JPH1045947A - Surface-treated flame-retardant organic powder and resin composition containing the same - Google Patents
Surface-treated flame-retardant organic powder and resin composition containing the sameInfo
- Publication number
- JPH1045947A JPH1045947A JP20577296A JP20577296A JPH1045947A JP H1045947 A JPH1045947 A JP H1045947A JP 20577296 A JP20577296 A JP 20577296A JP 20577296 A JP20577296 A JP 20577296A JP H1045947 A JPH1045947 A JP H1045947A
- Authority
- JP
- Japan
- Prior art keywords
- flame
- retardant
- powder
- treated
- resin
- 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.)
- Pending
Links
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】
本発明は、耐熱性ならびに表面処理により分散性が改善
された表面処理難燃性有機粉体、及び該表面処理難燃性
有機粉体を含有する熱可塑性または熱硬化性樹脂組成物
に関する。本発明の難燃性樹脂組成物は例えば電気およ
び電子部品用途、建築材料等の難燃性が要求される分野
等に有用である。TECHNICAL FIELD OF THE INVENTION
The present invention relates to a surface-treated flame-retardant organic powder having improved heat resistance and dispersibility by surface treatment, and a thermoplastic or thermosetting resin composition containing the surface-treated flame-retardant organic powder. The flame-retardant resin composition of the present invention is useful, for example, in fields requiring flame retardancy, such as electric and electronic component applications and building materials.
【０００２】[0002]
【従来の技術】各種樹脂の難燃化に各種難燃性塩素系化
合物、難燃性臭素系化合物、難燃性リン系化合物、難燃
性有機窒素系粉体化合物等の有機難燃剤、および酸化ア
ンチモン、水酸化アルミニウム、水酸化マグネシウム、
赤燐等の無機難燃剤が単独または併用して用いられてい
ることは周知の事実である。2. Description of the Related Art Various flame retardants such as chlorine-based compounds, flame-retardant bromine compounds, flame-retardant phosphorus compounds, flame-retardant organic nitrogen-based powder compounds, etc. Antimony oxide, aluminum hydroxide, magnesium hydroxide,
It is a well-known fact that inorganic flame retardants such as red phosphorus are used alone or in combination.
【０００３】上述の化合物は一般に固体（粉体）であり
且つ高融点であることが多く、それ故に液状化合物を用
いた場合と比較して樹脂への分散性がどうしても悪くな
ってしまう。その結果、これらの粉体を各種樹脂に配合
した場合、液状の難燃剤と比較して配合物の外観や物
性、例えば衝撃強度、難燃性等が低下してしまうことが
知られている。The above-mentioned compounds are generally solid (powder) and often have a high melting point, so that their dispersibility in resins is inevitably worse than when liquid compounds are used. As a result, it has been known that when these powders are blended with various resins, the appearance and physical properties of the blend, such as impact strength and flame retardancy, are reduced as compared with a liquid flame retardant.
【０００４】上記の問題に対し、例えば無機難燃剤の表
面処理を行うことで難燃剤の樹脂への分散性の改善、配
合物の物性や難燃性の向上、高充填化を行うことが報告
されている（特開昭６３−２６８７５２、特開昭５７−
１０８１６４等）。[0004] In order to solve the above problems, it has been reported that, for example, the surface treatment of an inorganic flame retardant improves the dispersibility of the flame retardant in a resin, improves the physical properties and flame retardancy of a compound, and increases the filling. (Japanese Unexamined Patent Application Publication No. 63-268752,
108164).
【０００５】また、有機難燃剤を脂肪酸やそのエステ
ル、脂肪酸アミド、非イオン性界面活性剤、両性界面活
性剤等の低分子化合物やメラミン／ホルムアルデヒド樹
脂等の高分子化合物により難燃剤をマイクロカプセル化
したり、表面をコーティングすることにより、分散性、
難燃性を改善できることが報告されている（特開昭６２
−２５３６１０、特開平７−１５７６５２、特公昭６１
−１１９７７、特開昭５８−１３８７４６、特開昭５４
−９０２４６、特公昭５６−１５７３８等）。The organic flame retardant is microencapsulated with a low molecular weight compound such as a fatty acid, an ester thereof, a fatty acid amide, a nonionic surfactant, an amphoteric surfactant or a high molecular weight compound such as a melamine / formaldehyde resin. Or, by coating the surface, dispersibility,
It has been reported that the flame retardancy can be improved (Japanese Patent Laid-Open No. Sho 62
253610, JP-A-7-157652, JP-B-61
-11977, JP-A-58-138746, JP-A-54
-90246, JP-B-56-15738, etc.).
【０００６】近年、難燃性樹脂組成物の製造において、
種々の要因から混練および成形時のハイフロー化、混練
温度や成形温度の向上等が求められている。この目的の
ため、特に樹脂に有機または無機フィラーが添加されて
いる場合、耐熱性良好な分散性改良剤の使用が必須であ
る。しかしながら、上記の低分子化合物を用いて難燃性
有機粉体を表面処理した場合、高温での混練、成形、加
工時に難燃性有機粉体の表面上の表面処理剤が揮発して
しまい、その結果粉体の分散不良や成形物の難燃性の低
下をもたらすという欠点があった。また、上記の高分子
化合物で難燃性有機粉体を表面処理しようとする際に
は、表面処理剤が逆に凝集剤として作用してしまい、難
燃性有機粉体の分散不良、配合物の難燃性低下となるば
かりではなく、増粘剤としても作用してしまい混練、成
形時の加工性を低下させてしまうという欠点があった。
更に、この高分子化合物で難燃性有機粉体を被覆する場
合には、例えばモノマーを懸濁重合させながら難燃性有
機粉体を被覆したり、ポリマーを溶解した溶媒中で一旦
難燃性有機粉体を被覆した後に溶媒を留去する必要があ
り、作業も繁雑で時間がかかるため、コストの面からも
実用的ではなかった。In recent years, in the production of flame-retardant resin compositions,
Due to various factors, high flow during kneading and molding, improvement of kneading temperature and molding temperature, and the like are required. For this purpose, especially when an organic or inorganic filler is added to the resin, it is essential to use a dispersibility improver having good heat resistance. However, when the surface treatment of the flame-retardant organic powder using the above low-molecular compound, kneading at a high temperature, molding, the surface treatment agent on the surface of the flame-retardant organic powder at the time of processing volatilizes, As a result, there are drawbacks in that the dispersion of the powder is poor and the flame retardancy of the molded product is reduced. Further, when the surface treatment of the flame-retardant organic powder with the above-mentioned polymer compound is performed, the surface treatment agent acts as a flocculant in reverse, resulting in poor dispersion of the flame-retardant organic powder, Not only lowers the flame retardancy, but also acts as a thickener, resulting in a reduction in kneading and workability during molding.
Further, when coating the flame-retardant organic powder with the polymer compound, for example, the flame-retardant organic powder is coated while the monomer is subjected to suspension polymerization, or the flame-retardant organic powder is once dissolved in a solvent in which the polymer is dissolved. It is necessary to distill off the solvent after coating the organic powder, and the operation is complicated and time-consuming, which is not practical in terms of cost.
【０００７】[0007]
【発明が解決しようとする課題】本発明の目的は、難燃
性塩素系粉体、難燃性臭素系粉体、難燃性有機リン系粉
体およびその金属塩、難燃性有機窒素系粉体の様な難燃
性有機粉体を上述の様な条件下使用する場合に、流動性
および耐熱性の優れた表面処理難燃性有機粉体を提供す
ること、ならびに該粉体を用いた難燃性、流動性、耐熱
性良好な難燃性樹脂組成物を提供することである。An object of the present invention is to provide a flame-retardant chlorine-based powder, a flame-retardant bromine-based powder, a flame-retardant organic phosphorus-based powder and a metal salt thereof, and a flame-retardant organic nitrogen-based powder. When a flame-retardant organic powder such as a powder is used under the above-described conditions, a surface-treated flame-retardant organic powder having excellent fluidity and heat resistance is provided. An object of the present invention is to provide a flame-retardant resin composition having excellent flame retardancy, fluidity and heat resistance.
【０００８】[0008]
【課題を解決するための手段】本発明者は上記の課題を
解決するために鋭意検討重ねた結果、表面処理に用いる
表面処理剤として塩基性官能基および／または中性官能
基を有する耐熱性の高い化合物を用いることにより、分
散性、流動性および耐熱性の優れた表面処理された難燃
性有機粉体が得られることを見出すとともに、該粉体を
用いることにより難燃性、耐熱性および流動性良好な難
燃性樹脂組成物が得られることを見出し本発明に至っ
た。The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, have found that a heat-resistant resin having a basic functional group and / or a neutral functional group as a surface treatment agent used for surface treatment. By using a compound having high dispersibility, it is found that a surface-treated flame-retardant organic powder excellent in dispersibility, fluidity and heat resistance can be obtained, and by using the powder, flame retardancy and heat resistance can be obtained. The inventors have found that a flame-retardant resin composition having good fluidity can be obtained, and have reached the present invention.
