JPH01203468A - Flame-retardant synthetic resin composition - Google Patents
Flame-retardant synthetic resin compositionInfo
- Publication number
- JPH01203468A JPH01203468A JP2741188A JP2741188A JPH01203468A JP H01203468 A JPH01203468 A JP H01203468A JP 2741188 A JP2741188 A JP 2741188A JP 2741188 A JP2741188 A JP 2741188A JP H01203468 A JPH01203468 A JP H01203468A
- Authority
- JP
- Japan
- Prior art keywords
- weight
- test
- flame
- temperature
- polymer
- 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
- 239000000203 mixture Substances 0.000 title claims abstract description 24
- 239000003063 flame retardant Substances 0.000 title claims description 18
- 239000000057 synthetic resin Substances 0.000 title claims description 17
- 229920003002 synthetic resin Polymers 0.000 title claims description 17
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims description 15
- 150000001875 compounds Chemical class 0.000 claims abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000002844 melting Methods 0.000 claims abstract description 16
- 230000008018 melting Effects 0.000 claims abstract description 16
- 229920000642 polymer Polymers 0.000 claims abstract description 16
- 229920000137 polyphosphoric acid Polymers 0.000 claims abstract description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 7
- 229920005992 thermoplastic resin Polymers 0.000 claims abstract description 7
- 230000006866 deterioration Effects 0.000 claims abstract description 4
- 238000002485 combustion reaction Methods 0.000 claims description 16
- 238000012545 processing Methods 0.000 claims description 14
- 229920005601 base polymer Polymers 0.000 claims description 6
- 229920006125 amorphous polymer Polymers 0.000 claims description 2
- -1 phosphoric acid compound Chemical class 0.000 abstract description 19
- 239000003054 catalyst Substances 0.000 abstract description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 abstract description 4
- 230000000704 physical effect Effects 0.000 abstract description 4
- 239000004114 Ammonium polyphosphate Substances 0.000 abstract description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 abstract description 3
- 150000001408 amides Chemical class 0.000 abstract description 3
- 235000019826 ammonium polyphosphate Nutrition 0.000 abstract description 3
- 229920001276 ammonium polyphosphate Polymers 0.000 abstract description 3
- 238000005187 foaming Methods 0.000 abstract description 3
- 229920006122 polyamide resin Polymers 0.000 abstract description 3
- 229920001225 polyester resin Polymers 0.000 abstract description 3
- 239000004645 polyester resin Substances 0.000 abstract description 3
- 238000010438 heat treatment Methods 0.000 abstract description 2
- 238000010000 carbonizing Methods 0.000 abstract 1
- 229920000098 polyolefin Polymers 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 48
- 229920001155 polypropylene Polymers 0.000 description 17
- 239000000779 smoke Substances 0.000 description 12
- 239000004743 Polypropylene Substances 0.000 description 11
- 238000004898 kneading Methods 0.000 description 11
- 238000000034 method Methods 0.000 description 9
- PTMHPRAIXMAOOB-UHFFFAOYSA-N phosphoramidic acid Chemical compound NP(O)(O)=O PTMHPRAIXMAOOB-UHFFFAOYSA-N 0.000 description 9
- 229920002292 Nylon 6 Polymers 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 239000000835 fiber Substances 0.000 description 8
- 239000008188 pellet Substances 0.000 description 7
- 238000000465 moulding Methods 0.000 description 6
- 238000009835 boiling Methods 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000004744 fabric Substances 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 238000001746 injection moulding Methods 0.000 description 3
- 229920001684 low density polyethylene Polymers 0.000 description 3
- 239000004702 low-density polyethylene Substances 0.000 description 3
- 229910000000 metal hydroxide Inorganic materials 0.000 description 3
- 150000004692 metal hydroxides Chemical class 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000009864 tensile test Methods 0.000 description 3
- 239000004677 Nylon Substances 0.000 description 2
- 150000001720 carbohydrates Chemical class 0.000 description 2
- 235000014633 carbohydrates Nutrition 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 150000002366 halogen compounds Chemical class 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 239000011342 resin composition Substances 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 206010003497 Asphyxia Diseases 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 1
- 239000004727 Noryl Substances 0.000 description 1
- 229920001207 Noryl Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229920000265 Polyparaphenylene Polymers 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 1
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000004035 construction material Substances 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920006350 polyacrylonitrile resin Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 229920006380 polyphenylene oxide Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、難燃性合成樹脂組成物に関する。さらに詳し
く述べるならば、本発明は、処理温度を高めることによ
って得られる、ハロゲンを含有しない難燃性合成樹脂組
成物に関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a flame-retardant synthetic resin composition. More specifically, the present invention relates to a halogen-free flame-retardant synthetic resin composition obtained by increasing the processing temperature.
