JP2017057276A - Flame resistant resin extrusion molded article - Google Patents
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本発明は、フィルム、シート、射出成型物、ブロー成型物、電線被覆材、繊維などの難燃性樹脂押し出し成型物に関するものである。 The present invention relates to a flame-retardant resin extruded product such as a film, a sheet, an injection-molded product, a blow-molded product, a wire coating material, and a fiber.
難燃性樹脂であるポリ塩化ビニル類(以下「ポリ塩化ビニル」と略記する)にはホモポリマーの硬質ポリ塩化ビニルと軟質ポリ塩化ビニルがあり、軟質ポリ塩化ビニルは硬質塩化ビニルに可塑剤を添加することによりゴム状態まで任意に機械的物性を柔らかく変化させられる。軟質ポリ塩化ビニルは成型加工性もよいが、硬質ポリ塩化ビニルは特殊な専用成型加工装置を使用する必要があり、一般的な成型加工装置では加工できない。
また、硬質ポリ塩化ビニルは常用耐熱温度が60−80℃と低く、常用耐熱温度を高めるためにはガラス繊維などとコンポジットにする必要があり、リサイクル利用を阻害する欠点があった。硬質ポリ塩化ビニルのヴィカット軟化点は92℃で、ポリエチレンの127℃、ポリプロピレンの152℃より低い。
Polyvinyl chlorides, which are flame retardant resins (hereinafter abbreviated as “polyvinyl chloride”), include homopolymers such as hard polyvinyl chloride and soft polyvinyl chloride. Soft polyvinyl chloride uses a plasticizer for hard polyvinyl chloride. By adding, the mechanical properties can be changed softly to the rubber state. Soft polyvinyl chloride has good moldability, but hard polyvinyl chloride needs to use a special dedicated molding apparatus and cannot be processed by a general molding apparatus.
Moreover, hard polyvinyl chloride has a low normal heat resistance temperature of 60 to 80 ° C., and in order to increase the normal heat resistance temperature, it is necessary to make it a composite with glass fiber or the like, which has a drawback of hindering recycling. Hard polyvinyl chloride has a Vicat softening point of 92 ° C, lower than 127 ° C for polyethylene and 152 ° C for polypropylene.
特許文献1には、1mm以下の粉黛に粉砕した可塑化ポリ塩化ビニルでバッキングしたカーペット廃材や可塑化ポリ塩化ビニルシート廃材をシート状にリサイクル成型加工する方法として、加熱混練、加熱加圧成型して成型する方法および装置が記載されている。カーペット廃材にはパイルを構成するポリプロピレン、PETなどの熱可塑性樹脂からなる繊維が含まれている。しかし、この文献では製品シートの補強材としてこれらの繊維を使用するため、これら繊維の融点以下で処理される。 In Patent Document 1, as a method for recycling and processing a carpet waste material or plasticized polyvinyl chloride sheet waste material backed with plasticized polyvinyl chloride pulverized into powder of 1 mm or less, it is heated and kneaded and heated and pressed. A method and apparatus for molding are described. The carpet waste material includes fibers made of a thermoplastic resin such as polypropylene and PET constituting the pile. However, in this document, since these fibers are used as a reinforcing material for the product sheet, the fibers are processed below the melting point of these fibers.
ポリ塩化ビニルとポリオレフィンやポリエステルとは相溶性がないため、単純に混練しても海島状に分散、相分離するだけで、燃焼時にドリップする。 Polyvinyl chloride and polyolefin and polyester are not compatible, so even if they are simply kneaded, they are simply dispersed and phase-separated in a sea-island state and drip during combustion.
解決しようとする問題点は、ポリ塩化ビニルの欠点である低い常用耐熱温度を改善しつつ、樹脂成型品にポリ塩化ビニルの特徴である難燃性を付与することである。 The problem to be solved is to impart flame retardancy, which is a characteristic of polyvinyl chloride, to a resin molded product while improving the low ordinary heat resistance temperature, which is a drawback of polyvinyl chloride.