【０００９】すなわち、本発明は難燃性塩素系粉体、難
燃性臭素系粉体、難燃性有機リン系粉体もしくはその金
属塩、または難燃性有機窒素系粉体のうちいずれか少な
くとも一つを塩基性官能基および／または中性官能基を
有する数平均分子量１，０００〜８，０００の高分子表
面処理剤により処理した表面処理難燃性有機粉体、なら
びに該表面処理難燃性有機粉体を熱可塑性樹脂および／
または熱硬化性樹脂１００重量部に対して０．１〜５０
重量部含有することを特徴とする難燃性樹脂組成物であ
る。That is, the present invention relates to any one of a flame-retardant chlorine powder, a flame-retardant bromine-based powder, a flame-retardant organic phosphorus-based powder or a metal salt thereof, and a flame-retardant organic nitrogen-based powder. Surface-treated flame-retardant organic powder, at least one of which has been treated with a polymer surface-treating agent having a number average molecular weight of 1,000 to 8,000 having a basic functional group and / or a neutral functional group; Combustible organic powder is converted to thermoplastic resin and / or
Alternatively, 0.1 to 50 parts by weight per 100 parts by weight of the thermosetting resin
It is a flame-retardant resin composition characterized by containing by weight.
【００１０】[0010]
【発明の実施の形態】本発明に用いる難燃性塩素系粉
体、難燃性臭素系粉体、有機リン系粉体およびその金属
塩、有機窒素系粉体とは、常温（２５℃）にて固体であ
って、さらにその平均粒径がおおよそ０．１μｍ〜１０
００μｍの粉体化合物である。BEST MODE FOR CARRYING OUT THE INVENTION Flame-retardant chlorine-based powder, flame-retardant bromine-based powder, organophosphorus-based powder and metal salts thereof, and organic nitrogen-based powder used in the present invention are ordinary temperature (25 ° C.). , And the average particle size is about 0.1 μm to 10
It is a powder compound of 00 μm.
【００１１】本発明に用いる難燃性塩素系粉体とは分子
中に塩素を含有し難燃性を示す化合物であるが、例えば
パークロロシクロペンタデカン、塩素化ポリエチレン樹
脂、塩素化パラフィン、塩化ビニル樹脂、塩素化塩化ビ
ニル樹脂が挙げられる。難燃性塩素系粉体における塩素
含有率は難燃性を示せば特に限定されるものではない
が、樹脂への難燃剤の配合量を考慮した場合、塩素含有
率が１０％以上のものが好ましい。The flame-retardant chlorine-based powder used in the present invention is a compound containing chlorine in the molecule and exhibiting flame retardancy. Examples thereof include perchlorocyclopentadecane, chlorinated polyethylene resin, chlorinated paraffin, and vinyl chloride. Resins and chlorinated vinyl chloride resins. The chlorine content of the flame-retardant chlorine-based powder is not particularly limited as long as it exhibits flame retardancy. However, considering the blending amount of the flame retardant in the resin, the chlorine content is preferably 10% or more. preferable.
【００１２】本発明に用いる難燃性臭素系粉体とは分子
中に臭素を含有し難燃性を示す化合物であるが、例えば
デカブロモジフェニルエーテル、オクタブロモジフェニ
ルエーテル、ヘキサブロモジフェニルエーテル、臭素化
ビスフェノール−Ａおよびそのオリゴマー、ヘキサブロ
モシクロドデカン、エチレンビステトラブロモフタルイ
ミド、エチレンビスペンタブロモジフェニルが挙げられ
る。難燃性臭素系粉体における臭素含有率は難燃性を示
せば特に限定されるものではないが、樹脂への難燃剤の
配合量を考慮した場合、臭素含有率が１０％以上のもの
が好ましい。The flame-retardant bromine-based powder used in the present invention is a compound containing bromine in the molecule and exhibiting flame retardancy. For example, decabromodiphenyl ether, octabromodiphenyl ether, hexabromodiphenyl ether, brominated bisphenol- A and its oligomers, hexabromocyclododecane, ethylenebistetrabromophthalimide, and ethylenebispentabromodiphenyl. The bromine content in the flame-retardant bromine-based powder is not particularly limited as long as it exhibits flame retardancy. However, in consideration of the blending amount of the flame retardant in the resin, the bromine content is preferably 10% or more. preferable.
【００１３】本発明に用いる難燃性有機リン系粉体とは
分子中にリンを含有し難燃性を示す化合物であるが、例
えばリン酸トリアリールエステル、リン酸ジアリールエ
ステルの金属塩、リン酸モノアリールエステルの金属
塩、リン酸ジアルキルエステルの金属塩、リン酸モノア
ルキルエステルの金属塩、リン酸ジアリールエステルの
アンモニウム塩、リン酸モノアリールエステルのアンモ
ニウム塩、リン酸ジアルキルエステルのアンモニウム
塩、リン酸モノアルキルエステルのアンモニウム塩、リ
ン酸ジアリールエステルのアミン塩、リン酸モノアリー
ルエステルのアミン塩、リン酸ジアルキルエステルのア
ミン塩、リン酸モノアルキルエステルのアミン塩、リン
酸のアミン塩等が挙げられる。難燃性有機リン系粉体に
おけるリン含有率は難燃性を示せば特に限定されるもの
ではないが、樹脂への難燃剤の配合量を考慮した場合、
リン含有率が１％以上のものが好ましい。The flame-retardant organic phosphorus-based powder used in the present invention is a compound containing phosphorus in the molecule and exhibiting flame retardancy. Examples thereof include a triaryl phosphate, a metal salt of a diaryl phosphate, and phosphorus. Metal salts of acid monoaryl esters, metal salts of dialkyl phosphates, metal salts of monoalkyl phosphates, ammonium salts of diaryl phosphates, ammonium salts of monoaryl phosphates, ammonium salts of dialkyl phosphates, Ammonium salts of monoalkyl phosphates, amine salts of diaryl phosphates, amine salts of monoaryl phosphates, amine salts of dialkyl phosphates, amine salts of monoalkyl phosphates, amine salts of phosphoric acid, etc. No. The phosphorus content in the flame-retardant organic phosphorus-based powder is not particularly limited as long as it shows flame retardancy, but when considering the blending amount of the flame retardant to the resin,
Those having a phosphorus content of 1% or more are preferred.
【００１４】具体的にはリン酸トリフェニル、リン酸ト
リス（２，６−キシレニル）、リン酸ジフェニルのＡｌ
塩、リン酸モノフェニルのＡｌ塩、リン酸ジブチルのＡ
ｌ塩、リン酸モノブチルのＡｌ塩、リン酸ジフェニルの
Ｍｇ塩、リン酸モノフェニルのＭｇ塩、リン酸ジブチル
のＭｇ塩、リン酸モノブチルのＭｇ塩、リン酸ジフェニ
ルのアンモニウム塩、リン酸モノフェニルのアンモニウ
ム塩、リン酸ジブチルのアンモニウム塩、リン酸モノブ
チルのアンモニウム塩、リン酸ジフェニルのトリエチル
アミン塩、リン酸モノフェニルのトリエチルアミン塩、
リン酸ジブチルのトリエチルアミン塩、リン酸モノブチ
ルのトリエチルアミン塩、リン酸のトリエチルアミン
塩、リン酸ジフェニルのメラミン塩、リン酸モノフェニ
ルのメラミン塩、リン酸のメラミン塩等が挙げられる。Specifically, triphenyl phosphate, tris (2,6-xylenyl) phosphate, diphenyl phosphate of Al
Salt, Al salt of monophenyl phosphate, A of dibutyl phosphate
1 salt, Al salt of monobutyl phosphate, Mg salt of diphenyl phosphate, Mg salt of monophenyl phosphate, Mg salt of dibutyl phosphate, Mg salt of monobutyl phosphate, ammonium salt of diphenyl phosphate, monophenyl phosphate Ammonium salt, dibutyl phosphate ammonium salt, monobutyl phosphate ammonium salt, diphenyl phosphate triethylamine salt, monophenyl phosphate triethylamine salt,
Examples thereof include tributylamine salt of dibutyl phosphate, triethylamine salt of monobutyl phosphate, triethylamine salt of phosphoric acid, melamine salt of diphenyl phosphate, melamine salt of monophenyl phosphate, and melamine salt of phosphoric acid.