合成樹脂を難燃化する方法として、ハロゲン化合物や金
属水酸化物等を内部添加する方法等の多数の方法が実施
されている。しかし、かかる従来の方法に従って、ハロ
ゲン化合物を添加して得られる難燃性合成樹脂組成物で
は、火災発生時にハロゲン化水素等の刺激ガスや有毒ガ
スが発生し、避難に支障をきたしたり、煙による窒息死
の危険があるなどの問題があり、また金属水酸化物を添
加する方法では樹脂組成物への大量添加によって物性が
低下するなどの問題がある。Many methods have been used to make synthetic resins flame retardant, such as adding halogen compounds, metal hydroxides, etc. internally. However, with flame-retardant synthetic resin compositions obtained by adding halogen compounds according to such conventional methods, irritating gases such as hydrogen halides and toxic gases are generated in the event of a fire, which may impede evacuation or smoke. There are problems such as the danger of death by suffocation due to metal hydroxides, and the method of adding metal hydroxides has problems such as deterioration of physical properties due to large amounts of addition to the resin composition.
このため、最近では、ノンハロゲン難燃剤即ちハロゲン
を含まない難燃剤を使用した組成物への要求が急速に高
まっており、なかでも発泡型難燃剤を添加した合成樹脂
組成物が注目されている。For this reason, recently there has been a rapid increase in demand for compositions using non-halogen flame retardants, that is, flame retardants that do not contain halogen, and among them, synthetic resin compositions containing foamed flame retardants are attracting attention.
これは、例えば、炭素源としてペンタエリスリトール等
の多価アルコールや炭水化物を使用し、発泡触媒として
ポリリン酸化合物を使用し、難燃時に燃焼部分を炭化発
泡させ、多孔質炭化層からなる断熱層を形成させること
により基材への熱伝導を妨げて、燃焼を防止する方法で
ある（特公昭６１−４７８７５、特開昭６０−３６５４
２等）。For example, this method uses a polyhydric alcohol such as pentaerythritol or a carbohydrate as a carbon source, a polyphosphoric acid compound as a foaming catalyst, carbonizes and foams the burning part when flame retardant, and creates a heat insulating layer made of a porous carbonized layer. This is a method of preventing combustion by preventing heat conduction to the base material by forming the
2nd prize).
しかし、これらの化合物のほとんどは吸湿性が高く、特
に多価アルコールや炭水化物は一般に水溶性であるので
、これらを配合した合成樹脂組成物は合成樹脂に要求さ
れる耐水性を満足しないばかりでなく、金型からの離型
性が悪く、成形効率を著しく低下させるという問題点が
あった。However, most of these compounds are highly hygroscopic, and polyhydric alcohols and carbohydrates in particular are generally water-soluble, so synthetic resin compositions containing these compounds not only do not satisfy the water resistance required of synthetic resins. However, there was a problem in that the releasability from the mold was poor and the molding efficiency was significantly reduced.
本発明者らは、前述の問題点を解決すべく鋭意研究した
結果、本発明に到達したものである。即ち、本発明は、
従来技術の問題点を解決し、物性や生産性に優れた、低
コストの、ハロゲンを含有しない、難燃性合成樹脂、組
成物を提供しようとするものである。The present inventors have arrived at the present invention as a result of intensive research to solve the above-mentioned problems. That is, the present invention
The present invention aims to solve the problems of the prior art and provide a flame-retardant synthetic resin and composition that is low-cost, does not contain halogen, and has excellent physical properties and productivity.
本発明は、ベースポリマーである熱可塑性樹脂４０〜９
５重量％に対して、燃焼時に炭素源となる高分子化合物
（Ａ＞と、耐水性の高いポリリン酸化合物（Ｂ）とを、
合計で５〜６０重量％の量となり、かつ（Ａ）／ （Ｂ
）の重量比が５／１〜１／２０の範囲となる量で配合し
、（Ａ）の融点（無定形高分子の場合は軟化温度）以上
でかつベースポリマーの実用上耐え得る劣化温度以下で
処理を行うことにより得られる難燃性合成樹脂組成物を
提供する。The present invention uses thermoplastic resin 40 to 9 as the base polymer.
5% by weight, a polymer compound (A>) that becomes a carbon source during combustion, and a polyphosphoric acid compound (B) with high water resistance,
The total amount is 5 to 60% by weight, and (A)/(B
) is blended in an amount such that the weight ratio of Provided is a flame-retardant synthetic resin composition obtained by processing.