本発明は、ポリ塩化ビニルが35重量%以上と等容量のポリオレフィン、ポリスチレン、ABS樹脂の少なくとも2種からなり、ポリ塩化ビニルが薄片状に分散している3者混合熱可塑性樹脂組成物であることを最も主要な特徴とする。
また、前記ポリ塩化ビニルがポリ塩化ビニルホモポリマーと可塑剤の混合物、塩化ビニルとコモノマーからなるコポリマーの1種である前記樹脂組成物である。好ましくは前記ポリ塩化ビニルが45重量%以上である前記樹脂組成物である。
The present invention is a three-component mixed thermoplastic resin composition in which polyvinyl chloride is composed of at least two types of polyolefin, polystyrene, and ABS resin having an equal volume of 35% by weight or more, and polyvinyl chloride is dispersed in the form of flakes. This is the main feature.
Further, in the resin composition, the polyvinyl chloride is a mixture of a polyvinyl chloride homopolymer and a plasticizer, or a copolymer composed of vinyl chloride and a comonomer. The resin composition is preferably 45% by weight or more of the polyvinyl chloride.
本発明の難燃性3者混合熱可塑性樹脂組成物は汎用樹脂と同様に加工性、耐熱性、難燃性に優れ、燃焼時のドリップもなく、廉価である。 The flame-retardant three-component mixed thermoplastic resin composition of the present invention is excellent in processability, heat resistance, and flame retardancy like general-purpose resins, is free from drip during combustion, and is inexpensive.
本発明の実施形態はポリ塩化ビニルが35重量%以上と、等容量のポリオレフィン、ポリスチレン、ABS樹脂の2種からなり、ポリ塩化ビニルが薄片状に分散している難燃性3者混合熱可塑性樹脂組成物(以下「樹脂組成物」と略記する。)である。
また、前記ポリ塩化ビニルがポリ塩化ビニルホモポリマーと可塑剤の混合物、または塩化ビニルとコモノマーからなるコポリマーである前記樹脂組成物である。
好ましくは前記ポリ塩化ビニル配合量が45重量%以上である前記樹脂組成物である。前記ポリ塩化ビニル配合量が35重量%未満の場合は難燃性が不足する。ポリ塩化ビニル配合量が増加するに従い、難燃性は向上する。難燃性の評価は酸素指数(LOI)とUL94法に準じて測定した。
ポリ塩化ビニル配合量が50容量%を越える場合、ポリ塩化ビニルの欠点である、特に常用耐熱温度やヴィカット軟化点などの耐熱性改善が見られない。
In the embodiment of the present invention, the polyvinyl chloride is composed of two kinds of polyolefin, polystyrene, and ABS resin having an equal volume of 35% by weight or more, and the flame retardant three-component mixed thermoplastic in which the polyvinyl chloride is dispersed in the form of flakes. It is a resin composition (hereinafter abbreviated as “resin composition”).
Further, in the resin composition, the polyvinyl chloride is a mixture of a polyvinyl chloride homopolymer and a plasticizer, or a copolymer composed of vinyl chloride and a comonomer.
Preferably, the resin composition has a polyvinyl chloride content of 45% by weight or more. When the amount of the polyvinyl chloride is less than 35% by weight, the flame retardancy is insufficient. Flame retardancy improves as the amount of polyvinyl chloride increases. The evaluation of flame retardancy was measured according to the oxygen index (LOI) and UL94 method.
When the amount of polyvinyl chloride exceeds 50% by volume, there is no improvement in heat resistance such as ordinary heat resistance temperature and Vicat softening point, which are disadvantages of polyvinyl chloride.
また、本発明の別の実施形態は樹脂組成物からなる前記樹脂組成物からなる射出成型品、繊維、シート、フィルム、および電線被覆材である。人工毛髪も繊維の1種であり、人毛の場合の太さは約50ミクロンである。 Another embodiment of the present invention is an injection-molded article, a fiber, a sheet, a film, and a wire covering material made of the resin composition made of the resin composition. Artificial hair is also a type of fiber, and in the case of human hair, the thickness is about 50 microns.
