JPH0776290B2 - Flame retardant polyolefin composition - Google Patents
Flame retardant polyolefin compositionInfo
- Publication number
- JPH0776290B2 JPH0776290B2 JP61154584A JP15458486A JPH0776290B2 JP H0776290 B2 JPH0776290 B2 JP H0776290B2 JP 61154584 A JP61154584 A JP 61154584A JP 15458486 A JP15458486 A JP 15458486A JP H0776290 B2 JPH0776290 B2 JP H0776290B2
- Authority
- JP
- Japan
- Prior art keywords
- flame retardant
- weight
- group
- polyolefin composition
- polyolefin
- 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.)
- Expired - Lifetime
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0066—Flame-proofing or flame-retarding additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/109—Esters; Ether-esters of carbonic acid, e.g. R-O-C(=O)-O-R
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は難燃性ポリオレフイン組成物に関する。詳しく
は難燃剤の浸み出し（ブリード）を防止した難燃性ポリ
オレフイン組成物に関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a flame-retardant polyolefin composition. Specifically, it relates to a flame-retardant polyolefin composition in which bleeding of a flame retardant is prevented.
従来、ポリオレフインを難燃化する方法として難燃剤を
添加する方法があり、難燃化剤としてはハロゲン原子を
含む有機化合物が有効であることが良く知られている。Heretofore, there has been a method of adding a flame retardant as a method for flame retarding a polyolefin, and it is well known that an organic compound containing a halogen atom is effective as a flame retardant.
しかしながら、有機ハロゲン系難燃剤をポリオレフイン
に配合した場合は、ポリオレフインの表面への難燃剤の
浸み出し、いわゆるブリードの発生という現象があり、
成形品の商品価値が著しく低下させる欠点があつた。However, when an organic halogen-based flame retardant is blended with polyolefin, there is a phenomenon of leaching of the flame retardant onto the surface of polyolefin, so-called bleeding occurs,
There is a drawback that the commercial value of the molded product is significantly reduced.
〔発明が解決しようとする問題点〕 ブリード現象は難燃剤とポリオレフインとの相溶性が乏
しいために両者が分離することに起因すると考えられ
る。本発明者らは有機ハロゲン系難燃剤及びポリオレフ
インのいずれに対しても溶解性を有する相互溶解剤を介
在させることによりブリードを防止することができるの
ではないかと鋭意検討を重ね、本発明に到達した。即
ち、本発明は難燃性及びその他の特性、例えば電気的特
性、機械的特性等を損なうことなくブリードを防止した
難燃性ポリオレフイン組成物を提供することを目的とす
る。[Problems to be Solved by the Invention] It is considered that the bleeding phenomenon is caused by the fact that the flame retardant and the polyolefin are poorly compatible with each other and thus are separated from each other. The inventors of the present invention have earnestly studied whether it is possible to prevent bleeding by interposing a mutual solubilizer having solubility in both organic halogen-based flame retardants and polyolefins, and arrived at the present invention. did. That is, an object of the present invention is to provide a flame-retardant polyolefin composition in which bleeding is prevented without impairing flame retardancy and other properties such as electrical properties and mechanical properties.
本発明によれば、有機ハロゲン系難燃剤と一般式（Ｉ） で表わされる炭酸エステルとをポリオレフインに配合す
ることにより、ブリードのない難燃性ポリオレフイン組
成物が得られる。以下、本発明を詳細に説明する。According to the present invention, the organic halogen-based flame retardant and the general formula (I) A flame-retardant polyolefin composition free from bleed can be obtained by blending the carbonate ester represented by the following formula with polyolefin. Hereinafter, the present invention will be described in detail.