本発明に有用なベースポリマーとしては、ポリエチレン
、ポリプロピレン等のポリオレフィン樹脂、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等のポ
リエステル樹脂、６−ナイロン、１２−ナイロン、芳香
族ポリアミド等のポリアミド樹脂やポリフェニレンオキ
シド、変性ポリフェニレンオキシド（ノリル）、アクリ
ロニトリル−ブタジェン−スチレンコポリマー、ポリス
チレン、ポリカーボネート、ポリメチルメタクリレート
、ポリ塩化ビニル等の通常用いられる熱可塑性樹脂を挙
げることができる。Base polymers useful in the present invention include polyolefin resins such as polyethylene and polypropylene, polyester resins such as polyethylene terephthalate and polybutylene terephthalate, polyamide resins such as 6-nylon, 12-nylon, and aromatic polyamides, polyphenylene oxide, and modified polyphenylene. Commonly used thermoplastic resins include oxide (noryl), acrylonitrile-butadiene-styrene copolymer, polystyrene, polycarbonate, polymethyl methacrylate, and polyvinyl chloride.
本発明に有用な、燃焼時に炭素源となる高分子化合物（
Ａ）としては、ポリアミド系樹脂、ポリエステル系樹脂
、ポリアクリロニトリル系樹脂、ポリビニルアルコール
系樹脂、ポリウレタン系樹脂等の合成樹脂やアセテート
等の半合成樹脂等の熱可塑性樹脂であって、単独でまた
は適当な触媒（例えば、燐酸化合物）等と併用すること
によって、燃焼時に炭化発泡するものが挙げられる。A polymer compound useful in the present invention that serves as a carbon source during combustion (
Examples of A) include thermoplastic resins such as synthetic resins such as polyamide resins, polyester resins, polyacrylonitrile resins, polyvinyl alcohol resins, and polyurethane resins, and semi-synthetic resins such as acetate, which may be used alone or as appropriate. Examples include those that carbonize and foam during combustion when used in combination with a catalyst (for example, a phosphoric acid compound).
本発明において、耐水性の高いポリリン酸化合物（Ｂ）
は炭化発泡触媒として用いられ、このような化合物とし
ては、ポリリン酸アミド、ポリリン酸アンモニウム、メ
ラミン変性ポリリン酸アンモニウム、ポリリン酸カルバ
メート等を使用することができる。In the present invention, a highly water resistant polyphosphoric acid compound (B)
is used as a carbonization foaming catalyst, and examples of such compounds include polyphosphoric acid amide, ammonium polyphosphate, melamine-modified ammonium polyphosphate, and polyphosphoric acid carbamate.
本発明の合成樹脂組成物には、さらに、必要に応じて滑
剤、可塑剤、酸化防止剤、紫外線吸収剤、改質剤等の添
加剤を添加することもできる。The synthetic resin composition of the present invention may further contain additives such as lubricants, plasticizers, antioxidants, ultraviolet absorbers, and modifiers, if necessary.
本発明においては、高分子化合物（Ａ）を発泡炭素源に
使用することにより、従来の発泡型難燃性合成樹脂組成
物の問題点であった耐水性を飛躍的に向上させることが
できる。この高分子化合物（Ａ）は、原材料の形態であ
るペレット状、チップ状、粉末状、フレーク状等の形態
でそのまま使用することができる。あるいは、高分子化
合物（Ａ）は、短繊維状であってもよい。In the present invention, by using the polymer compound (A) as a foamed carbon source, water resistance, which has been a problem with conventional foamed flame-retardant synthetic resin compositions, can be dramatically improved. This polymer compound (A) can be used as it is in the form of raw materials such as pellets, chips, powders, flakes, etc. Alternatively, the polymer compound (A) may be in the form of short fibers.
本発明の合成樹脂組成物は、ベースポリマーである熱可
塑性樹脂にこれらの高分子化合物（Ａ）およびポリリン
酸化合物（Ｂ）を配合し、次いで高分子化合物（Ａ）の
融点または軟化温度以上でかつベースポリマーの実用上
耐え得る劣化温度以下で処理を行うことにより得られる
。本発明においては、即ち、高分子化合物（Ａ）が結晶
性高分子化合物である場合には、その融点以上で処理さ
れる。ここに、融点とは、示差走査熱量測定法（ＤＳＣ
法）により測定される融点である（田中誠之、飯田芳男
著、機器分析、裳華房、昭和５７年４月２５日発行）。The synthetic resin composition of the present invention is prepared by blending the polymer compound (A) and the polyphosphoric acid compound (B) into a thermoplastic resin as a base polymer, and then heating the polymer compound (A) at a temperature higher than the melting point or softening temperature of the polymer compound (A). And it can be obtained by processing at a temperature below the deterioration temperature that the base polymer can withstand in practice. In the present invention, that is, when the polymer compound (A) is a crystalline polymer compound, it is treated at a temperature equal to or higher than its melting point. Here, melting point refers to differential scanning calorimetry (DSC).
It is the melting point measured by the method (Masayuki Tanaka, Yoshio Iida, Instrumental Analysis, Shokabo, published April 25, 1980).