【００１５】本発明に於ける難燃性有機窒素系粉体は例
えばメラミン、メラミンシアヌレート、サクシノグアナ
ミン、アジポグアナミン、メチルグルタログアナミン、
ＣＴＵ−グアナミン等が挙げられる。難燃性有機窒素系
粉体における窒素含有率は難燃性を示せば特に限定され
るものではないが、樹脂への難燃剤の配合量を考慮した
場合、窒素含有率が１０％以上であることが好ましい。The flame-retardant organic nitrogen-based powder in the present invention is, for example, melamine, melamine cyanurate, succinoguanamine, adipoguanamine, methylglutaloganamin,
CTU-guanamine and the like. The nitrogen content in the flame-retardant organic nitrogen-based powder is not particularly limited as long as it exhibits flame retardancy. However, in consideration of the amount of the flame retardant mixed with the resin, the nitrogen content is 10% or more. Is preferred.
【００１６】これら列挙した難燃性有機粉体は、単独で
使用しても複数を併用して使用しても良く、その配合物
が難燃性を示すものであれば良い。These listed flame-retardant organic powders may be used alone or in combination of two or more as long as the compound shows flame retardancy.
【００１７】本発明に於ける塩基性官能基を有する高分
子表面処理剤とは、 １）アミノ基を有するポリエステル系高分子分散剤がポ
リエポキシ化合物、平均分子量が５００〜７，０００の
片末端にカルボキシル基を有する化合物及び２級アミノ
基を１個有する化合物とを反応させて得られるアミン価
が５〜２００ｍｇＫＯＨ／ｇ、数平均分子量が１，００
０〜８，０００の範囲にある高分子表面処理剤、 ２）アミノ基を有するポリエステル系高分子分散剤がポ
リエステル、アクリルポリマー成分とから成り、該ポリ
エステル系高分子分散剤のアクリルポリマー成分が３級
アミノ基及び／又は塩基性を示す含窒素複素環を有する
アクリルポリマー成分と、ポリエステルとを反応させて
得られるアミン価が１０〜２００ｍｇＫＯＨ／ｇ、数平
均分子量１，０００〜８，０００の範囲である高分子表
面処理剤、 ３）アミノ基を有するポリエステル系高分子分散剤がポ
リエステル、ポリイソシアネートから成り、該ポリエス
テル系高分子分散剤のポリイソシアネート成分が、平均
２．５〜６の官能性を有するポリイソシアネート成分で
ある高分子表面処理剤、 が挙げられる。当該分散剤は公知の技術に基づき調製す
ればよく、例えば特公平２−１９８４４、特公平４−２
２７７７４に基づき調製すればよい。また、当該高分子
表面処理剤を調製する際、例えば用いる原料または合成
中間体の化合物の分子量の調整や、反応時間の調整等の
反応条件の調整により所望の数平均分子量の高分子表面
処理剤を得ることができる。The polymer surface treating agent having a basic functional group in the present invention is as follows: 1) A polyester polymer dispersant having an amino group is a polyepoxy compound, and one terminal having an average molecular weight of 500 to 7,000. The compound having a carboxyl group and a compound having one secondary amino group has an amine value of 5-200 mgKOH / g and a number average molecular weight of 1,000.
A polymer surface treating agent in the range of 0 to 8,000, 2) a polyester polymer dispersant having an amino group comprises a polyester and an acrylic polymer component, and the acrylic polymer component of the polyester polymer dispersant is 3 An amine value obtained by reacting an acrylic polymer component having a primary amino group and / or a nitrogen-containing heterocyclic ring showing basicity with a polyester has a range of 10 to 200 mgKOH / g and a number average molecular weight of 1,000 to 8,000. 3) The polyester polymer dispersant having an amino group comprises a polyester and a polyisocyanate, and the polyisocyanate component of the polyester polymer dispersant has an average functionality of 2.5 to 6. And a polymer surface treating agent which is a polyisocyanate component having the formula: The dispersant may be prepared based on a known technique, for example, Japanese Patent Publication No. 2-198444 and Japanese Patent Publication No. 4-2.
It may be prepared based on 27774. When preparing the polymer surface treating agent, the polymer surface treating agent having a desired number average molecular weight can be obtained by adjusting the reaction conditions such as adjusting the molecular weight of the starting material or the compound of the synthetic intermediate to be used or adjusting the reaction time. Can be obtained.
【００１８】本発明における中性官能基を有する高分子
表面処理剤とは末端にカルボキシル基を有するオキシ酸
のポリエステル化合物と一般式（１）The polymer surface treating agent having a neutral functional group in the present invention is a polyester compound of an oxyacid having a carboxyl group at a terminal and a compound represented by the general formula (1):
【００１９】[0019]
【化１】 Embedded image
【００２０】（式中ｎは０ないし１５の整数を表す）で
表される多価アルコールとの反応生成物のことである。
ここで原料となるオキシ酸とはヒドロキシル基を有する
カルボン酸で、１２−ヒドロキシステアリン酸またはリ
シノール酸が好ましい。これらのポリエステル化合物
は、１２−ヒドロキシステアリン酸および／またはリシ
ノール酸を加熱脱水することにより容易に得られる。こ
の脱水縮合反応は公知の触媒、例えばリン酸、亜リン
酸、ｐ−トルエンスルホン酸、テトラ−ｎ−ブチルチタ
ネート、テトライソプロピルチタネ−トなどの存在下ま
たは無触媒で１２０〜２５０℃、好ましくは１４０〜２
１０℃の範囲で加熱しつつ生成する水を系外に除去する
ことによって行われる。反応はトルエン等の共沸溶媒中
で行うのが望ましい。これらの分子間脱水によるエステ
ル化反応の進行度合いは、留出した水の量と反応物の酸
価によって判定することが出来る。工業的に１２−ヒド
ロキシステアリン酸とリシノール酸は、それぞれ硬化ヒ
マシ油および精製ヒマシ油を加水分解して得られるので
通常不純物として少量のパルミチン酸やステアリン酸等
の脂肪酸を含有しているが、これらの不純物脂肪酸が本
表面処理剤の原料として支障をきたすことはない。他方
の原料である一般式（１）の多価アルコールはグリセリ
ンまたはポリグリセリンである。ポリグリセリンはグリ
セリンの縮合により容易に得られる。原料として好まし
い一般式（１）の多価アルコールはグリセリンおよび平
均組成で一般式（１）のｎが１〜１５、好ましくは１〜
１０のもので、例えばジグリセリン、テトラグリセリ
ン、ヘキサグリセリン、デカグリセリンなどである。一
般式（１）の多価アルコールとオキシ酸のポリエステル
化合物との反応比率（多価アルコール／オキシ酸のポリ
エステル化合物）は１．０以上で、当該表面処理剤分子
中に平均として０．５個以上の水酸基が存在することが
望ましい。(Wherein n represents an integer of 0 to 15) and is a reaction product with a polyhydric alcohol.
Here, the oxyacid used as a raw material is a carboxylic acid having a hydroxyl group, preferably 12-hydroxystearic acid or ricinoleic acid. These polyester compounds can be easily obtained by heating and dehydrating 12-hydroxystearic acid and / or ricinoleic acid. This dehydration condensation reaction is carried out in the presence or absence of a known catalyst, for example, phosphoric acid, phosphorous acid, p-toluenesulfonic acid, tetra-n-butyl titanate, tetraisopropyl titanate or the like, at 120 to 250 ° C., preferably. Is 140-2
This is performed by removing water generated outside the system while heating at a temperature of 10 ° C. The reaction is desirably performed in an azeotropic solvent such as toluene. The degree of progress of the esterification reaction due to the intermolecular dehydration can be determined by the amount of distilled water and the acid value of the reactant. Industrially, 12-hydroxystearic acid and ricinoleic acid are obtained by hydrolyzing hardened castor oil and refined castor oil, respectively, and therefore usually contain small amounts of fatty acids such as palmitic acid and stearic acid as impurities. The impurity fatty acid does not cause any trouble as a raw material of the present surface treatment agent. The other raw material, the polyhydric alcohol of the general formula (1), is glycerin or polyglycerin. Polyglycerin is easily obtained by condensation of glycerin. Preferred polyhydric alcohols of the general formula (1) as raw materials are glycerin and n of the general formula (1) having an average composition of 1 to 15, preferably 1 to 15.
And 10 such as diglycerin, tetraglycerin, hexaglycerin, decaglycerin and the like. The reaction ratio between the polyhydric alcohol of the general formula (1) and the oxyacid polyester compound (polyhydric alcohol / oxyacid polyester compound) is 1.0 or more, and 0.5 on average in the surface treatment agent molecule. It is desirable that the above hydroxyl groups be present.