本発明の組成物を構成するポリオレフインとしては、熱
可塑性ポリマーで結晶性のもの及び非結晶性のもの、或
はこれらを化学的処理または物理的処理して得られる各
種ポリオレフイン誘導体を使用することができる。例え
ば高圧法ポリエチレン、中低圧法ポリエチレン、低圧法
ポリエチレン、アイソタクチツクポリプロピレン、シン
ジオタクチツクパリプロピレン、アタクチツクポリプロ
ピレン、ポリブテン、ポリエチレンに無水マレイン酸、
フマル酸、アクリル酸、メタクリル酸などをグラフト化
させたグラフト化ポリエチレン等が挙げられる。また、
エチレンとα−オレフインとのランダム共重合体及びこ
れらのブロツク共重合体、エチレン又はα−オレフイン
とその他のビニルモノマーとの共重合体、エチレン又は
α−オレフインと共役ジエン類との交互共重合体等も使
用しうる。これら共重合体の例としてはエチレン−プロ
ピレン共重合体、エチレン−酢酸ビニル共重合体、エチ
レン−アクリル酸共重合体、エチレン−メタクリル酸共
重合体、プロピレン−ブタジエン交互共重合体、エチレ
ン−ジアリルエステル共重合体等が挙げられる。As the polyolefin which constitutes the composition of the present invention, it is possible to use crystalline and non-crystalline thermoplastic polymers, or various polyolefin derivatives obtained by chemically or physically treating them. it can. For example, high-pressure polyethylene, medium-low-pressure polyethylene, low-pressure polyethylene, isotactic polypropylene, syndiotactic polypropylene, atactic polypropylene, polybutene, polyethylene and maleic anhydride,
Examples thereof include grafted polyethylene obtained by grafting fumaric acid, acrylic acid, methacrylic acid and the like. Also,
Random copolymer of ethylene and α-olefin and block copolymers thereof, copolymer of ethylene or α-olefin and other vinyl monomer, alternating copolymer of ethylene or α-olefin and conjugated dienes Etc. can also be used. Examples of these copolymers include ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer, propylene-butadiene alternating copolymer, ethylene-diallyl copolymer. Examples thereof include ester copolymers.
有機ハロゲン系難燃剤としては公知の種々のものが使用
しうる。例えば、ヘキサブロムベンゼン、デカブロムビ
フエニル、デガブロムビフエニルエーテル、テトラブロ
ムビスフエノールＡ、ヘキサブロムシクロドデカン、ド
デカクロロペンタシクロデカン、2,2−ビス〔3,5−ジブ
ロモ−４−（アリルオキシ）フエニル〕プロパン、2,2
−ビス〔3,5−ジブロモ−４−（2,3−ジブロモプロポキ
シ（フエニル〕プロパン、トリス−（2,3−ジブロモプ
ロピル）イソシアヌレート、1,1′−スルホニルビス
〔3,5−ジブロモ−４−（2,3−ジブロモプロポキシ）〕
ベンゼン等が挙げられる。As the organic halogen-based flame retardant, various known ones can be used. For example, hexabromobenzene, decabromobiphenyl, degabromobiphenyl ether, tetrabromobisphenol A, hexabromocyclododecane, dodecachloropentacyclodecane, 2,2-bis [3,5-dibromo-4- ( Allyloxy) phenyl] propane, 2,2
-Bis [3,5-dibromo-4- (2,3-dibromopropoxy (phenyl) propane, tris- (2,3-dibromopropyl) isocyanurate, 1,1'-sulfonylbis [3,5-dibromo- 4- (2,3-dibromopropoxy)]
Examples thereof include benzene.
炭酸エステルとしては一般式（Ｉ） で表わされる化合物が使用される。ここで、Ｒ、Ｒ′は
アルキル基、アルケニル基、アルキニル基、シクロアル
キル基、アラルキル基またはアリール基を表わし、Ｒ、
Ｒ′は同一であつても異なつてもよい。Ｚは脂肪族、芳
香族または脂環式ジオールの残基を表わし、ｎは０また
は１の整数を示す。Ｚの代表例を具体的に例示するなら
ば以下のものが挙げられる。The carbonic acid ester has the general formula (I) The compound represented by is used. Here, R and R'represent an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, an aralkyl group or an aryl group, and R,
R'may be the same or different. Z represents a residue of an aliphatic, aromatic or alicyclic diol, and n represents an integer of 0 or 1. Specific examples of representative examples of Z include the following.
