Embedded image (In the formula, n is an integer of 0 to 10, and R1 to R4 are each independently a phenyl group, a tolyl group, or a xylyl group.
When n is 2 or more, a plurality of R4s may be the same or different. )

【化2】 (式中、R1、R2は各々独立に、フェニル基、トリル
基またはキシリル基である。)
Embedded image (In the formula, R1 and R2 are each independently a phenyl group, a tolyl group, or a xylyl group.)

【手続補正2】[Procedure amendment 2]

【補正対象書類名】明細書[Document name to be amended] Statement

【補正対象項目名】0010[Correction target item name] 0010

【補正方法】変更[Correction method] Change

【補正内容】[Correction contents]

【0010】[0010]

【課題を解決するための手段】本発明者らは、前記課題
を解決するため、難燃剤の熱安定性の低下がいかなる原
因によるものかを検討した。その結果、燐酸エステルそ
のものの分解温度及び揮発温度は十分高いものの、合成
時に副生する下記式(2)で表されるジアリール燐酸
と、触媒などに由来する金属分が加熱時に燐酸エステル
のエステル交換反応による低分子量化と加水分解反応を
促進する作用を持ち、この結果発生する揮発成分が金型
の汚染を引き起こすことを突き止めた。そして、難燃剤
の熱安定性を大幅に改善するためには、金属分とジアリ
ール燐酸の含有量を共に各々特定の値以下とすることが
必要であり、これにより成形加工時の金型の汚染や腐
食、樹脂組成物の電気絶縁性低下等の問題も解決できる
ことを見いだし、本発明を完成するに至った。
Means for Solving the Problems In order to solve the above problems, the present inventors have studied what causes the decrease in the thermal stability of the flame retardant. As a result, although the decomposition temperature and the volatilization temperature of the phosphate ester itself are sufficiently high, the diarylphosphoric acid represented by the following formula (2) by-produced during the synthesis and the metal derived from the catalyst and the like transesterify the phosphate ester during heating. It has been found that it has the effect of accelerating the reduction of molecular weight and the hydrolysis reaction by the reaction, and the resulting volatile components cause mold contamination. In order to greatly improve the thermal stability of the flame retardant, it is necessary that both the content of the metal and the content of the diarylphosphoric acid are each equal to or less than a specific value. The inventors have found that problems such as corrosion, corrosion, and a decrease in the electrical insulation of the resin composition can be solved, and have completed the present invention.

【手続補正3】[Procedure amendment 3]

【補正対象書類名】明細書[Document name to be amended] Statement

【補正対象項目名】0011[Correction target item name] 0011

【補正方法】変更[Correction method] Change

【補正内容】[Correction contents]

【0011】すなわち本発明は、以下の通りである。 1.(A)下記一般式(1)で表され、nが0から10
の整数である燐酸エステルの混合物からなり、下記一般
式(2)で表されるジアリール燐酸の含有量が1重量%
以下で、金属分の含有量合計が30重量ppm以下であ
り、かつ、TGAによる、不活性ガス雰囲気中100℃
/分の昇温速度で300℃まで加熱し、そのままその温
度に保持した時の、加熱開始から20分間の重量減少率
が15重量%以下である樹脂用の難燃剤と、(B)非ハ
ロゲン合成樹脂からなる難燃性樹脂組成物。
That is, the present invention is as follows. 1. (A) represented by the following general formula (1), wherein n is from 0 to 10
Wherein the content of diarylphosphoric acid represented by the following general formula (2) is 1% by weight.
Below, the total content of the metal content is 30 ppm by weight or less, and 100 ° C. in an inert gas atmosphere by TGA.
A flame retardant for a resin that has a weight loss rate of 15% by weight or less for 20 minutes from the start of heating when heated to 300 ° C. at a rate of temperature rise per minute and (B) non-halogen A flame-retardant resin composition comprising a synthetic resin.