前記、本発明で使用するポリ塩化ビニルに使用する可塑剤はジ(2−エチルヘキシル)フタレート、ジイソノニルフタレートなどのフタル酸エステル、アジピン酸、トリメリット酸、クエン酸、安息香酸、テレフタル酸、リン酸などのエステルまたはポリエステルなど、油脂のエステル類、油脂のアミド類またはエポキシ化大豆油などのエポキシ化物の少なくとも1種である。可塑剤は用途によりポリ塩化ビニルホモポリマーの等量程度まで使用されるが、難燃性を低下させるため少ない使用量が好ましい。難燃性の低下が著しくないようにするためにはポリ塩化ビニルホモポリマーに対して10重量%以下の配合が好ましい。 The plasticizers used in the polyvinyl chloride used in the present invention are phthalic acid esters such as di (2-ethylhexyl) phthalate and diisononylphthalate, adipic acid, trimellitic acid, citric acid, benzoic acid, terephthalic acid, and phosphoric acid. And at least one of epoxidized products such as fat esters, fat amides or epoxidized soybean oil. The plasticizer is used up to an equivalent amount of the polyvinyl chloride homopolymer depending on the use, but a small amount is preferable because it reduces the flame retardancy. In order to prevent a significant decrease in flame retardancy, a blending amount of 10% by weight or less with respect to the polyvinyl chloride homopolymer is preferable.
前記ポリ塩化ビニルコポリマーのコモノマーは主モノマーの塩化ビニルモノマー以外に難燃性コモノマーである塩化ビニリデン、臭化ビニル、臭化ビニリデン、フッ化ビニル、フッ化ビニリデンなどのビニルハロゲンコモノマー以外に、酢酸ビニル、メチルアクリレート、メチルメタクリレート、スチレン、ブタジエン、ブチレン、イソプロピレン、プロピレン、エチレン、ペンテン、ヘキセンなどの柔軟性付与コモノマー、アリルスルホン酸ナトリウム、メタアリルスルホン酸ナトリウム、スチレンスルホン酸ナトリウム、アリルスルホン酸カリウム、メタアリルスルホン酸カリウム、スチレンスルホン酸カリウム、アクリル酸ナトリウム、メタクリル酸ナトリウム、アクリル酸カリウム、メタクリル酸カリウム、アクリル酸、メタクリル酸などの染着性付与コモノマーの少なくとも1種が共重合された本発明ポリ塩化ビニル系組成物である。
染着性付与コモノマーは少なくとも0.5重量%ポリ塩化ビニル系組成物中に含有されていると染色が容易となり、好ましい。
In addition to the main monomer vinyl chloride monomer, the polyvinyl chloride copolymer comonomer is not only vinyl halide comonomer, but also vinyl acetate other than vinyl halogen comonomer such as vinylidene chloride, vinyl bromide, vinylidene bromide, vinyl fluoride, vinylidene fluoride. , Methyl acrylate, methyl methacrylate, styrene, butadiene, butylene, isopropylene, propylene, ethylene, pentene, hexene, etc. , Potassium methallyl sulfonate, potassium styrene sulfonate, sodium acrylate, sodium methacrylate, potassium acrylate, potassium methacrylate, acrylic acid, methacryl Is the invention a polyvinyl chloride composition in which at least one is copolymerized dyeing imparting comonomers such.
When the dyeability-imparting comonomer is contained in at least 0.5% by weight of the polyvinyl chloride composition, dyeing is facilitated, which is preferable.
