TWI320793B - - Google Patents

Description

1320793 九、發明說明： 【發明所屬之技術領域】 本發明係有關於一種難燃性聚烯烴類樹脂組成物，尤 指一種無自難燃性聚烯烴類樹脂組成物，其配方簡單，用 料量較一般難燃性樹脂材料少，並同時具有優越的難燃性 及機械強度。 【先前技術】 聚稀烴（polyolefins)類高分子聚合物由於有優越的 耐水性、耐藥性、電絕緣性、機械強度，且成形加工容易， 因此在曰常生活中應用非常廣泛，舉凡電線、電纜的絕緣 披覆、電器產品的外殼、車輛内部使用的面板或内裝、室 内用的些建材、豕具用品、容器'機械零件、汽車零件、 或電子電器設備等。由於用途非常廣泛且是人人生活所必 會接觸的塑膠材料，為了提高其安全性，對這一類的高分 子聚合物產品有必要作各種難燃化的處理。根據統計資料 貝不，在過去十年來這類產品的市場每年以的成長率在 成長’極具應用潛力。 一般常用的阻燃劑為含氣或溴的南素系阻燃劑，或是 會釋放Μ或c〇2的無機填充劑。雖然使用含氣或漠的齒 素系阻燃劑，阻燃效果相當不錯，但是這類阻燃劑在加工 時或燃燒時會產生大4的有錢體，尤其在燃燒時所產生 2量濃煙，i會阻礙逃生。此外自料阻燃劑在加入塑 :村料製成難燃產品的過程中，會產生腐酸氣而 腐钮機器，使得卿損耗速度加快，間接增加㈣的成本。 5 U20793 另外’齒素難燃劑常搭配三氧化二銻混合使用以增強阻燃 效果，不過銻元素因具有致癌危險性而有安全上的顧慮， 因此非自素難燃劑遂成為目前主要的發展趨勢。 常用的非齒素難燃劑大致可分為有機物及無機物兩大 類’有機物方面主要集中在磷系及氮系化合物。而無機物 則主要為氫氧化金屬及氧化金屬化合物，例如氫氧化铭、 氫氧化鎂、或碳酸鈣等。這些化合物可單獨使用或互相搭 配使用來當作難燃劑’主要是利用高溫受熱時分解產生的 碟酸、硝酸來達到脫水作用，以及氨氣、Νζ、Η"或c〇2等 消火性氣體與生成發泡碳化膜來降低燃燒性，而達到阻燃 的目的。這類阻燃劑沒有i素系阻燃劑的缺點，但是必須 大量添加或是另外添加紅磷或金屬氧化合物才能產生阻燃 的效果，因此也使得高分子聚合物樹脂組成物或塑膠材料 的機械強度降低、比重增大’直接地影響高分子材料的特 性及使用範圍，同時更增加材料的使用成本。此外，紅碟 因具有自燃的特性，無形中也增加這類阻燃劑使用的危險 性。 因此未來阻燃劑的開發必須滿足下列幾個特性：（i) 難燃性需符合UL94-V0標準，（2)不含鹵素，（3)不含錄元 素，（4)不含紅磷》 膨脹型阻燃技術是目前被認為能實現無由阻燃且能滿 足上述條件最有希望的途徑之一。膨脹型阻燃劑 (intumescent flame retardant)主要是由酸源（促進劑或 催化劑）、破源（成碳劑）及氣源（發泡劑）三者混合組成， 6 1320793 藉由形成多孔泡珠碳層而在凝聚相達到阻燃作用，多孔泡 沫碳層則是經由下列幾個步驟形成：（1)燃燒初期在較低 溫下，由酸源放出能酯化多元醇和可作為脫水劑的無機 酸’（2)在稍高於放出酸源的溫度下，無機酸與多元醇進 行醋化反應’同時酸源成分中的胺則作為酯化反應的催化 劑’（3)燃燒物在酯化反應的過程中開始熔化，（4)反應過 程中產生的水蒸汽和由氣源產生的不燃性氣體使已處於炫 融狀態的燃燒物膨脹發泡，（5)反應接近完成時，燃燒物 開始焦化和固化，最後形成多孔泡沫碳層。 由於形成的多孔泡沐碳層具有隔熱、隔氧、無溶融滴 洛並且有使火焰自德的作用，因此能達到阻燃的效果。 目前，常用的酸源有礙酸敍（ammonium phosphate)、 聚鱗酸敍（ammonium polyphosphate)、三聚氰胺雄酸 (melamine phosphate)、三聚氰胺焦碟酸（meiamine pyrophosphate)、棚酸鋅、酸鎮、蝴酸猛、棚酸納等。 碳源有季戊四醇（pentaerythritol) '雙季戊四醇 (dipentaerythritol) 、 三季 戊四醇 (tripentaerythritol)、可膨脹性石墨（expandable graphite)等 ° 氣源有三聚氰胺（melamine)、三聚氰胺碟酸（meiamine phosphate)、尿素（urea)等。 中華民國公告第00472071號專利揭露了利用可膨脹 性石墨為碳源，磷酸銨、聚磷酸銨、三聚氰胺磷酸、或三 聚氰胺焦磷酸為酸源，同時加入少量之硼酸辞、硼酸鎂、 7 1320793 硼酸錳、或硼酸鈉，以及磷酸酯類可塑劑於聚烯烴類樹脂 中’可製備限氧指數（L0I) 28~31，且符合（JL94-V0標準 的難燃性聚烯烴類樹脂，但其機械性能不確定》1320793 IX. Description of the Invention: [Technical Field] The present invention relates to a flame-retardant polyolefin resin composition, and more particularly to a non-flammable polyolefin resin composition, which has a simple formulation and a material The amount is less than that of general flame retardant resin materials, and at the same time has superior flame retardancy and mechanical strength. [Prior Art] Polyolefins polymers have excellent water resistance, chemical resistance, electrical insulation, mechanical strength, and easy forming, so they are widely used in everyday life. Insulation coating of cables, outer casings of electrical products, panels or interiors used in vehicles, building materials for interior use, cookware supplies, containers 'mechanical parts, auto parts, or electrical and electronic equipment. Due to the wide range of uses and the plastic materials that must be in contact with everyone's lives, in order to improve their