また、高分子化合物（Ａ）が無定形高分子化合物である
場合には、その軟化温度以上で処理される。ここに、軟
化温度とは、ＪＩＳ Ｋ−２２０７の環球法により測
定される温度である。Furthermore, when the polymer compound (A) is an amorphous polymer compound, it is treated at a temperature equal to or higher than its softening temperature. Here, the softening temperature is a temperature measured by the ring and ball method of JIS K-2207.
配合は、混合または混練等に際して通常の方法により行
うことができる。引き続く所定温度での処理は、典型的
には、上記の配合により得られた組成物の成形処理であ
る。かかる成形処理は、通常の成形手段、例えば、射出
成形、押出し成形、圧縮成形等により、所望の形状の成
形物とすることにより行うことができる。The blending can be carried out by conventional methods such as mixing or kneading. The subsequent treatment at a predetermined temperature is typically a molding treatment of the composition obtained by the above formulation. Such molding treatment can be carried out by forming a molded product into a desired shape using a conventional molding method such as injection molding, extrusion molding, compression molding, or the like.
このようにして高分子化合物（Ａ＞の融点または軟化温
度以上の高温で配合物を処理することにより、極めて均
一な樹脂組成物を得ることができ、この組成物は耐水性
や離型性に優れたものとなる。In this way, by treating the formulation at a high temperature higher than the melting point or softening temperature of the polymer compound (A>), an extremely uniform resin composition can be obtained, and this composition has excellent water resistance and mold release properties. It will be excellent.
また、この組成物から得られる樹脂成形品は、優れた難
燃性とともに良好な物性を有するものとなる。Moreover, the resin molded article obtained from this composition has excellent flame retardancy and good physical properties.
また、本発明においては、前記の所定温度における処理
は、上記の配合により得られる組成物を通常の温度によ
り成形して得られるシート、プレート、シャフト、ブロ
ック、ペレット等の成形品の、ヒートプレス等により行
う曲げ加工や補強材とのサンドインチ加工等の二次加工
であってもよい。特に、高分子化合物（Ａ）を短繊維状
で配合した組成物においては、かかる二次加工の際に繊
維の配向によって製品に異方性やひずみ残存応力が生じ
て悪影響を及ぼすことがあるけれども、本発明において
はこの二次加工を前記に所定の高い温度で行うので、異
方性やひずみ残存応力の小さい製品を得ることができる
。In addition, in the present invention, the treatment at the predetermined temperature refers to the heat press treatment of molded products such as sheets, plates, shafts, blocks, and pellets obtained by molding the composition obtained by the above-mentioned formulation at a normal temperature. Secondary processing such as bending or sandwich processing with a reinforcing material may also be used. In particular, in compositions containing the polymer compound (A) in the form of short fibers, the orientation of the fibers during such secondary processing may cause anisotropy or strain residual stress in the product, which may have an adverse effect. In the present invention, since this secondary processing is carried out at the predetermined high temperature described above, a product with low anisotropy, strain and residual stress can be obtained.
本発明の難燃性合成樹脂組成物は、電気機器用材、自動
車用部品、インテリア用品、建築用材、衣料用品、雑貨
用品その他に利用することができる。The flame-retardant synthetic resin composition of the present invention can be used for electrical equipment materials, automobile parts, interior goods, construction materials, clothing goods, miscellaneous goods, and others.
実施例１
ポリプロピレン（ＵＢＥポリプロＪ８１５ＨＫ、宇部興
産株式会社）７０重量％にアミドリン酸の高次縮合物（
タイエンＳ、太平化学産業株式会社）２１重量％および
ナイロン６ペレット（融点２１４℃、１０１３Ｂ、宇部
興産株式会社）９重量％を加えた。次いで、ニーダ−（
Ｐ Ｂ Ｖ −０，３Ｈ１入江商会株式会社）を用いて
２４０℃で１０分間混練した後、２００℃の温度および
１００ｋｇ／ｃｍ２の圧力下に３分間プレスし、厚さ３
＋＋＋ｍのプレートを作製した。Example 1 A higher condensate of amidophosphoric acid (
21% by weight of Taien S (Taihei Kagaku Sangyo Co., Ltd.) and 9% by weight of nylon 6 pellets (melting point 214°C, 1013B, Ube Industries Co., Ltd.) were added. Next, kneader (
P B V -0,3H1 (Irie Shokai Co., Ltd.) was kneaded at 240°C for 10 minutes, and then pressed for 3 minutes at a temperature of 200°C and a pressure of 100 kg/cm2 to a thickness of 3.
+++m plates were prepared.
このプレートについて燃焼試験、耐水試験および発煙試
験を行った。A combustion test, a water resistance test, and a smoke test were conducted on this plate.