前記、本発明で言う等容量のポリオレフィン、ポリスチレン、ABS樹脂の少なくとも2種からなるとは2種類の容量差が5%以内であることを意味する。例えば前記2者がHDPE20容量%とLDPE19容量%であっても、実質的に本発明で言う等容量を意味する。ポリオレフィンにはHDPE、LDPEやLLDPEなどのポリエチレン、変性ポリエチレンなどがあり、ポリプロピレンにはホモポリマーやコポリマーがある。ポリスチレンはホモポリマーであってもタクティシティーが異なる場合があり、タクティシティーが異なれば別種のポリスチレンとして本発明では取り扱う。ABS樹脂もその組成が異なれば別種のABS樹脂として本発明では取り扱う。 The term “consisting of at least two kinds of polyolefin, polystyrene, and ABS resin” in the present invention means that the difference between the two kinds of capacity is within 5%. For example, even if the two are 20% by volume of HDPE and 19% by volume of LDPE, it means substantially the same capacity as used in the present invention. Examples of polyolefin include polyethylene such as HDPE, LDPE and LLDPE, and modified polyethylene. Polypropylene includes homopolymer and copolymer. Even if the polystyrene is a homopolymer, the tacticity may be different, and if the tacticity is different, it is treated as another type of polystyrene in the present invention. If the ABS resin has a different composition, it is handled as another type of ABS resin in the present invention.
本発明では芳香族ハロゲン化合物類、リン系化合物類、3酸化アンチモン、5酸化アンチモン、酸化亜鉛などの無機塩類、などの難燃添加剤を配合しても良い。 In the present invention, flame retardant additives such as aromatic halogen compounds, phosphorus compounds, antimony trioxide, antimony pentoxide, and inorganic salts such as zinc oxide may be blended.
前記、本発明で使用する塩化ビニルホモポリマーは信越化学工業(株)や(株)カネカなどから市販されている。塩化ビニリデンと塩化ビニルとのコポリマーは約70%の塩化ビニリデンと30%の塩化ビニルとからなる乳化重合コポリマーや、約80%の塩化ビニリデンと20%の塩化ビニルとからなる懸濁重合コポリマーがDow Chemical社やSolvey社から市販されている。また、(株)カネカから塩化ビニルと酢酸ビニルが5から10%共重合された熱可塑性のコポリマー「カネビニールM」(商標名)などが市販されている。またエチレンをコモノマーとしたコポリマーも市販されている。これらのコポリマーを使用すると可塑剤を全く使用しなくても本発明ポリ塩化ビニル系組成物およびそれからなる成型物を製造できるため好ましい。 The vinyl chloride homopolymer used in the present invention is commercially available from Shin-Etsu Chemical Co., Ltd., Kaneka Co., Ltd. and the like. Copolymers of vinylidene chloride and vinyl chloride are emulsion polymerization copolymers composed of about 70% vinylidene chloride and 30% vinyl chloride, and suspension polymerization copolymers composed of about 80% vinylidene chloride and 20% vinyl chloride. Commercially available from Chemical and Solvey. Also, Kaneka Co., Ltd. sells a thermoplastic copolymer “Kane Vinyl M” (trade name) in which 5 to 10% of vinyl chloride and vinyl acetate are copolymerized. Copolymers using ethylene as a comonomer are also commercially available. Use of these copolymers is preferred because the polyvinyl chloride composition of the present invention and a molded product comprising the same can be produced without using any plasticizer.
前記アリルスルホン酸ナトリウム、メタアリルスルホン酸ナトリウム、スチレンスルホン酸ナトリウム、アリルスルホン酸カリウム、メタアリルスルホン酸カリウム、スチレンスルホン酸カリウム、アクリル酸ナトリウム、メタクリル酸ナトリウム、アクリル酸カリウム、メタクリル酸カリウムはカチオン染料の染着官能基となり、後染め加工に適している。人工毛髪の場合染色が可能であると人毛同様に部分染めが可能であり、付加価値が高い。 The sodium allyl sulfonate, sodium methallyl sulfonate, sodium styrene sulfonate, potassium allyl sulfonate, potassium methallyl sulfonate, potassium styrene sulfonate, sodium acrylate, sodium methacrylate, potassium acrylate, potassium methacrylate are cations It becomes a dyeing functional group for dyes and is suitable for post-dyeing. In the case of artificial hair, if it can be dyed, it can be partially dyed in the same way as human hair, and the added value is high.