safety, it is necessary to treat various types of high molecular polymer products with various flame retardants. According to statistics, Beibu has been growing in growth in the market for such products over the past decade. Commonly used flame retardants are gas- or bromine-containing flame retardants, or inorganic fillers that release barium or c〇2. Although the use of gas or desert fangs flame retardant, the flame retardant effect is quite good, but this type of flame retardant will produce a large 4 wealthy body during processing or burning, especially when burning 2 amount of concentrated Smoke, i will hinder escape. In addition, the self-feeding flame retardant in the process of adding plastic: the village material into a flame retardant product, will produce a sulphuric acid gas and a corrosion button machine, so that the speed of the loss of the Qing, and indirectly increase the cost of (four). 5 U20793 In addition, the 'dental flame retardant is often used in combination with antimony trioxide to enhance the flame retardant effect. However, the antimony element has safety concerns due to its carcinogenic risk. Therefore, the non-self-inflammable agent has become the main one. development trend. Commonly used non-dentate flame retardants are roughly classified into two categories: organic matter and inorganic matter. The organic matter is mainly concentrated in phosphorus and nitrogen compounds. The inorganic substances are mainly metal hydroxides and metal oxide compounds such as hydroxide, magnesium hydroxide or calcium carbonate. These compounds can be used alone or in combination with each other to be used as a flame retardant. The main reason is to use the acid and nitric acid produced by decomposition at high temperature to achieve dehydration, as well as aeration gas such as ammonia gas, hydrazine, hydrazine or c〇2. A foamed carbonized film is formed to reduce the flammability and achieve the purpose of flame retardancy. Such flame retardants do not have the disadvantages of i-based flame retardants, but it is necessary to add a large amount of red phosphorus or a metal oxide compound in order to produce a flame retardant effect, thereby also making a polymer resin composition or a plastic material. The decrease in mechanical strength and the increase in specific gravity directly affect the characteristics and use range of the polymer material, and at the same time increase the use cost of the material. In addition, due to the self-ignition characteristics of red discs, the danger of the use of such flame retardants is also invisibly increased. Therefore, the development of future flame retardants must meet the following characteristics: (i) flame retardancy needs to comply with UL94-V0 standards, (2) halogen-free, (3) no recorded elements, (4) no red phosphorus Intumescent flame retardant technology is one of the most promising ways to achieve flame retardant and meet