実施例２
ポリプロピレン（ＵＢＥポリプロＪ８１５ＨＫ）７０重
量％にアミドリン酸の高次縮合物（タイエン５）２１重
量％およびナイロン６パウダー（融点２１４℃、８０〜
１００メツシユが８０％以上、宇部興産株式会社）９重
量％を加え、以下の加工は実施例１と同様にし、得られ
たプレートについて燃焼試験、耐水試験および発煙試験
を行った。Example 2 70% by weight of polypropylene (UBE Polypro J815HK), 21% by weight of a higher condensate of amidophosphoric acid (Tyen 5) and nylon 6 powder (melting point 214°C, 80~
100 mesh (80% or more, Ube Industries, Ltd.) was added, 9% by weight was added, the following processing was the same as in Example 1, and the obtained plate was subjected to a combustion test, a water resistance test, and a smoke generation test.
実施例３
ポリプロピレン（ＵＢＥポリプロＪ８１５ＨＫ）７０重
量％にアミドリン酸の高次縮合物（タイエン５）２１重
量％およびナイロン６繊維（融点２１４℃、単糸デニー
ル４．２、ユニチカ株式会社）を１１１ｍ長にカットし
たちの９重量％を加え、以下の加工を実施例１と同様に
行い、得られたプレートについて燃焼試験、耐水試験お
よび発煙試験を行った。Example 3 70% by weight of polypropylene (UBE Polypro J815HK), 21% by weight of a high-order condensate of amidophosphoric acid (TAIEN 5) and nylon 6 fiber (melting point 214°C, single yarn denier 4.2, Unitika Co., Ltd.) were made into a 111 m long product. The following processing was performed in the same manner as in Example 1, and the resulting plates were subjected to a combustion test, a water resistance test, and a smoke test.
実施例４
低密度ポリエチレン（Ｍ−４２０、三菱化成工業株式会
社）６２重量％にアミドリン酸の高次縮合物（タイエン
５）２８重景気およびナイロン６ペレット（融点２１４
℃、１０１３Ｂ）１０重量％を加えた。以下の加工を実
施例１と同様に行い、得られたプレートについて燃焼試
験、耐水試験および発煙試験を行った。Example 4 Low density polyethylene (M-420, Mitsubishi Chemical Industries, Ltd.) 62% by weight, a higher order condensate of amide phosphoric acid (Tyen 5) 28% by weight and nylon 6 pellets (melting point 214%)
℃, 1013B) was added. The following processing was performed in the same manner as in Example 1, and the resulting plate was subjected to a combustion test, a water resistance test, and a smoke test.
実施例５
低密度ポリエチレン（Ｍ−４２０）６２重量％にアミド
リン酸の高次縮合物（タイエン５）２８重量％およびナ
イロン６パウダー（融点２１４℃、８０〜１００メツシ
ユが８０％以上、宇部興産株式会社）１０重量％を加え
た。以下の加工を実施例１と同様に行い、得られたプレ
ートについて燃焼試験、耐水試験および発煙試験を行っ
た。Example 5 62% by weight of low density polyethylene (M-420), 28% by weight of a high-order condensate of amidophosphoric acid (Tyene 5) and nylon 6 powder (melting point 214°C, 80-100 mesh of 80% or more, Ube Industries, Ltd.) Company) 10% by weight was added. The following processing was performed in the same manner as in Example 1, and the resulting plate was subjected to a combustion test, a water resistance test, and a smoke test.
実施例６
低密度ポリエチレン（Ｍ−４２０）６２重量％にアミド
リン酸の高次縮合物（タイエン５）２８重量％およびナ
イロン６繊維（融点２１４℃、単糸デニール４．２、ユ
ニチカ株式会社）１０重量％を加え、以下の加工は実施
例１と同様にし、得られたプレートについて燃焼試験、
耐水試験および発煙試験を行った。Example 6 62% by weight of low density polyethylene (M-420), 28% by weight of a high-order condensate of amidophosphoric acid (Tyen 5) and 10% by weight of nylon 6 fiber (melting point 214°C, single yarn denier 4.2, Unitika Co., Ltd.) % by weight, the following processing was carried out in the same manner as in Example 1, and the obtained plate was subjected to a combustion test,
A water resistance test and a smoke test were conducted.
実施例７
ポリプロピレン（ＵＢＥポリプロＪ８１５ＨＫ）６０重
量％にアミドリン酸の高次縮合物（タイエン５）３０重
量％およびポリエステル繊維（融点２５４℃、単糸デニ
ール２．１、ユニチカ株式会社）をＩＩＩＩＩにカット
したもの１０重量％を加え、ニーダ−（ＰＢＶ−０３）
を用いて２６５℃で１０分間混練した後、２００℃で１
００ｋｇ／ｃｍ２の圧力下に３分間プレスし、厚さ３麟
−のプレートを作製した。Example 7 60% by weight of polypropylene (UBE Polypro J815HK), 30% by weight of a higher condensate of amidophosphoric acid (Tyen 5) and polyester fiber (melting point 254°C, single yarn denier 2.1, Unitika Co., Ltd.) were cut into III. Add 10% by weight of the
After kneading at 265℃ for 10 minutes using
The plate was pressed for 3 minutes under a pressure of 00 kg/cm2 to produce a plate with a thickness of 3 mm.