【００２１】上記の塩基性官能基および／または中性官
能基を有する高分子表面処理剤の数均分子量は１，００
０〜８，０００の範囲にあることが望ましい。数平均分
子量が１，０００未満の場合には、表面処理難燃性有機
粉体を加熱した時に処理粉体表面から表面処理剤が揮発
により処理効果が低下してしまい、熱可塑性および／ま
たは熱硬化性樹脂に配合した際、難燃性有機粉体の分散
不良や難燃性の低下を引き起こす。また、数平均分子量
が８，０００を越えた場合、逆に凝集剤、増粘剤として
作用する場合があり好ましくない。The number average molecular weight of the high molecular surface treating agent having a basic functional group and / or a neutral functional group is 1,000 or less.
It is desirably in the range of 0 to 8,000. When the number average molecular weight is less than 1,000, the surface treatment agent is volatilized from the surface of the treated powder when the surface-treated flame-retardant organic powder is heated, and the treatment effect is reduced. When blended in a curable resin, it causes poor dispersion of the flame-retardant organic powder and lowers the flame retardancy. On the other hand, if the number average molecular weight exceeds 8,000, it may act as a flocculant and a thickener, which is not preferable.
【００２２】これらの表面処理剤は塩基性または中性で
あり、本発明に用いる難燃性有機粉体を含め有機粉体の
表面は一般に酸性であることから互いの親和性が非常に
高く、従って高い表面処理効果を達成することが出来
る。酸性の表面処理剤を用いた場合、表面処理剤と被処
理粉体との電気的反発により所望の処理効果を得ること
が出来ない。These surface treatment agents are basic or neutral, and the surfaces of organic powders, including the flame-retardant organic powder used in the present invention, are generally acidic, and therefore have a very high affinity for each other. Therefore, a high surface treatment effect can be achieved. When an acidic surface treatment agent is used, a desired treatment effect cannot be obtained due to electric repulsion between the surface treatment agent and the powder to be treated.
【００２３】本発明の上記表面処理剤以外の表面処理剤
や、本発明の異なる複数の表面処理剤とを問題のない範
囲で併用しても何ら差し支えない。本発明に用いられる
表面処理剤の添加量は難燃性塩素系粉体、難燃性臭素系
粉体、難燃性有機リン系粉体およびその金属塩、難燃性
有機窒素系粉体の種類、比表面積及びその表面に結合し
た水分量によっても異なるが、用いる粉体化合物に対し
て０．０５〜２０重量％、好ましくは０．２〜１０重量
％である。又、表面処理法としては、１）難燃性有機粉
体に本表面処理剤をそのまま添加しヘンシェルミキサ
ー、ボールミル、アトマイザー、コロイドミル等の粉砕
機を用いて共粉砕する方法、２）トルエン、キシレン、
ベンゼン、ヘキサン、シクロヘキサン、メチルエチルケ
トン、アセトン、アセトニトリル、四塩化炭素、クロロ
ホルム、塩化メチレン、トリクロロエチレン、ジエチル
エーテル、テトラヒドロフラン等の適当な有機溶媒中に
難燃性有機粉体と共に加え、撹拌、混合後、溶媒を除去
する方法、３）熱可塑性および／または熱硬化性樹脂と
被表面処理難燃性有機粉体の混合物中に直接本表面処理
剤を添加し、一軸混練機、二軸混練機、バンバリーミキ
サー、熱ロール等で混合処理する方法等が挙げられる。A surface treating agent other than the above-mentioned surface treating agent of the present invention, or a plurality of different surface treating agents of the present invention may be used in combination without any problem. The addition amount of the surface treatment agent used in the present invention is a flame-retardant chlorine-based powder, a flame-retardant bromine-based powder, a flame-retardant organic phosphorus-based powder and its metal salt, a flame-retardant organic nitrogen-based powder. Depending on the type, specific surface area and the amount of water bound to the surface, it is 0.05 to 20% by weight, preferably 0.2 to 10% by weight, based on the powder compound used. As the surface treatment method, 1) a method in which the present surface treatment agent is directly added to a flame-retardant organic powder and co-ground using a pulverizer such as a Henschel mixer, a ball mill, an atomizer, and a colloid mill; Xylene,
Add in a suitable organic solvent such as benzene, hexane, cyclohexane, methyl ethyl ketone, acetone, acetonitrile, carbon tetrachloride, chloroform, methylene chloride, trichloroethylene, diethyl ether, tetrahydrofuran, etc. together with the flame-retardant organic powder, stir, mix, 3) The present surface treatment agent is directly added to a mixture of a thermoplastic and / or thermosetting resin and a surface-treated flame-retardant organic powder, and a single-screw kneader, a twin-screw kneader, a Banbury mixer is used. And a method of mixing with a hot roll or the like.
【００２４】熱可塑性樹脂とはスチレン樹脂、ポリエチ
レン樹脂、ポリプロピレン樹脂、アクリル樹脂、メタク
リル樹脂、塩化ビニル樹脂、塩素化ポリエチレン樹脂、
酢酸ビニル樹脂、ポリアミド樹脂、ポリエチレンテレフ
タレート樹脂、ポリブチレンテレフタレート樹脂、ポリ
カーボネート樹脂、ポリスルホン樹脂、ポリフェニレン
エーテル樹脂、変性ポリフェニレンエーテル樹脂、ポリ
フェニレンサルファイド樹脂等であるが、これらに限定
されるものではない。Thermoplastic resins include styrene resins, polyethylene resins, polypropylene resins, acrylic resins, methacrylic resins, vinyl chloride resins, chlorinated polyethylene resins,
Examples include, but are not limited to, vinyl acetate resin, polyamide resin, polyethylene terephthalate resin, polybutylene terephthalate resin, polycarbonate resin, polysulfone resin, polyphenylene ether resin, modified polyphenylene ether resin, polyphenylene sulfide resin, and the like.
【００２５】熱硬化性樹脂とはエポキシ樹脂、フェノー
ル樹脂、不飽和ポリエステル樹脂、ポリイミド樹脂、ポ
リウレタン樹脂等があるが、これに限定されるものでは
ない。The thermosetting resin includes, but is not limited to, epoxy resin, phenol resin, unsaturated polyester resin, polyimide resin, polyurethane resin and the like.
【００２６】また上述の熱可塑性樹脂、熱硬化性樹脂は
単独でも２種類以上を組み合わせて用いてもよく、例え
ば熱硬化性ウレタンエラストマーが挙げられるが、これ
に限定されるものではない。The above-mentioned thermoplastic resins and thermosetting resins may be used alone or in combination of two or more. Examples thereof include thermosetting urethane elastomers, but are not limited thereto.
【００２７】また本発明の表面処理難燃性有機粉体は、
必要に応じて液状の難燃剤、例えばトリクレジルホスフ
ェート、レゾルシノールビスジフェニルホスフェート、
トリブチルホスフェート、トリスクロロエチルホスフェ
ート、ジメチルメチルホスホネート、トリブチルホスフ
ィンオキシド等の液状リン化合物、塩素化パラフィン等
の液状塩素化合物と併用することが出来、これらの液状
化合物の併用は本発明の特徴を損なうものではない。The surface-treated flame-retardant organic powder of the present invention comprises:
If necessary, a liquid flame retardant, such as tricresyl phosphate, resorcinol bisdiphenyl phosphate,
It can be used in combination with liquid phosphorus compounds such as tributyl phosphate, trischloroethyl phosphate, dimethylmethylphosphonate and tributyl phosphine oxide, and liquid chlorine compounds such as chlorinated paraffin, and the use of these liquid compounds impairs the characteristics of the present invention. is not.
【００２８】さらに、本発明の難燃性樹脂組成物は、必
要に応じて通常各種樹脂への添加剤として用いられる、
安定剤、顔料、可塑剤、滑剤、整泡剤、発泡剤等と併用
することが出来、これらの各種添加剤の併用は本発明の
特徴を損なうものでもない。Further, the flame-retardant resin composition of the present invention may be used as an additive to various resins, if necessary.
It can be used in combination with stabilizers, pigments, plasticizers, lubricants, foam stabilizers, foaming agents, and the like, and the use of these various additives does not impair the features of the present invention.
【００２９】本発明の表面処理難燃性有機粉体を熱可塑
性樹脂および／または熱硬化性樹脂へ混練する方法とし
ては、例えば、一軸混練機、二軸混練機、バンバリーミ
キサー、熱ロール等で混合処理する方法等が挙げられる
が、通常混連に用いられる方法であれば特に限定されな
い。As a method of kneading the surface-treated flame-retardant organic powder of the present invention into a thermoplastic resin and / or a thermosetting resin, for example, a single-screw kneader, a twin-screw kneader, a Banbury mixer, a hot roll, or the like is used. Although a method of performing a mixing treatment and the like can be mentioned, the method is not particularly limited as long as it is a method usually used for mixing.