ポリ塩化ビニルはホモポリマーのまま使用する硬質塩ビの場合、特殊な押し出し機を使用する必要がある。しかし、本発明で使用するように、可塑剤をホモポリマーに配合すると通常使用される押し出し機などの加工機で使用できる。ポリ塩化ビニルは非晶性で、結晶が融解する融点を持たない。可塑剤を加えた加熱状態であっても軟化するだけであり、チクソトロピー効果を示す。 When polyvinyl chloride is used as a homopolymer, it is necessary to use a special extruder. However, as used in the present invention, when a plasticizer is blended with a homopolymer, it can be used in a processing machine such as an extruder that is usually used. Polyvinyl chloride is amorphous and does not have a melting point at which crystals melt. Even in the heated state with the addition of a plasticizer, it only softens and exhibits a thixotropic effect.
溶融ポリマーに薄片状もしくはL/Dの大きい柱状の微細な粒子を適当量配合するとチクソトロピー効果が得られ、見掛け粘度上昇させることができる。薄片状の微粒子としては例えばモンモリロナイトやベントナイトなどがある。これらの微粒子が単層の場合は0.5重量%を総量に対して混練することでチクソトロピー硬化を樹脂に付与することができる。本発明においてもこれらの微粒子を配合することもできる。 When a suitable amount of flaky or columnar fine particles having a large L / D is blended in the molten polymer, a thixotropic effect can be obtained and the apparent viscosity can be increased. Examples of the flaky fine particles include montmorillonite and bentonite. When these fine particles are a single layer, thixotropic curing can be imparted to the resin by kneading 0.5% by weight with respect to the total amount. In the present invention, these fine particles can also be blended.
熱可塑性ポリ塩化ビニルと相分離する他のポリマーとを混練すると海島構造になり、島成分は表面エネルギーを最小にすべく、球状に近い形態となる。L/Dが小さいため、前記チクソトロピー効果は得られない。またこれらの組み合わせは相分離しているため、島成分の配合量だけ機械物性が損なわれる。 When kneaded with thermoplastic polyvinyl chloride and another polymer that is phase-separated, a sea-island structure is formed, and the island component has a nearly spherical shape in order to minimize surface energy. Since L / D is small, the thixotropic effect cannot be obtained. Moreover, since these combinations are phase-separated, mechanical properties are impaired by the amount of the island component.
相分離する2種類の等量の熱可塑性樹脂と、これらと相分離する熱可塑性ポリ塩化ビニルを混合するとMinimal surface structureが構成され、あたかも溶融ポリマーに薄片状の微細な粒子を適当量配合し、チクソトロピー効果が得られたようになり、粘度上昇させることができる。チクソトロピーは一定以上の力が作用しないと流動しない状態を意味する。この場合、海島構造より機械的物性の低下は抑制される。本発明の樹脂組成物成型品はEPMAなどで塩素分布を観察することにより、上記特殊構造の発現を確認できる。 Mixing two equal amounts of phase-separated thermoplastic resins with these phase-separated thermoplastic polyvinyl chloride forms a minimal surface structure, as if blending an appropriate amount of flaky fine particles into the molten polymer, A thixotropy effect is obtained and the viscosity can be increased. Thixotropy means a state that does not flow unless a certain force is applied. In this case, the deterioration of mechanical properties is suppressed from the sea-island structure. The resin composition molded product of the present invention can confirm the expression of the special structure by observing the chlorine distribution with EPMA or the like.