このプレートについて燃焼試験、耐水試験および発煙試
験を行った。A combustion test, a water resistance test, and a smoke test were conducted on this plate.
実施例８
ポリプロピレン（ＵＢＥポリプロＪ８１５ＨＫ）６０重
量％にアミドリン酸の高次縮合物（タイエン５）３０重
量％および飽和共重合ポリエステルペレット（軟化温度
１１５℃、ＵＥ−３２２１、ユニチカ株式会社）１０重
量％を加えた。次いで、ニーダ−（ＰＢＶ−０３）を用
いて１８０℃で１５分間混練した後、２００℃および１
００ｋｇ／Ｃｍ２の圧力下に３分間プレスし、厚さ３Ｉ
ＩＩ１１のプレートを作製した。Example 8 60% by weight of polypropylene (UBE Polypro J815HK), 30% by weight of a higher-order condensate of amidophosphoric acid (TAIEN 5) and 10% by weight of saturated copolymerized polyester pellets (softening temperature 115°C, UE-3221, Unitika Co., Ltd.) added. Next, after kneading at 180°C for 15 minutes using a kneader (PBV-03), kneading at 200°C and 1
Pressed for 3 minutes under a pressure of 00kg/Cm2 to a thickness of 3I.
A plate II11 was prepared.
このプレートについて燃焼試験、耐水試験および発煙試
験を行った。A combustion test, a water resistance test, and a smoke test were conducted on this plate.
比較例１
実施例１におけるニーダ−混練温度を１８０℃とし、同
様の試験を行った。Comparative Example 1 The same test as in Example 1 was conducted except that the kneader kneading temperature was set to 180°C.
比較例２
実施例２におけるニーダ−混練温度を１８０℃とし、同
様の試験を行った。Comparative Example 2 The same test as in Example 2 was conducted except that the kneader kneading temperature was 180°C.
比較例３
実施例３におけるニーダ−混練温度を１８０℃とし、同
様の試験を行った。Comparative Example 3 The same test as in Example 3 was conducted except that the kneader kneading temperature was 180°C.
比較例４
実施例４におけるニーダ−混練温度を１８０℃とし、同
様の試験を行った。Comparative Example 4 The same test as in Example 4 was conducted except that the kneader kneading temperature was 180°C.
比較例５
実施例５におけるニーダ−混練温度を１８０℃とし、同
様の試験を行った。Comparative Example 5 The same test as in Example 5 was conducted except that the kneader kneading temperature was set to 180°C.
比較例６
実施例６におけるニーダ−混練温度を１８０℃とし、同
様の試験を行った。Comparative Example 6 The same test as in Example 6 was conducted except that the kneader kneading temperature was set to 180°C.
実施例９
ポリプロピレン（ＵＢＥポリプロＪ８１５ＨＫ）７０重
量％にアミドリン酸の高次縮合物（タイエン５）２１重
量％およびナイロン６繊維（融点２１４℃、単糸デニー
ル４．２、ユニチカ株式会社）を１１１ｍ１にカットし
たちの９重量％を加え、押出機（ＶＳ−２０、田辺プラ
スチックス機械株式会社）の温度を１８０℃に設定して
、混練押出により、難燃化ポリプロピレンのペレットを
得た１次に、このペレットをシリンダーの温度を２４０
℃に設定した射出成形機（ＷＳＡＶ−６０Ａ、株式会社
山域精機製作所）で成形して、厚さ３ｆｉおよび２ｍ１
ｍの試験片を得た。厚さ３ｆｉの試験片については燃焼
試験、耐水試験および発煙試験を行い、厚さ２鶴の試験
片については引張試験を行った。Example 9 70% by weight of polypropylene (UBE Polypro J815HK), 21% by weight of a higher-order condensate of amidophosphoric acid (Tyen 5) and nylon 6 fiber (melting point 214°C, single yarn denier 4.2, Unitika Co., Ltd.) were added to 111 m1. Adding 9% by weight of the cut material, setting the temperature of an extruder (VS-20, Tanabe Plastics Machinery Co., Ltd.) to 180°C, and kneading and extruding it to obtain flame-retardant polypropylene pellets. , this pellet was heated to a cylinder temperature of 240
Molded with an injection molding machine (WSAV-60A, Yamagu Seiki Seisakusho Co., Ltd.) set at ℃ to a thickness of 3fi and 2m1.
A test piece of m was obtained. A combustion test, a water resistance test, and a smoke generation test were conducted on a 3-fi thick test piece, and a tensile test was conducted on a 2-fi thick test piece.