【００３０】熱可塑性樹脂および／または熱硬化性樹脂
への本発明の表面処理された難燃性有機粉体の添加量
は、樹脂１００重量部に対して０．１〜５０重量部含有
することが好ましい。添加量が樹脂１００重量部に対し
て０．１重量部未満の場合、添加する樹脂に対して所望
の難燃性を付与することが出来ない。また添加量が樹脂
１００重量部に対して５０重量部より多い場合、配合物
の諸物性、例えば機械的強度等の低下を引き起こす。The amount of the surface-treated flame-retardant organic powder of the present invention added to the thermoplastic resin and / or the thermosetting resin is 0.1 to 50 parts by weight based on 100 parts by weight of the resin. Is preferred. If the amount is less than 0.1 part by weight with respect to 100 parts by weight of the resin, the desired flame retardancy cannot be imparted to the added resin. If the amount is more than 50 parts by weight with respect to 100 parts by weight of the resin, the physical properties of the compound, for example, the mechanical strength and the like are reduced.
【００３１】尚、上述の表面処理剤により表面処理され
た難燃性有機粉体と熱可塑性および／または熱硬化性樹
脂との混練、混合に際しては周知の方法によって行うこ
とが出来る。The kneading and mixing of the flame-retardant organic powder surface-treated with the above-mentioned surface treating agent and a thermoplastic and / or thermosetting resin can be carried out by a known method.
【００３２】本発明の表面処理された難燃性有機粉体
は、上述の様に被処理難燃性有機粉体は耐熱性が高く、
かつ被処理難燃性有機粉体の表面と親和性の高い表面処
理剤を用いて処理しているため、混練、成形加工時の温
度が高い場合でも表面処理剤の揮発による処理効果の低
減が抑制され、同粉体の配合物が混練、成形加工時に高
い流動性、分散性を保持することができ、従って樹脂を
難燃化する際に必要な難燃性有機粉体の添加量を未表面
処理難燃性有機粉体と比較して減らすことが可能とな
る。The flame-retardant organic powder of the present invention, which has been subjected to surface treatment, has a high heat resistance as described above.
In addition, since the treatment is performed using a surface treatment agent that has a high affinity for the surface of the flame-retardant organic powder to be treated, even if the temperature at the time of kneading and molding is high, the treatment effect due to volatilization of the surface treatment agent is reduced. Therefore, the compound of the powder can maintain high fluidity and dispersibility at the time of kneading and molding, and therefore, the amount of the flame-retardant organic powder necessary for making the resin flame-retardant is not controlled. It becomes possible to reduce as compared with the surface-treated flame-retardant organic powder.
【００３３】[0033]
【実施例】以下、製造例、実施例、比較例により本発明
を具体的に説明する。尚、各例における「部」および
「％」はいずれも重量基準によるものとする。EXAMPLES The present invention will be specifically described below with reference to Production Examples, Examples and Comparative Examples. In each example, “parts” and “%” are based on weight.
【００３４】製造例１．塩基性官能基を有する高分子表
面処理剤の合成１ 攪はん機、還流管、温度計、窒素ガス導入管を備えた４
ツ口フラスコにキシレン１５０．０部、テトラブトキシ
チタネート０．３部、オクチル酸４４．０部、ｅ−カプ
ロラクトン５５６．０部を仕込み１４０〜１６０℃まで
昇温した。次いで１６０℃のまま反応を行い、固形分が
７９％になった時点で反応を終了した。室温まで冷却し
た後、キシレン２４９．７部を加えて片末端にカルボキ
シル基を有するボリエステル化合物Ａを得た。得られた
ポリエステル化合物Ａは数平均分子量が１５００、固形
分が６０．０％、酸価が２９．０ｍｇＫＯＨ／ｇであっ
た。Production Example 1 Synthesis of Polymer Surface Treatment Agent Having Basic Functional Group 1 4 equipped with a stirrer, reflux tube, thermometer, and nitrogen gas introduction tube
150.0 parts of xylene, 0.3 part of tetrabutoxytitanate, 44.0 parts of octylic acid, and 556.0 parts of e-caprolactone were charged into a one-necked flask and heated to 140 to 160 ° C. Next, the reaction was carried out at 160 ° C., and the reaction was terminated when the solid content became 79%. After cooling to room temperature, 249.7 parts of xylene was added to obtain a polyester compound A having a carboxyl group at one end. The obtained polyester compound A had a number average molecular weight of 1500, a solid content of 60.0%, and an acid value of 29.0 mgKOH / g.
【００３５】攪はん機、還流管、温度計、窒素ガス導入
管を備えたフラスコにキシレン３００．０部を仕込み１
３０〜１３５℃まで昇温した．グリシジルメタアクリレ
ート３９０．０部、ブチルメタアクリレート２１０．０
部、ターシャリーブチルパーオキシ−２−エチルヘキサ
エート３６．０部の混合液を２時問かけて滴下した後、
１３５℃で１時間重合させた。その後ターシャリーブチ
ルパーオキシ−２−エチルヘキサエート３．０部をキシ
レン１０．０部に溶解させた混合液を加え、さらに１２
０℃、５時間重合反応を行い反応を終了した。室温まで
冷却した後、キシレン５１．０部を加えてポリエポキシ
化合物Ｂを得た。得られたポリエポキシ化合物Ｂは、固
形分が６２．０％、数平均分子量が３０００、エポキシ
価が２５０．０ｍｇＫＯＨ／ｇであった．A flask equipped with a stirrer, a reflux tube, a thermometer, and a nitrogen gas inlet tube was charged with 300.0 parts of xylene.
The temperature was raised to 30 to 135 ° C. Glycidyl methacrylate 390.0 parts, butyl methacrylate 210.0
And a mixture of 36.0 parts of tert-butylperoxy-2-ethylhexaate was dropped over 2 hours.
Polymerization was performed at 135 ° C. for 1 hour. Thereafter, a mixed solution obtained by dissolving 3.0 parts of tertiary butyl peroxy-2-ethylhexaate in 10.0 parts of xylene was added.
A polymerization reaction was performed at 0 ° C. for 5 hours to complete the reaction. After cooling to room temperature, 51.0 parts of xylene was added to obtain a polyepoxy compound B. The obtained polyepoxy compound B had a solid content of 62.0%, a number average molecular weight of 3000, and an epoxy value of 250.0 mgKOH / g.
【００３６】攪はん機、還流管、温度計、窒素ガス導入
菅を備えたフラスコに、キシレン３５．７部と上記で得
られたポリエステルＡ４５．１部、及び上記で得られた
ポリエポキシ化合物Ｂ１５．７部を仕込み、１２０℃ま
で昇温し反応を行った。酸価が１ｍｇＫＯＨ／ｇ以下に
なった時点で６０℃まで冷却し、ジ−ｎ−ブチルアミン
３．５部を加え、１００℃まで昇温した。１００℃で４
〜５時問反応させ、塩基性官能基を有する表面処理剤
（以下、表面処理剤Ａとする）を得た。得られた表面処
理剤Ａは、固形分が４０．１％、数平均分子量が７５０
０でアミン価が３８．５ｍｇＫＯＨ／ｇであった．In a flask equipped with a stirrer, a reflux tube, a thermometer, and a nitrogen gas inlet tube, 35.7 parts of xylene, 45.1 parts of the polyester A obtained above, and the polyepoxy compound obtained above B15.7 parts were charged and the temperature was raised to 120 ° C. to carry out a reaction. When the acid value became 1 mgKOH / g or less, the mixture was cooled to 60 ° C, 3.5 parts of di-n-butylamine was added, and the temperature was raised to 100 ° C. 4 at 100 ° C
The reaction was performed for about 5 to 5 hours to obtain a surface treating agent having a basic functional group (hereinafter, referred to as a surface treating agent A). The obtained surface treatment agent A has a solid content of 40.1% and a number average molecular weight of 750.
At 0, the amine value was 38.5 mgKOH / g.