【手続補正4】[Procedure amendment 4]

【補正対象書類名】明細書[Document name to be amended] Statement

【補正対象項目名】0015[Correction target item name] 0015

【補正方法】変更[Correction method] Change

【補正内容】[Correction contents]

【0015】以下本発明を詳述する。まず、本発明の樹
脂用難燃剤について説明する。上記一般式(1)で表さ
れる燐酸エステルは、米国特許第2520090号明細
書や特公昭62−25706号公報、特開昭63−22
7632号公報などに記載されている公知の方法で製造
できる。すなわち、塩化マグネシウムや塩化アルミニウ
ムなどのルイス酸触媒存在下に、オキシ塩化燐とビスフ
ェノールA及び1価フェノール類を反応させて合成す
る。1価フェノール類としてはフェノール、クレゾー
ル、キシレノールを単独または混合して、または段階的
に加えて反応させることができる。合成した粗燐酸エス
テルは、通常洗浄精製によって塩素分と触媒を除いた
後、脱水乾燥して製品とする。上記一般式(2)で表さ
れるジアリール燐酸は、触媒やフェノール類に含有され
る水分と、オキシ塩化燐及び1価フェノール類の反応、
および、洗浄工程などで引き起こされる燐酸エステルの
加水分解によって生成し、製造条件によりその生成量が
異なる。
Hereinafter, the present invention will be described in detail. First, the flame retardant for resin of the present invention will be described. Phosphoric esters represented by the above general formula (1) are disclosed in U.S. Pat. No. 252,090, JP-B-62-25706, and JP-A-63-22.
It can be manufactured by a known method described in, for example, U.S. Pat. That is, it is synthesized by reacting phosphorus oxychloride with bisphenol A and a monohydric phenol in the presence of a Lewis acid catalyst such as magnesium chloride or aluminum chloride. As the monohydric phenols, phenol, cresol, and xylenol can be reacted alone or in a mixture or in a stepwise manner. The synthesized crude phosphoric acid ester is usually dehydrated and dried after removing the chlorine content and the catalyst by washing and purification to obtain a product. The diaryl phosphoric acid represented by the general formula (2) is obtained by reacting water contained in a catalyst or phenol with phosphorus oxychloride and a monohydric phenol,
Further, it is produced by hydrolysis of a phosphoric acid ester caused in a washing step and the like, and the produced amount varies depending on production conditions.

【手続補正5】[Procedure amendment 5]

【補正対象書類名】明細書[Document name to be amended] Statement

【補正対象項目名】0016[Correction target item name] 0016

【補正方法】変更[Correction method] Change

【補正内容】[Correction contents]

【0016】ジアリール燐酸を含む燐酸エステル組成物
は、難燃作用とともに、樹脂組成物の物性を低下させる
ことなく帯電防止性を与えることが、特公昭62−25
706号公報に記載されている。しかし本発明者らの研
究によると、ジアリール燐酸は燐酸エステルに比べて揮
発性が高い上、加熱条件下で燐酸エステルの不均化反応
による低分子量成分とゲル状物の生成を促進する作用が
あることが判明した。また、プロトンを放出しやすく、
樹脂の分解を引き起こしたり、成形加工時の腐食の原因
となるほか、水や金属との親和性が強く、洗浄精製工程
に於けるエマルジョン化の原因や電気特性を低下させる
原因となるために好ましくない。難燃剤の熱安定性と電
気絶縁性を確保するためには、ジアリール燐酸の含有量
を1重量%以下とすることが必要であり、0.5重量%
以下とすることがさらに好ましい。
The phosphoric ester composition containing a diaryl phosphoric acid can provide an antistatic property without deteriorating the physical properties of the resin composition together with the flame retardant action.
No. 706. However, according to the study of the present inventors, diarylphosphoric acid has a higher volatility than a phosphoric acid ester and has an effect of promoting the formation of a low molecular weight component and a gel-like substance by a disproportionation reaction of the phosphoric acid ester under heating conditions. It turned out to be. In addition, it is easy to release protons,
In addition to causing decomposition of the resin and causing corrosion during molding, it has a strong affinity with water and metals, and is preferable because it causes emulsification in cleaning and purification processes and causes deterioration in electrical properties. Absent. In order to ensure the thermal stability and electrical insulation of the flame retardant, the content of diarylphosphoric acid must be 1% by weight or less, and 0.5% by weight.
It is more preferable to set the following.