炭酸エステルとしては、難揮発性でかつポリオレフイン
組成物の成形温度で液体であるものを用いるのが好まし
い。従つて通常は常温（25℃）で液体であるか、又は常
温で固体であつても融点が220℃以下のものが用いられ
る。このような炭酸エステルとしては例えば下記のよう
なものがある。 As the carbonate ester, it is preferable to use one which is hardly volatile and which is liquid at the molding temperature of the polyolefin composition. Therefore, it is usually liquid at room temperature (25 ° C), or solid at room temperature but having a melting point of 220 ° C or less. Examples of such carbonic acid ester are as follows.
有機ハロゲン系難燃剤は通常、ポリオレフイン100重量
部に対しハロゲン原子として１〜40重量部の範囲で添加
される。 The organic halogen-based flame retardant is usually added in the range of 1 to 40 parts by weight as a halogen atom with respect to 100 parts by weight of polyolefin.
また、炭酸エステルのポリオレフインに対する添加量
は、ポリオレフインの種類、有機ハロゲン系難燃剤の種
類と添加量によつて異なるが、通常ポリオレフイン100
重量部に対し１〜５重量部の範囲から選択される。添加
量が１重量部以下ではブリード防止効果が小さく、また
５重量部以上添加してもブリード防止効果が著しく増大
することはない。The amount of carbonic acid ester added to polyolefin depends on the type of polyolefin, the type of organic halogen-based flame retardant and the amount added.
It is selected from the range of 1 to 5 parts by weight with respect to parts by weight. If the addition amount is 1 part by weight or less, the bleeding preventing effect is small, and even if 5 parts by weight or more is added, the bleeding preventing effect does not remarkably increase.
本発明の組成物は通常、ミキシングロール、カレンダー
ロール、ニーダー、押出機等の混合機を用い、加熱下に
ポリオレフイン、難燃剤及び炭酸エステルを混練して製
造される。難燃剤及び炭酸エステルを予め混合してポリ
オレフインに添加してもよい。また、混練の際に充填
材、安定剤、抗酸化剤、紫外線吸収剤、顔料、滑剤、ま
た通常有機ハロゲン系難燃剤と併用される酸化アンチモ
ン、水酸化アルミニウム、水酸化マグネシウム等の難燃
化補助剤等を添加しても何ら差支えない。The composition of the present invention is usually produced by kneading a polyolefin, a flame retardant and a carbonic acid ester under heating with a mixer such as a mixing roll, a calender roll, a kneader or an extruder. The flame retardant and carbonate ester may be premixed and added to the polyolefin. In addition, when kneading, flame retardants such as fillers, stabilizers, antioxidants, UV absorbers, pigments, lubricants, and antimony oxide, aluminum hydroxide, magnesium hydroxide, etc., which are usually used in combination with organic halogen-based flame retardants. There is no problem even if an auxiliary agent or the like is added.
以下に実施例を挙げて本発明を更に詳細に説明する。Hereinafter, the present invention will be described in more detail with reference to examples.