比較例７
実施例９において、射出成形機のシリンダーの温度を１
９０℃として同様の試験を行った。Comparative Example 7 In Example 9, the temperature of the cylinder of the injection molding machine was
A similar test was conducted at 90°C.
実施例１０
ポリプロピレン（ＵＢＥポリプロＪ８１５ＨＫ）７０重
量％にアミドリン酸の高次縮合物（タイエン５）２１重
量％およびナイロン６繊維（融点２１４℃、単糸デニー
ル２．９、ユニチカ株式会社）を１ＩＩ１１にカットし
たもの１０重量％を加え、ニーダー（ＰＢＶ−０，３Ｈ
）を用いて１８０℃で１５分間混練した後、２００℃の
温度および１００ｋｇ／ｃｍ２の圧力下に３分間プレス
し、厚さ１．５ｍａｒの難燃化ポリプロピレンプレート
を２枚作製した。Example 10 70% by weight of polypropylene (UBE Polypro J815HK), 21% by weight of a higher-order condensate of amidophosphoric acid (Tyen 5) and nylon 6 fiber (melting point 214°C, single yarn denier 2.9, Unitika Co., Ltd.) were added to 1II11. Add 10% by weight of the cut material and kneader (PBV-0,3H
) at 180° C. for 15 minutes, and then pressed for 3 minutes at a temperature of 200° C. and a pressure of 100 kg/cm 2 to produce two flame-retardant polypropylene plates with a thickness of 1.5 mar.
次に、これらのプレートの間にガラスロービングクロス
（ＥＲＷ−５８０−５５４Ａ、セントラルガラス株式会
社）をサンドインチして、２６０℃で３分間ホットプレ
ス（１５０ｋ ｇ／ ｃｍ２）し、厚さ３１Ｉ１１のガ
ラス繊維強化難燃性ポリプロピレンプレートを作製した
。Next, a glass roving cloth (ERW-580-554A, Central Glass Co., Ltd.) was sandwiched between these plates and hot pressed (150 kg/cm2) at 260°C for 3 minutes to form a glass roving cloth with a thickness of 31I11. A fiber-reinforced flame-retardant polypropylene plate was fabricated.
得られたプレートについてそりや変形の有無を確認し、
燃焼試験、耐水試験および発煙試験を行った。Check the obtained plate for warpage or deformation,
A combustion test, a water resistance test and a smoke test were conducted.
比較例８
ガラスロービングクロスをサンドインチして圧縮成形す
る場合の温度を２００℃にしたこと以外は実施例１０と
同じ操作を繰り返して、ガラス繊維強化難燃性ポリプロ
ピレンプレートを作製し、試験した。Comparative Example 8 A glass fiber-reinforced flame-retardant polypropylene plate was produced and tested by repeating the same operation as in Example 10, except that the temperature when compressing and molding the glass roving cloth was 200°C.
ｉ 法および士
１、燃焼試験および分散度合
ＵＬ−９４による燃焼試験の判定結果および分散度合を
表１に示す。Table 1 shows the determination results and degree of dispersion of the combustion test using UL-94 method and UL-94.
２、 耐水試験
沸騰水中で６０分煮沸したのち、８０℃で３０分間乾燥
し、試料の減量を求めた。また、煮沸後の試料について
、ＵＬ−９４により燃焼性と外観の変化を調べた。その
結果を表２に示す。この場合、煮沸を６０分以上行って
も重量変化は認められなかった。2. Water resistance test After boiling in boiling water for 60 minutes, the sample was dried at 80°C for 30 minutes to determine the weight loss of the sample. In addition, the samples after boiling were examined for flammability and changes in appearance using UL-94. The results are shown in Table 2. In this case, no weight change was observed even after boiling for 60 minutes or more.
また、試験試料としては１５０Ｘ１５０Ｘ３ｍのプレー
トより、１５０Ｘ１３Ｘ３ｍｍの大きさにカッターで切
断したものを５本作製し、同時に使用した。切断面は、
カッターで切断したため他面に比べなめらかさに欠ける
が、そのまま試験に使用した。Further, as test samples, five test samples were prepared by cutting a 150 x 150 x 3 m plate into a size of 150 x 13 x 3 mm using a cutter, and used at the same time. The cut surface is
Although it was cut with a cutter and was less smooth than the other surfaces, it was used as is for testing.
３、発煙試験
建設省告示第１８２８号および１２３１号（ＪＩＳ
Ａ１３２１−１９７５）法の表面試験を行った。試料と
して２２０ Ｘ ２２０ Ｘ ３ 龍の大きさで、重量
５５０〜５８０ｇの範囲のものを使用した。結果を表２
に示す。3. Smoke emission test Ministry of Construction Notification No. 1828 and No. 1231 (JIS
A1321-1975) surface test was conducted. A sample having a size of 220 x 220 x 3 dragons and a weight in the range of 550 to 580 g was used. Table 2 shows the results.