Claims (4)

【特許請求の範囲】[Claims] 【請求項1】 (A)下記一般式(1)で表される燐酸
エステルオリゴマーの混合物からなり、下記一般式
(2)で表されるジアリール燐酸の含有量が1重量%以
下で、金属分の含有量合計が30重量ppm以下であ
り、かつ、TGAによる、不活性ガス雰囲気中100℃
/分の昇温速度で300℃まで加熱し、そのままその温
度に保持した時の、加熱開始から20分間の重量減少率
が15重量%以下である樹脂用の難燃剤と、(B)非ハ
ロゲン合成樹脂からなる難燃性樹脂組成物。 【化1】 (式中、nは0〜10の整数であり、R1〜R4は各々
独立に、フェニル基、トリル基又はキシリル基である。
またnが2以上の場合、複数あるR4は各々同一でも異
なっても良い。) 【化2】 (式中、R1、R2は各々独立に、フェニル基、トリル
基またはキシリル基である。)
(A) a mixture of a phosphate ester oligomer represented by the following general formula (1), wherein the content of a diarylphosphoric acid represented by the following general formula (2) is 1% by weight or less, Is not more than 30 ppm by weight, and 100 ° C. in an inert gas atmosphere by TGA.
A flame retardant for a resin that has a weight loss rate of 15% by weight or less for 20 minutes from the start of heating when heated to 300 ° C. at a rate of temperature rise per minute and (B) non-halogen A flame-retardant resin composition comprising a synthetic resin. Embedded image (In the formula, n is an integer of 0 to 10, and R1 to R4 are each independently a phenyl group, a tolyl group, or a xylyl group.
When n is 2 or more, a plurality of R4s may be the same or different. ) (In the formula, R1 and R2 are each independently a phenyl group, a tolyl group, or a xylyl group.)
【請求項2】 (B)非ハロゲン合成樹脂が、ポリフェ
ニレンエーテル樹脂、ポリカーボネート樹脂、ポリスチ
レン系樹脂、ポリエステル樹脂、ポリアミド樹脂から選
ばれる1種またはこれらを含む複数の樹脂の組み合わせ
である請求項1記載の難燃性樹脂組成物。
2. The non-halogen synthetic resin (B) is one selected from a polyphenylene ether resin, a polycarbonate resin, a polystyrene resin, a polyester resin, and a polyamide resin, or a combination of a plurality of resins containing these. Flame-retardant resin composition.
【請求項3】 (B)非ハロゲン合成樹脂が、ポリフェ
ニレンエーテル樹脂及び/又はポリスチレン系樹脂であ
る請求項1記載の難燃性樹脂組成物。
3. The flame-retardant resin composition according to claim 1, wherein the non-halogen synthetic resin (B) is a polyphenylene ether resin and / or a polystyrene resin.
【請求項4】 (B)非ハロゲン合成樹脂が、ポリカー
ボネート樹脂及びABS樹脂である請求項1記載の難燃
性樹脂組成物。
4. The flame-retardant resin composition according to claim 1, wherein the non-halogen synthetic resin (B) is a polycarbonate resin or an ABS resin.
JP2000368515A 1996-01-12 2000-12-04 Flame retardant for resin and flame retardant resin composition Expired - Lifetime JP3193029B2 (en)

Priority Applications (1)

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Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP8-4037 1996-01-12
JP403796 1996-01-12
JP2000368515A JP3193029B2 (en) 1996-01-12 2000-12-04 Flame retardant for resin and flame retardant resin composition

Related Parent Applications (1)

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JP3193029B2 JP3193029B2 (en) 2001-07-30

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003025064A1 (en) * 2001-09-14 2003-03-27 Asahi Kasei Chemicals Corporation Polyphenylene ether composition
KR100462530B1 (en) * 2002-06-12 2004-12-17 제일모직주식회사 Flame Retardant Thermoplastic Resin Composition Showing Good Chemical Resistance
KR101139387B1 (en) * 2010-05-31 2012-04-27 합자회사 거광산업 Composition of the celling finishing materials having flane-retardation and method for manufacturing of the celling finishing materials using there of

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003025064A1 (en) * 2001-09-14 2003-03-27 Asahi Kasei Chemicals Corporation Polyphenylene ether composition
US7371790B2 (en) * 2001-09-14 2008-05-13 Asahi Kasei Chemicals Corporation Polyphenylene ether composition
KR100462530B1 (en) * 2002-06-12 2004-12-17 제일모직주식회사 Flame Retardant Thermoplastic Resin Composition Showing Good Chemical Resistance
KR101139387B1 (en) * 2010-05-31 2012-04-27 합자회사 거광산업 Composition of the celling finishing materials having flane-retardation and method for manufacturing of the celling finishing materials using there of

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