本発明の熱可塑性組成物はこのチクソトロピー効果により、燃焼時温度上昇による粘度低下が発生するにもかかわらず、ドリップしない状態を保持させることができる。本発明は成型加工しやすい熱可塑性樹脂組成物でありながら、燃焼時ドリップしないと言う、一見矛盾する課題を解決することができた。 Due to this thixotropic effect, the thermoplastic composition of the present invention can maintain a state where it does not drip despite a decrease in viscosity due to an increase in temperature during combustion. Although the present invention is a thermoplastic resin composition that is easy to mold, it can solve a seemingly contradictory problem that it does not drip during combustion.
本発明のポリ塩化ビニル系組成物の製造方法は一般的な1軸、2軸混練押出し機などを使用して製造することができる。また適当な混練部分を持つ射出成型機などを使用して製造することができる。
本発明の熱可塑性樹脂組成物の製造時にはポリ塩化ビニルが熱安定性に欠けるため、適当な熱安定剤を配合して製造する。
また必要に応じ、滑剤、着色剤、難燃剤、抗菌剤、防カビ剤、防臭剤などの添加剤を配合する。
前記安定剤としては酸化亜鉛、酢酸亜鉛メルカプト錫系熱安定剤、マレエート錫系熱安定剤、ラウレート錫系熱安定剤、ヒンダードアミン、ヒンダードフェノールなどがあり、滑剤としては金属石鹸系、ポリエチレンワックス系、高級脂肪酸系、エステル系、高級アルコール系滑剤などがある。
The method for producing the polyvinyl chloride composition of the present invention can be produced using a general uniaxial, biaxial kneading extruder or the like. Moreover, it can manufacture using the injection molding machine etc. which have a suitable kneading part.
Since polyvinyl chloride lacks thermal stability during the production of the thermoplastic resin composition of the present invention, it is produced by blending an appropriate thermal stabilizer.
If necessary, additives such as lubricants, colorants, flame retardants, antibacterial agents, fungicides, and deodorants are blended.
Examples of the stabilizer include zinc oxide, zinc acetate mercaptotin heat stabilizer, maleate tin heat stabilizer, laurate tin heat stabilizer, hindered amine, hindered phenol, and the like. Metallic soap and polyethylene wax are used as lubricants. , Higher fatty acid-based, ester-based and higher alcohol-based lubricants.
押し出し成型物が繊維、フィルム、シート、射出成型品、パイプなどの押し出し成型品である本発明樹脂組成物の製造には一般的に使用される製造機、例えば繊維であれば紡糸機、射出成型品であれば射出成型機、シートであればTダイ押し出し機などを使用すれば良い。
熱可塑性樹脂に難燃化剤を配合した難燃製品は燃焼時ドリップする欠点がある。本発明ポリ塩化ビニル系組成物はチクソトロピー性を示し、燃焼時ドリップしない。
Machines generally used for the production of the resin composition of the present invention in which the extruded product is an extruded product such as a fiber, film, sheet, injection molded product, pipe, etc. For example, if it is a fiber, a spinning machine, injection molding If it is a product, an injection molding machine may be used, and if it is a sheet, a T-die extruder may be used.
A flame retardant product in which a flame retardant is blended with a thermoplastic resin has a drawback of drip during combustion. The polyvinyl chloride composition of the present invention exhibits thixotropic properties and does not drip during combustion.