Shown below.
４、 そり、変形の有無と引張試験 試験試料のそり、変形の有無を目視で確認した。4. Warpage, deformation and tensile test The presence or absence of warpage or deformation of the test sample was visually confirmed.
また、ＪＩＳ Ｋ７１１３法により引張試験を行った
。以上の結果を表３に示す。In addition, a tensile test was conducted according to the JIS K7113 method. The above results are shown in Table 3.
表−±（続き） ＊ 二次加工温度（℃） 本市 二次加工品での分散度合 本本率軟化温度 表−１ 表−叉（続き）Table - ± (continued) *Secondary processing temperature (℃) Motoichi: Degree of dispersion in secondary processed products Book rate softening temperature Table-1 Table - fork (continued)
Claims (1)
％に対して、燃焼時に炭素源となる高分子化合物（Ａ）
と、耐水性の高いポリリン酸化合物（Ｂ）とを、合計で
５〜６０重量％の量となり、かつ（Ａ）／（Ｂ）の重量
比が５／１〜１／２０の範囲となる量で配合し、（Ａ）
の融点（無定形高分子の場合は軟化温度）以上でかつベ
ースポリマーの実用上耐え得る劣化温度以下で処理を行
うことにより得られる難燃性合成樹脂組成物。1. A polymer compound (A) that serves as a carbon source during combustion based on 40 to 95% by weight of the thermoplastic resin that is the base polymer.
and a highly water-resistant polyphosphoric acid compound (B) in a total amount of 5 to 60% by weight, and an amount such that the weight ratio of (A) / (B) is in the range of 5/1 to 1/20. (A)
A flame-retardant synthetic resin composition obtained by processing at a temperature above the melting point (softening temperature in the case of an amorphous polymer) and below the deterioration temperature that the base polymer can withstand for practical purposes.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2741188A JPH01203468A (en) | 1988-02-10 | 1988-02-10 | Flame-retardant synthetic resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2741188A JPH01203468A (en) | 1988-02-10 | 1988-02-10 | Flame-retardant synthetic resin composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01203468A true JPH01203468A (en) | 1989-08-16 |
Family
ID=12220343
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2741188A Pending JPH01203468A (en) | 1988-02-10 | 1988-02-10 | Flame-retardant synthetic resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01203468A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0856551A1 (en) * | 1997-01-30 | 1998-08-05 | Air Products And Chemicals, Inc. | Polyphosphoric acid as a stabilizer for polyurethane prepolymers |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS50159540A (en) * | 1974-06-18 | 1975-12-24 | ||
| JPS5286449A (en) * | 1976-01-12 | 1977-07-18 | Asahi Chem Ind Co Ltd | Flame-retardant glass-fiber reinforced resin composition |
| JPS5751748A (en) * | 1980-09-11 | 1982-03-26 | Idemitsu Kosan Co Ltd | Flame-retardant resin composition |
| JPS57115450A (en) * | 1981-01-07 | 1982-07-17 | Mitsubishi Chem Ind Ltd | Polybutylene terephthalate resin composition |
| JPS59202240A (en) * | 1983-05-02 | 1984-11-16 | Daihachi Kagaku Kogyosho:Kk | Flame-retardant thermoplastic resin composition |
| JPS6295335A (en) * | 1985-10-22 | 1987-05-01 | Ube Ind Ltd | Flame-retardant resin composition |
| JPS62220555A (en) * | 1986-03-22 | 1987-09-28 | Fujikura Ltd | Sheet for molding mechanical closure case of cable |
-
1988
- 1988-02-10 JP JP2741188A patent/JPH01203468A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS50159540A (en) * | 1974-06-18 | 1975-12-24 | ||
| JPS5286449A (en) * | 1976-01-12 | 1977-07-18 | Asahi Chem Ind Co Ltd | Flame-retardant glass-fiber reinforced resin composition |
| JPS5751748A (en) * | 1980-09-11 | 1982-03-26 | Idemitsu Kosan Co Ltd | Flame-retardant resin composition |
| JPS57115450A (en) * | 1981-01-07 | 1982-07-17 | Mitsubishi Chem Ind Ltd | Polybutylene terephthalate resin composition |
| JPS59202240A (en) * | 1983-05-02 | 1984-11-16 | Daihachi Kagaku Kogyosho:Kk | Flame-retardant thermoplastic resin composition |
| JPS6295335A (en) * | 1985-10-22 | 1987-05-01 | Ube Ind Ltd | Flame-retardant resin composition |
| JPS62220555A (en) * | 1986-03-22 | 1987-09-28 | Fujikura Ltd | Sheet for molding mechanical closure case of cable |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0856551A1 (en) * | 1997-01-30 | 1998-08-05 | Air Products And Chemicals, Inc. | Polyphosphoric acid as a stabilizer for polyurethane prepolymers |
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