実施例１〜６、比較例１ ポリプロピレン（三菱化成工業株式会社製、ノバテツク
Ｐ−4500J）100重量部、安定剤として塩基性マグネシウ
ム・アルミニウムハイドロオキシカーボネート（協和化
学工業株式会社製、DHT−4A−２）１重量部、カーボン
ブラツク（三菱化成工業株式会社製、Ｎ−760M）1.5重
量部、三酸化アンチモン７重量部、有機ハロゲン系難燃
剤として、2,2−ビス〔3,5−ジブロモ−４−（2,3−ジ
ブロモプロポキシ）フエニル〕プロパン７重量部及びト
リス−（2,3−ジブロモプロピル）イソシアヌレート７
重量部、及び第１表に示す各種の炭酸エステル３重量部
を二軸押出機（池貝鉄工株式会社製、PCM−30）を用い
て200℃で混練し、次いで射出成形機（株式会社新潟鉄
工所製、SN−45）を用いて210℃で試験片を成形した。
これらの試験片のブリード性、難燃性、電気特性、引張
り強度の試験結果は第１表に示す通りであつた。Examples 1 to 6 and Comparative Example 1 100 parts by weight of polypropylene (manufactured by Mitsubishi Kasei Kogyo Co., Ltd., Novatec P-4500J), basic magnesium aluminum hydroxycarbonate as a stabilizer (manufactured by Kyowa Chemical Industry Co., Ltd., DHT-4A-). 2) 1 part by weight, carbon black (manufactured by Mitsubishi Kasei Kogyo Co., Ltd., N-760M) 1.5 parts by weight, antimony trioxide 7 parts by weight, as an organic halogen-based flame retardant, 2,2-bis [3,5-dibromo- 7 parts by weight of 4- (2,3-dibromopropoxy) phenyl] propane and tris- (2,3-dibromopropyl) isocyanurate 7
Parts by weight, and 3 parts by weight of various carbonates shown in Table 1 were kneaded at 200 ° C. using a twin-screw extruder (PCM-30 manufactured by Ikegai Tekko Co., Ltd.), and then an injection molding machine (Niigata Tekko Co., Ltd.). A test piece was molded at 210 ° C. using SN-45) manufactured by Mitsui.
The test results of the bleeding property, flame retardancy, electrical properties, and tensile strength of these test pieces are as shown in Table 1.
なお、ブリード性の試験は、促進のため、試験片を90℃
のオーブン中で96時間加熱後、室温に戻し、表面を目視
により観察した。また、ブリード率の測定は、巾12mm、
長さ125mm、厚さ3mmの試験片を秤量してから100℃のギ
ヤーオーブン中に７日間置いた後、ベンゼンで表面にブ
リードしている難燃剤を拭き取り、拭き取る前後の試験
片を重量変化から、次式によりブリード率を計算した。In addition, the bleeding test was performed at 90 ° C.
After heating in an oven for 96 hours, the temperature was returned to room temperature and the surface was visually observed. The bleed rate is measured with a width of 12 mm,
After weighing a 125 mm long and 3 mm thick test piece in a gear oven at 100 ° C for 7 days, wipe off the flame retardant bleeding on the surface with benzene and change the weight of the test piece before and after wiping The bleed rate was calculated by the following formula.
実施例７〜10、比較例２ ポリエチレン（三菱化成工業株式会社製、ET−010M）10
0重量部、難燃剤としてデカブロモビフエニルエーテル4
0重量部、三酸化アンチモン20重量部、ベンゾトリアゾ
ール系紫外線吸収剤（チバガイギー社製、チヌビンＰ−
326）05部、ヒンダードフエノール系酸化防止剤（チバ
ガイギー社製、イルガノツクス−1010）01重量部、及び
第２表に示す各種の炭酸エステル３重量部を用い、実施
例１〜６と同様の二軸押出機と射出成形機を用いて同様
の温度で試験品を成形し、実施例１〜６と同様にして試
験片のブリード性、難燃性、電気特性、引張り強度の試
験を行なつた。結果を第２表に示す。なお、ブリード率
は実施例１〜６と同様に測定した。 Examples 7 to 10 and Comparative Example 2 Polyethylene (ET-010M manufactured by Mitsubishi Kasei Kogyo Co., Ltd.) 10
0 parts by weight, decabromobiphenyl ether 4 as flame retardant
0 parts by weight, 20 parts by weight of antimony trioxide, benzotriazole-based ultraviolet absorber (Ciba Geigy, Tinuvin P-
326) 05 parts, hindered phenol type antioxidant (manufactured by Ciba Geigy Co., Irganox-1010) 01 parts by weight, and 3 parts by weight of various carbonic acid esters shown in Table 2 were used to prepare the same two components as in Examples 1 to 6. A test product was molded at the same temperature using a shaft extruder and an injection molding machine, and the bleeding property, flame retardancy, electrical properties, and tensile strength of the test piece were tested in the same manner as in Examples 1 to 6. . The results are shown in Table 2. The bleed rate was measured as in Examples 1-6.