【００３７】製造例２．塩基性官能基を有する高分子表
面処理剤の合成２ 攪はん機、還流管、温度計、窒素ガス導入菅、滴下槽を
備えたフラスコに、キシレン３６．８部、デカノール
１．０部、ナトリウムメチラート０．１部を仕込み、１
３０〜１４０℃まで窒素気流下で昇温した。還流状態に
おいてｅ−カプロラクトン３５．７部を１時間かけ滴下
槽よリ滴下した．さらに還流状態で４時間攪拝し、１４
０℃で３０分加熱乾燥後の固形分が４５％に達したのを
確認し、ブチルグリシジルェーテル１５．５部を１時問
かけ滴下槽よリ滴下した．トリレンジイソシアネート
４．５部を添加し３０℃で２時問攪はんし、イソシアネ
ート基が５０％反応したのを確認し、２−ヒドロキシエ
チルメタクリレート１．５部を添加した。これを６０℃
まで昇温し、３時間反応を行いイソシアネート基が１０
０％反応した時点で反応を終了した．得られたものをマ
クロマーＡとする。Production Example 2 Synthesis of polymer surface treating agent having basic functional group 2 In a flask equipped with a stirrer, a reflux tube, a thermometer, a nitrogen gas inlet tube, and a dropping tank, 36.8 parts of xylene, 1.0 part of decanol, Charge 0.1 part of sodium methylate, 1
The temperature was raised to 30 to 140 ° C under a nitrogen stream. In a reflux state, 35.7 parts of e-caprolactone was added dropwise from the dropping tank over 1 hour. After 4 hours of further stirring under reflux, 14
After confirming that the solid content after heating and drying at 0 ° C. for 30 minutes reached 45%, 15.5 parts of butyl glycidyl ether was dropped in the dropping tank over 1 hour. Toluene diisocyanate (4.5 parts) was added and the mixture was stirred at 30 ° C. for 2 hours. After confirming that 50% of the isocyanate group had reacted, 1.5 parts of 2-hydroxyethyl methacrylate was added. 60 ℃
And reacted for 3 hours to reduce the isocyanate groups to 10
The reaction was terminated when 0% was reacted. The resultant is designated as Macromer A.
【００３８】攪はん機、還流管、温度計、窒素ガス導入
管を備えたフラスコに、キシレン３９．０部を仕込み８
５℃まで昇温し、そこヘ、上記で得られたマクロマーＡ
とジメチルアミノプロピルアクリルアミド１．０部と
２、２’−アゾビス（２，４ジメチルバレロニトリル）
０．８部の２０％溶液を別々の滴下槽より２時間をかけ
滴下した。滴下後、８５℃で２時間反応させ塩基性官能
基を有する高分子表面処理剤（以下、表面処理剤Ｂとす
る）を得た．39.0 parts of xylene was charged into a flask equipped with a stirrer, a reflux tube, a thermometer, and a nitrogen gas inlet tube.
The temperature was raised to 5 ° C., and the macromer A obtained above was added thereto.
And dimethylaminopropylacrylamide 1.0 part and 2,2'-azobis (2,4 dimethylvaleronitrile)
0.8 parts of a 20% solution was added dropwise from separate dropping tanks over 2 hours. After the dropwise addition, the mixture was reacted at 85 ° C. for 2 hours to obtain a polymer surface treating agent having a basic functional group (hereinafter, referred to as a surface treating agent B).
【００３９】製造例３．中性官能基を有する高分子表面
処理剤の合成 合成は特開平１−２７０９３２記載の製造例２に基づき
行った。工業用リシノール酸（中和価１８０）１５０ｇ
とキシレン９５ｇの混合物を１９０〜２００℃で２０時
間加熱し、生成する水を留去した。次いでキシレンを減
圧下に１５０℃で留去した。こうして淡赤褐色の粘ちょ
うなポリリシノール酸Ａ１４１．１ｇが得られた。この
ものの酸価は３８．０であった。酸価から求めた縮合度
は４．７であった。次に、攪拌機、温度計、窒素ガス導
入管を備えたフラスコにポリリシノール酸Ａ１３３部
（０．１モル）とテトラグリセリン６２．８部（０．２
モル）に仕込み混合し、窒素気流下２００℃で７時間撹
拌混合してエステル化反応を行った。こうして得られた
高分子表面処理剤Ｃ（以下、表面処理剤Ｃとする）は淡
褐色液体で、酸価は２．５ｍｇＫＯＨ／ｇ、水酸基価は
７７．１ｍｇＫＯＨ／ｇであった。Production Example 3 Synthesis of Polymer Surface Treatment Agent Having Neutral Functional Group Synthesis was performed based on Production Example 2 described in JP-A-1-270932. 150 g of industrial ricinoleic acid (neutralization value 180)
And a mixture of 95 g of xylene were heated at 190 to 200 [deg.] C. for 20 hours to evaporate generated water. Then xylene was distilled off at 150 ° C. under reduced pressure. Thus, 141.1 g of a light reddish brown viscous polyricinoleic acid A was obtained. Its acid value was 38.0. The degree of condensation determined from the acid value was 4.7. Next, 133 parts (0.1 mol) of polyricinoleic acid A and 62.8 parts (0.2 mol) of tetraglycerin were placed in a flask equipped with a stirrer, a thermometer, and a nitrogen gas inlet tube.
Mol), and the mixture was stirred and mixed at 200 ° C. for 7 hours under a nitrogen stream to carry out an esterification reaction. The polymer surface treating agent C thus obtained (hereinafter referred to as surface treating agent C) was a light brown liquid, and had an acid value of 2.5 mgKOH / g and a hydroxyl value of 77.1 mgKOH / g.
【００４０】実施例１．製造例１による表面処理剤Ａを
１０℃／ｍｉｎの昇温速度で熱重量分析を行い、１０
０、２００、３００℃での重量減少率（重量％）を測定
した。（使用機器：（株）リガク製、ＴＡＳ−２００シ
ステム）Embodiment 1 The thermogravimetric analysis of the surface treatment agent A according to Production Example 1 was performed at a heating rate of 10 ° C./min.
The weight loss rates (% by weight) at 0, 200 and 300 ° C. were measured. (Equipment: Rigaku Corporation, TAS-200 system)
【００４１】実施例２．表面処理剤として製造例２によ
る表面処理剤Ｂを用いる以外は実施例１と同様の操作を
行った。Embodiment 2 FIG. The same operation as in Example 1 was performed except that the surface treatment agent B according to Production Example 2 was used as the surface treatment agent.
【００４２】実施例３．表面処理剤として製造例３によ
る表面処理剤Ｃを用いる以外は実施例１と同様の操作を
行った。Embodiment 3 FIG. The same operation as in Example 1 was performed except that the surface treatment agent C according to Production Example 3 was used as the surface treatment agent.
【００４３】比較例１．表面処理剤としてステアリン酸
（試薬、和光純薬工業（株）製）を用いる以外は実施例
１と同様の操作を行った。Comparative Example 1 The same operation as in Example 1 was performed except that stearic acid (reagent, manufactured by Wako Pure Chemical Industries, Ltd.) was used as a surface treatment agent.
【００４４】比較例２．表面処理剤としてポリアミド樹
脂（三洋化成工業（株）製、ポリマイドＳ−４０Ｅ、数
平均分子量約３０，０００）を用いる以外は実施例１と
同様の操作を行った。Comparative Example 2 The same operation as in Example 1 was performed except that a polyamide resin (manufactured by Sanyo Chemical Industry Co., Ltd., Polyamide S-40E, number average molecular weight: about 30,000) was used as the surface treatment agent.
【００４５】実施例１〜３、比較例１〜２の結果を表
１、２に示す。Tables 1 and 2 show the results of Examples 1 to 3 and Comparative Examples 1 and 2.
【００４６】[0046]
【表１】 [Table 1]
【００４７】[0047]
【表２】 [Table 2]
【００４８】表１、２から実施例１〜３および比較例２
に使用した表面処理剤は、比較例１で使用の表面処理剤
と比較して、より優れた耐熱性を有していることが判明
した。From Tables 1 and 2, Examples 1-3 and Comparative Example 2
It was found that the surface treating agent used in Comparative Example 1 had better heat resistance than the surface treating agent used in Comparative Example 1.
【００４９】実施例４．難燃性粉体としてエチレンビス
ペンタブロモジフェニル（アルベマール社製、ＳＡＹＴ
ＥＸ８０１０）１０００ｇを製造例１による表面処理剤
Ａ４０ｇ（固形分換算１０ｇ）でヘンシェルミキサー
（岡田精工（株）製、ＳＫ−１５０）を用いて１５分間
表面処理を行い処理粉体Ａを得た。得られた処理粉体Ａ
を６０℃、１ｍｍＨｇにて１２時間減圧乾燥後、試験管
に同処理粉体０．５ｇ秤量し、トルエン１０ｍＬを加え
た後に試験管内を均一に懸濁させ、３０分間静置後の分
散の状態を上澄みの厚みを測定することにより沈降安定
性の評価を行った。Embodiment 4 FIG. Ethylene bispentabromodiphenyl (Albemarle Co., SAYT
(EX8010) 1000 g was subjected to a surface treatment for 15 minutes using 40 g of the surface treating agent A (10 g in terms of solid content) according to Production Example 1 using a Henschel mixer (SK-150, manufactured by Okada Seiko Co., Ltd.) to obtain treated powder A. Obtained treated powder A
After drying under reduced pressure at 60 ° C. and 1 mmHg for 12 hours, 0.5 g of the same treated powder was weighed into a test tube, 10 mL of toluene was added, and the inside of the test tube was uniformly suspended. Was evaluated for sedimentation stability by measuring the thickness of the supernatant.