(実施例1)射出成型品
MIが30の射出成型用、市販ポリプロピレンホモポリマーとコポリマーペレット各25重量部と「カネビニールM1008」粉末50重量部とヒンダードアミン0.5重量部を2軸押し出し機にホッパーから定量供給し、最高温度180℃で策状に押出し、水中で急冷後カッターで切断し、本発明樹脂組成物コンパウンドペレットを製造した。このペレットを使用し、190℃で射出成型機を使用し幅12.5mm、長さ125mm、厚さ1.25mmの本発明の樹脂組成物射出成型品を製造した。この燃焼試験サンプルをUL94法にに準じて燃焼試験を行った結果、垂直試験で消火時間3秒、ドリップは認められず、V0規格に合格した。EPMAによる切断面および各面の観察で層状に塩素分布が認められ、ポリ塩化ビニルが薄片状に分散していることを確認できた。このサンプルのLOI値は33であった。このサンプルの耐熱性(ヴィカット軟化点)はポリプロピレンとほとんど変わらず良好であった。
(Example 1) For injection molding with an injection molded product MI of 30, 25 parts by weight of commercially available polypropylene homopolymer and copolymer pellets, 50 parts by weight of “Kane Vinyl M1008” powder, and 0.5 parts by weight of hindered amine were added to a biaxial extruder. A fixed amount was supplied from a hopper, extruded in a shape at a maximum temperature of 180 ° C., rapidly cooled in water, and then cut with a cutter to produce resin composition compound pellets of the present invention. Using this pellet, an injection molding machine having a width of 12.5 mm, a length of 125 mm, and a thickness of 1.25 mm was produced at 190 ° C. using an injection molding machine. This combustion test sample was subjected to a combustion test according to the UL94 method. As a result, the fire extinguishing time was 3 seconds in the vertical test, no drip was observed, and the sample passed the V0 standard. Observation of the cut surface and each surface by EPMA showed a chlorine distribution in a layered manner, and it was confirmed that polyvinyl chloride was dispersed in the form of flakes. The LOI value for this sample was 33. The heat resistance (Vicat softening point) of this sample was almost the same as that of polypropylene.
(比較例1)射出成型品
実施例1と同様にして市販ポリプロピレンホモポリマーとコポリマーペレット各25重量部を、市販ポリプロピレンホモポリマーを50重量部にのみ変更し、燃焼試験サンプルを製造した。この燃焼試験サンプルをUL94法にに準じて燃焼試験を行った結果、垂直試験で着火時からドリップが始まり、V0不適合であった。
(Comparative Example 1) Injection molded product In the same manner as in Example 1, 25 parts by weight of the commercially available polypropylene homopolymer and copolymer pellets were changed to 50 parts by weight of the commercially available polypropylene homopolymer, and a combustion test sample was produced. This combustion test sample was subjected to a combustion test according to the UL94 method. As a result, drip started from the ignition in the vertical test, and V0 was incompatible.
射出成型品
(比較例2)
実施例1と同様にして市販ポリプロピレンホモポリマーとコポリマーペレット各15重量部を、市販ポリプロピレンホモポリマーを70重量部(59容量%)にのみ変更し、燃焼試験サンプルを製造した。この燃焼試験サンプルをUL94法にに準じて燃焼試験を行った結果、垂直試験で着火せず、ドリップもなく、V0適合であったが、耐熱性が不足し、ヴィカット軟化点はポリ塩化ビニルとほとんど変わらなかった。
Injection molded product (Comparative Example 2)
In the same manner as in Example 1, 15 parts by weight of the commercially available polypropylene homopolymer and copolymer pellets were changed to only 70 parts by weight (59% by volume) of the commercially available polypropylene homopolymer, and a combustion test sample was produced. This combustion test sample was subjected to a combustion test according to the UL94 method. As a result, it was not ignited in the vertical test, was not drip, was V0 compatible, but lacked heat resistance, and the Vicat softening point was polyvinyl chloride. Almost unchanged.