また、比較のために炭酸エステルを添加しない組成物を
成形した試験片の試験結果も第２表に示す。In addition, for comparison, Table 2 also shows the test results of the test pieces formed by molding the composition to which the carbonate ester was not added.
〔発明の効果〕 本発明によれば、有機ハロゲン系難燃剤を含有するポリ
オレフイン組成物に炭酸エステルを併用することによ
り、ポリオレフイン組成物の難燃性及びその他の特性を
損うことなく、難燃剤のブリードを防止した難燃性ポリ
オレフイン組成物を得ることができる。 [Effect of the Invention] According to the present invention, by using a carbonate together with a polyolefin composition containing an organic halogen-based flame retardant, the flame retardant can be obtained without impairing the flame retardancy and other properties of the polyolefin composition. It is possible to obtain a flame-retardant polyolefin composition in which bleeding is prevented.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 昭54−106557（ＪＰ，Ａ) ─────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-54-106557 (JP, A)
Claims (1)
ニル基、シクロアルキル基、アラルキル基またはアリー
ル基を表わし、Ｒ、Ｒ′は同一であっても異なってもよ
い。Ｚは脂肪族、芳香族または脂環式ジオールの残基を
表わし、ｎは０または１の整数を示す）で表わされる炭
酸エステルとを含有する難燃性ポリオレフィン組成物。1. An organic halogen-based flame retardant and a general formula (I). (In the formula, R and R'represent an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, an aralkyl group or an aryl group, and R and R'may be the same or different. Z is an aliphatic, A flame-retardant polyolefin composition containing a carbonic acid ester represented by an aromatic or alicyclic diol residue, and n represents an integer of 0 or 1.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US06/897,931 US4753970A (en) | 1986-04-21 | 1986-08-19 | Fire-retardant polyolefin composition |
| KR1019860006907A KR920000171B1 (en) | 1986-04-21 | 1986-08-21 | Fire-retardant polyolefin composition |
| CA000516640A CA1300795C (en) | 1986-04-21 | 1986-08-22 | Fire-retardant polyolefin composition |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9166586 | 1986-04-21 | ||
| JP61-91665 | 1986-04-21 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6399253A JPS6399253A (en) | 1988-04-30 |
| JPH0776290B2 true JPH0776290B2 (en) | 1995-08-16 |
Family
ID=14032776
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61154584A Expired - Lifetime JPH0776290B2 (en) | 1986-04-21 | 1986-07-01 | Flame retardant polyolefin composition |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JPH0776290B2 (en) |
| KR (1) | KR920000171B1 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5216059A (en) * | 1992-04-13 | 1993-06-01 | Great Lakes Chemical Corp. | Flame retardant additive composition useful with polyolefins |
| EP1360229B1 (en) * | 2001-01-26 | 2006-01-11 | Albemarle Corporation | Method of producing flame-retardant plastics |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS54106557A (en) * | 1978-02-08 | 1979-08-21 | Teijin Chem Ltd | Flame-retardant polypropylene composition |
-
1986
- 1986-07-01 JP JP61154584A patent/JPH0776290B2/en not_active Expired - Lifetime
- 1986-08-21 KR KR1019860006907A patent/KR920000171B1/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| KR870010114A (en) | 1987-11-30 |
| JPS6399253A (en) | 1988-04-30 |
| KR920000171B1 (en) | 1992-01-09 |
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