【００５０】実施例５．表面処理剤として製造例２によ
る表面処理剤Ｂ１０ｇを用いる以外は実施例４同様の操
作を行った（表面処理された処理粉体を処理粉体Ｂとよ
ぶ）。Embodiment 5 FIG. The same operation as in Example 4 was performed except that 10 g of the surface treating agent B according to Production Example 2 was used as the surface treating agent (the treated powder subjected to the surface treatment is referred to as treated powder B).
【００５１】実施例６．表面処理剤として製造例３によ
る表面処理剤Ｃ１０ｇを用いる以外は実施例４同様の操
作を行った（表面処理された処理粉体を処理粉体Ｃとよ
ぶ）。Embodiment 6 FIG. The same operation as in Example 4 was performed except that 10 g of the surface treating agent C according to Production Example 3 was used as the surface treating agent (the treated powder having been subjected to the surface treatment is referred to as treated powder C).
【００５２】実施例７．難燃性粉体としてパークロロシ
クロペンタデカン（オキシデンタルケミカル社製、デク
ロランプラス２５）１，０００ｇを用いる以外は実施例
４と同様の操作を行った（表面処理された処理粉体を処
理粉体Ｄとよぶ）。Embodiment 7 FIG. The same operation as in Example 4 was performed except that 1,000 g of perchlorocyclopentadecane (Dechlorane Plus 25, manufactured by Oxydental Chemical Co., Ltd.) was used as the flame-retardant powder. Body D).
【００５３】実施例８．難燃性粉体としてメラミンホス
フェート（Ａ＆Ｗ社製、ＡＭＧＡＲＤ ＮＨ）１，００
０ｇを用いる以外は実施例４と同様の操作を行った（表
面処理された処理粉体を処理粉体Ｅとよぶ）。Embodiment 8 FIG. Melamine phosphate (A & W, AMGARD NH) 1,00 as flame-retardant powder
The same operation as in Example 4 was performed except that 0 g was used (the surface-treated powder was referred to as treated powder E).
【００５４】実施例９．難燃性粉体としてメラミンシア
ヌレート（日産化学工業（株）製、ＭＣ−６１０）１，
０００ｇを用いる以外は実施例４と同様の操作を行った
（表面処理された処理粉体を処理粉体Ｆとよぶ）。Embodiment 9 FIG. Melamine cyanurate (MC-610, manufactured by Nissan Chemical Industries, Ltd.) 1 as a flame-retardant powder
The same operation as in Example 4 was performed except that 000 g was used (the treated powder having been subjected to the surface treatment is referred to as treated powder F).
【００５５】比較例３．表面処理剤を用いず、実施例４
と同様の操作で沈降安定性の評価を行った。Comparative Example 3 Example 4 without using a surface treatment agent
The sedimentation stability was evaluated by the same operation as described above.
【００５６】比較例４．表面処理剤として酸性表面処理
剤であるステアリン酸１０ｇ（試薬、和光純薬工業
（株）製）を用いる以外は実施例４と同様の操作を行っ
た（表面処理された処理粉体を処理粉体Ｇとよぶ）。Comparative Example 4 The same operation as in Example 4 was performed except that 10 g of stearic acid (reagent, manufactured by Wako Pure Chemical Industries, Ltd.) as an acidic surface treatment agent was used as the surface treatment agent. Body G).
【００５７】比較例５．表面処理剤として酸性表面処理
剤であるステアリン酸１０ｇを用いる以外は実施例７と
同様の操作を行った（表面処理された処理粉体を処理粉
体Ｈとよぶ）。Comparative Example 5 The same operation as in Example 7 was performed except that 10 g of stearic acid as an acidic surface treating agent was used as the surface treating agent (the treated powder having been subjected to the surface treatment is referred to as treated powder H).
【００５８】比較例６ 表面処理剤としてポリアミド樹脂（三洋化成工業（株）
製、ポリマイドＳ−４０Ｅ、数平均分子量約３０，００
０）／トルエン／イソプロパノール＝５０／２５／２５
（重量比率）の溶液２０ｇを用いる以外は実施例４と同
様の操作を行った（表面処理された処理粉体を処理粉体
Ｉとよぶ）。Comparative Example 6 A polyamide resin (Sanyo Chemical Industry Co., Ltd.) was used as a surface treating agent.
Polyamide S-40E, number average molecular weight about 30,00
0) / toluene / isopropanol = 50/25/25
The same operation as in Example 4 was performed except that 20 g of the solution (weight ratio) was used (the treated powder having been subjected to the surface treatment is referred to as treated powder I).
【００５９】実施例４〜９、比較例３〜６の結果を表
３、４に示す。Tables 3 and 4 show the results of Examples 4 to 9 and Comparative Examples 3 to 6.
【００６０】[0060]
【表３】 [Table 3]
【００６１】[0061]
【表４】 [Table 4]
【００６２】表３、４から実施例４〜９の表面処理粉体
は比較例３〜６の表面処理粉体と比較して、より高い沈
降安定性を有していることが判明した。From Tables 3 and 4, it was found that the surface-treated powders of Examples 4 to 9 had higher sedimentation stability than the surface-treated powders of Comparative Examples 3 to 6.
【００６３】実施例１０．ポリスチレン樹脂（旭化成
（株）製、Ｈ８６５２）１００部に対して難燃性有機粉
体として実施例４で得られた処理粉体Ａを１３部、三酸
化アンチモン（三工（株）製、ポリセーフ１００−Ｔ）
４部の比率でラボプラストミル（東洋精機製作所（株）
製、ＭＲタイプ）、２軸混練機（東洋精機製作所（株）
製、２Ｄ２０Ｓ型）およびペレタイザー（東洋精機製作
所（株）製、ＭＣ１）を用いて、２１０℃で混練、次い
でペレット化を行った。この時２軸混練機のダイから出
てくるストランドの外観を目視にて観察した。得られた
ペレットから射出成形機（日本製鋼所、Ｎ４０−ＢII）
を用い、ＪＩＳ Ｋ ７１１０の２号試験片（Ａ切欠
き）およびＪＩＳ Ｋ ７２０１のＡ−１号試験片を調
製した。得られた試験片の外観を目視にて評価するとと
もに、アイゾッド衝撃強度試験機を用いて衝撃強度を測
定した。さらに配合した同ペレットのメルトフローレー
トをメルトフローインデクサー（東洋精機製作所（株）
製、メルトインデクサーＰ１０１型）を用いて測定し
た。次に調製した試験片の難燃性を酸素指数測定装置
（東洋精機製作所（株）製、Ｄ型キャンドル燃焼試験
機）を用いて測定した。Embodiment 10 FIG. 13 parts of the treated powder A obtained in Example 4 as a flame-retardant organic powder with respect to 100 parts of a polystyrene resin (H8652 manufactured by Asahi Kasei Corporation), antimony trioxide (manufactured by Sanko Co., Ltd., Polysafe 100-T)
Labo Plast Mill (Toyo Seiki Seisakusho Co., Ltd.)
, MR type), 2-axis kneader (Toyo Seiki Seisakusho Co., Ltd.)
And 2P20S) and a pelletizer (MC1 manufactured by Toyo Seiki Seisaku-sho, Ltd.) at 210 ° C., and then pelletized. At this time, the appearance of the strand coming out of the die of the twin-screw kneader was visually observed. Injection molding machine (Nihon Steel Works, N40-BII) from the obtained pellets
Was used to prepare JIS K 7110 No. 2 test piece (A notch) and JIS K 7201 A-1 test piece. The appearance of the obtained test piece was visually evaluated, and the impact strength was measured using an Izod impact strength tester. Furthermore, the melt flow rate of the blended pellets is calculated using a melt flow indexer (Toyo Seiki Seisakusho Co., Ltd.)
And a melt indexer (Model P101). Next, the flame retardancy of the prepared test piece was measured using an oxygen index measuring device (D-type candle burning tester, manufactured by Toyo Seiki Seisaku-sho, Ltd.).