(実施例2)押出しシート
実施例1と同様にして、MIが30の射出成型用、市販ポリスチレンホモポリマーとコポリマーペレット各25重量部と「カネビニールM」粉末50重量部をMIが1から2のシート成型用、市販ポリプロピレンホモポリマーとコポリマーペレット各30重量部と「カネビニールM」粉末40重量部にのみ変更し、Tダイ法で厚さ3mm幅10cmの本発明の樹脂組成物シートを製造した。幅12.5mm、長さ125mmの燃焼試験サンプルをこのシートから切り出し、UL94法にに準じて燃焼試験を行った結果、垂直試験で消火時間9秒、ドリップは認められず、V0規格に合格した。EPMAによる切断面および各面の観察で層状に塩素分布が認められ、ポリ塩化ビニルが薄片状に分散していることを確認できた。このサンプルのLOI値は28であった。このサンプルの耐熱性(ヴィカット軟化点)はポリスチレンとほとんど変わらず良好であった。
(Example 2) Extruded sheet In the same manner as in Example 1, 25 parts by weight of commercially available polystyrene homopolymer and copolymer pellets for MI having an MI of 30 and 50 parts by weight of “Kane Vinyl M” powder had an MI of 1 to 2 The resin composition sheet of the present invention having a thickness of 3 mm and a width of 10 cm is manufactured by the T-die method by changing only 30 parts by weight of commercially available polypropylene homopolymer and copolymer pellets and 40 parts by weight of “Kane Vinyl M” powder. did. A combustion test sample having a width of 12.5 mm and a length of 125 mm was cut out from this sheet and subjected to a combustion test according to the UL94 method. As a result, in a vertical test, the fire extinguishing time was 9 seconds, no drip was observed, and it passed the V0 standard. . Observation of the cut surface and each surface by EPMA showed a chlorine distribution in a layered manner, and it was confirmed that polyvinyl chloride was dispersed in the form of flakes. The LOI value for this sample was 28. The heat resistance (Vicat softening point) of this sample was almost the same as polystyrene.
(実施例3)人工毛髪
実施例1と同様にして、MIが30の射出成型用、市販ポリプロピレンホモポリマーとコポリマーペレット各25重量部と「カネビニールM」粉末50重量部をMIが30の紡糸用、市販ポリプロピレンホモポリマーとコポリマーペレット各30重量部と「カネビニールM」粉末40重量部にのみ変更し、紡糸機で定法により亜鈴型ノズルから180℃で紡糸、延伸後、アニールし、得られた糸を集束し、本発明の人工毛髪、単糸太さ55DTX、70万DTXのトウを製造した。この人工毛髪はライターで着火後、自己消火し、ドリップしなかった。このサンプルのLOI値は29であった。
(Example 3) Artificial hair In the same manner as in Example 1, 25 parts by weight of commercially available polypropylene homopolymer and copolymer pellets and 50 parts by weight of "Kane Vinyl M" powder were spun for MI of 30. For commercial use, we changed only 30 parts by weight of polypropylene homopolymer and copolymer pellets and 40 parts by weight of “Kane Vinyl M” powder. The artificial hair of the present invention, a single yarn thickness of 55 DTX, and a 700,000 DTX tow were produced. This artificial hair was ignited with a lighter, then self-extinguished and did not drip. The LOI value for this sample was 29.
(比較例4)人工毛髪
実施例3と同様にして、MIが30の紡糸用、市販ポリプロピレンホモポリマーとコポリマーペレット各35重量部と「カネビニールM」粉末30重量部にのみ変更し、紡糸機で定法により亜鈴型ノズルから180℃で紡糸、延伸後、アニールし、得られた糸を集束し、本発明の人工毛髪、単糸太さ55DTX、70万DTXのトウを製造した。この人工毛髪はライターで着火後、自己消火しなかった。このサンプルのLOI値は24であった。
(Comparative Example 4) Artificial hair In the same manner as in Example 3, only 35 parts by weight of commercially available polypropylene homopolymer and copolymer pellets for spinning with MI of 30 and 30 parts by weight of “Kane Vinyl M” powder were changed to a spinning machine. After spinning and drawing from a dumbbell-shaped nozzle at 180 ° C. by a conventional method, annealing was performed, and the obtained yarn was converged to produce an artificial hair of the present invention, a single yarn thickness of 55 DTX, and 700,000 DTX tow. The artificial hair did not self-extinguish after igniting with a lighter. The LOI value for this sample was 24.
本発明樹脂組成物は熱可塑性樹脂を使用する汎用製造機で射出成型品、シート、フィルム、電線被覆材などとして製造できる。 The resin composition of the present invention can be produced as an injection molded product, a sheet, a film, an electric wire covering material, etc. by a general-purpose production machine using a thermoplastic resin.
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