【００６４】実施例１１．難燃性有機粉体として実施例
５で得られた処理粉体Ｂを用いる以外は実施例１０と同
様の操作を行った。Embodiment 11 FIG. The same operation as in Example 10 was performed except that the treated powder B obtained in Example 5 was used as the flame-retardant organic powder.
【００６５】実施例１２．難燃性有機粉体として実施例
６で得られた処理粉体Ｃを用いる以外は実施例１０と同
様の操作を行った。Embodiment 12 FIG. The same operation as in Example 10 was performed except that the treated powder C obtained in Example 6 was used as the flame-retardant organic powder.
【００６６】比較例７．難燃性有機粉体として比較例４
で得られた処理粉体Ｇを用いる以外は実施例１０と同様
の操作を行った。Comparative Example 7 Comparative example 4 as flame retardant organic powder
The same operation as in Example 10 was performed except that the treated powder G obtained in the above was used.
【００６７】比較例８．難燃性有機粉体として比較例６
で得られた処理粉体Ｉを用いる以外は実施例１０と同様
の操作を行った。Comparative Example 8 Comparative Example 6 as flame retardant organic powder
The same operation as in Example 10 was performed except that the treated powder I obtained in the above was used.
【００６８】比較例９．難燃性有機粉体としてエチレン
ビスペンタブロモジフェニルの未処理粉体を用いること
以外は実施例１０と同様の操作を行った。Comparative Example 9 The same operation as in Example 10 was performed except that untreated powder of ethylenebispentabromodiphenyl was used as the flame-retardant organic powder.
【００６９】実施例１０〜１２、比較例７〜９の結果を
表５、６に示す。Tables 5 and 6 show the results of Examples 10 to 12 and Comparative Examples 7 to 9.
【００７０】[0070]
【表５】 [Table 5]
【００７１】[0071]
【表６】 [Table 6]
【００７２】表５、６から実施例１０〜１２の成形物は
比較例７〜９の成形物と比較して、より良好な外観、お
よびより高い難燃性、流動性、衝撃強度を有しているこ
とが判明した。Tables 5 and 6 show that the molded products of Examples 10 to 12 have better appearance, higher flame retardancy, flowability and impact strength than those of Comparative Examples 7 to 9. Turned out to be.
【００７３】[0073]
【発明の効果】本発明の表面処理難燃性有機粉体は、耐
熱性、分散性に優れており、この表面処理難燃性有機粉
体の熱可塑性樹脂および／または熱硬化性樹脂への混
練、成形加工時に高い流動性や耐熱性を有し、さらに配
合物、成形物は、良好な外観、高い難燃性、流動性、衝
撃強度を有している。The surface-treated flame-retardant organic powder of the present invention is excellent in heat resistance and dispersibility, and the surface-treated flame-retardant organic powder is applied to a thermoplastic resin and / or a thermosetting resin. It has high fluidity and heat resistance at the time of kneading and molding, and the compound and the molded product have good appearance, high flame retardancy, fluidity, and impact strength.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｃ０９Ｋ 21/12 Ｃ０９Ｋ 21/12 // Ｃ０８Ｌ 33/08 ＬＪＥ Ｃ０８Ｌ 33/08 ＬＪＥ ──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 6 Identification code Agency reference number FI Technical display location C09K 21/12 C09K 21/12 // C08L 33/08 LJE C08L 33/08 LJE
Claims (2)
難燃性有機リン系粉体もしくはその金属塩、または難燃
性有機窒素系粉体のうちいずれか少なくとも一つを塩基
性官能基および／または中性官能基を有する数平均分子
量１，０００〜８，０００の高分子表面処理剤により処
理した表面処理難燃性有機粉体。1. A flame-retardant chlorine-based powder, a flame-retardant bromine-based powder,
At least one of the flame-retardant organic phosphorus-based powder or its metal salt, or the flame-retardant organic nitrogen-based powder has a number average molecular weight of 1,000 to 1,000 having a basic functional group and / or a neutral functional group. Surface-treated flame-retardant organic powder treated with 8,000 polymer surface-treating agents.
を熱可塑性樹脂および／または熱硬化性樹脂１００重量
部に対して０．１〜５０重量部含有することを特徴とす
る難燃性樹脂組成物。2. The composition according to claim 1, wherein the surface-treated flame-retardant organic powder is contained in an amount of 0.1 to 50 parts by weight based on 100 parts by weight of the thermoplastic resin and / or the thermosetting resin. Flammable resin composition.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20577296A JPH1045947A (en) | 1996-08-05 | 1996-08-05 | Surface-treated flame-retardant organic powder and resin composition containing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20577296A JPH1045947A (en) | 1996-08-05 | 1996-08-05 | Surface-treated flame-retardant organic powder and resin composition containing the same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH1045947A true JPH1045947A (en) | 1998-02-17 |
Family
ID=16512421
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP20577296A Pending JPH1045947A (en) | 1996-08-05 | 1996-08-05 | Surface-treated flame-retardant organic powder and resin composition containing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH1045947A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002212433A (en) * | 2001-01-12 | 2002-07-31 | Polyplastics Co | Flame-resistant resin composition |
| JP2012131948A (en) * | 2010-12-24 | 2012-07-12 | Sumitomo Bakelite Co Ltd | Resin composition, prepreg, laminate plate, resin sheet, printed wiring board, and semiconductor device |
-
1996
- 1996-08-05 JP JP20577296A patent/JPH1045947A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002212433A (en) * | 2001-01-12 | 2002-07-31 | Polyplastics Co | Flame-resistant resin composition |
| JP2012131948A (en) * | 2010-12-24 | 2012-07-12 | Sumitomo Bakelite Co Ltd | Resin composition, prepreg, laminate plate, resin sheet, printed wiring board, and semiconductor device |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104093724B (en) | Mixtures of dialkylphosphinic acids and alkylphosphonic acids, a process for preparation thereof and use thereof | |
| EP2581379B1 (en) | Halogen-free material containing phosphorous | |
| EP2284208B1 (en) | Flame-retardant material containing phosphorous | |
| CN104093725B (en) | Mixtures of diphosphinic acids and alkylphosphinic acids, a process for the preparation thereof and the use thereof | |
| TWI782135B (en) | Flame retardant composition and flame retardant thermoplastic resin composition containing the same | |
| CN104093726B (en) | Mixture, the Its Preparation Method And Use of diphosphinic acid and alkyl phosphonic acid | |
| EP1916286A2 (en) | Flame retardant, hardening moulding materials | |
| DE10321297B4 (en) | Flame retardant thermosetting compounds, a process for their preparation and their use | |
| DE3808493A1 (en) | AROMATIC POLYAMIDES AS FLAME RETARDANT SYNERGISTS WITH ANTIDRIPPING EFFECT FOR ALIPHATIC POLYAMIDE MOLDING MATERIALS AND THEIR USE | |
| JPH10182875A (en) | Flame-retardant thermoplastic resin composition improved in resistances to moisture and heat | |
| JP2013532205A (en) | Flame retardant polyester resin composition and molded article thereof | |
| JP2003055434A (en) | Flame retardant for synthetic resin, and flame- retardant resin composition containing the flame retardant | |
| DE19635489C2 (en) | Flame-retardant, unsaturated polyester resins, processes for their production and their use for the production of moldings, laminates or coatings | |
| DE102015209451A1 (en) | Flame-retardant polyamides | |
| JPH1045947A (en) | Surface-treated flame-retardant organic powder and resin composition containing the same | |
| JP2000351906A (en) | Composite flame retardant for non-halogen-based resin | |
| JP3767070B2 (en) | Surface-treated composite flame retardant powder | |
| JPH1046152A (en) | Surface-treated flame-retardant organic powder and resin composition containing the same | |
| CN116547330A (en) | Flame retardant polydiketoenamines | |
| JPH059376A (en) | Flame-retardant urethane composition | |
| WO1998039339A1 (en) | Alkyl-1-alkoxyethylphosphinous acid aluminium salts | |
| WO2006011784A1 (en) | Flame-retardant composition | |
| JP6713272B2 (en) | Polycarbonate-based resin composition, product, housing-forming resin, method of using polycarbonate-based resin composition as housing-forming resin, and method of manufacturing polycarbonate-based resin composition | |
| JPH09296120A (en) | Flame-retardant resin composition | |
| JPS6213381B2 (en) |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20040722 |
|
| A131 | Notification of reasons for refusal |
Effective date: 20040803 Free format text: JAPANESE INTERMEDIATE CODE: A131 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20041004 |
|
| A02 | Decision of refusal |
Effective date: 20050315 Free format text: JAPANESE INTERMEDIATE CODE: A02 |