the above conditions. Intumescent flame retardant is mainly composed of an acid source (accelerator or catalyst), a source of destruction (carbonization agent) and a gas source (foaming agent), 6 1320793 by forming porous beads The carbon layer and the condensed phase reach the flame retardant effect, and the porous foamed carbon layer is formed through the following steps: (1) at the lower temperature of the combustion, the acidified source can release the esterified polyol and the inorganic acid which can be used as the dehydrating agent. '(2) At a temperature slightly higher than the temperature at which the acid source is released, the inorganic acid is subjected to a acetification reaction with the polyol 'while the amine in the acid source component acts as a catalyst for the esterification reaction' (3) in the esterification reaction of the combustion product The process begins to melt, (4) the water vapor generated during the reaction and the incombustible gas generated by the gas source expand and foam the combustion products that have been in a molten state, and (5) when the reaction is near completion, the combustion products begin to coke and Curing, finally forming a porous foamed carbon layer. Since the formed porous foam carbon layer has heat insulation, oxygen barrier, no melting and dripping, and has a function of self-destruction of the flame, the flame retardant effect can be achieved. At present, commonly used acid sources hinder ammonium phosphate, ammonium polyphosphate, melamine phosphate, melamine pyrophosphate, zinc phthalate, acid acid, and acid. Meng, shed sour and so on. The carbon source is pentaerythritol 'dipentaerythritol, tripentaerythritol, expandable graphite, etc. Gas source is melamine, melamine phosphate, urea (urea) Wait. The Republic of China Announcement No. 00472071 discloses the use of expandable graphite as a carbon source, ammonium phosphate, ammonium polyphosphate, melamine phosphate, or melamine pyrophosphate as an acid source, while adding a small amount of boric acid, magnesium borate, 7 1320793 manganese borate Or sodium borate, and phosphate ester plasticizer in the polyolefin resin' can be prepared to limit the oxygen index (L0I) 28~31, and meet the (JL94-V0 standard flame retardant polyolefin resin, but its mechanical properties uncertain"

Wu(2001 )等人利用氮磷化合物Np28為膨脹型阻燃劑， 以矽鎢酸（siHcotiingstic acid)為催化劑，混合加入聚 丙烯樹脂中，可製備限氧指數（L0I) 3〇~34,且符合UL94_ V0標準的難燃性聚丙烯樹脂，但其機械性能不確定。Wu (2001) et al. used the nitrogen-phosphorus compound Np28 as an intumescent flame retardant, and used siHcotiingstic acid as a catalyst to be mixed into a polypropylene resin to prepare an oxygen-limited index (L0I) of 3〇~34. Flame retardant polypropylene resin in accordance with UL94_ V0, but its mechanical properties are uncertain.

Lv (2005)等人利用二聚氰胺碟酸（meiami ne ph〇Sphate) 為膨脹型阻燃劑的酸源及氣源，以季戊四醇 (pentaerythritol)、雙季戊四醇（dipentaerythrit〇1)、 三季戊四醇（tripentaerythritol)為碳源，混合加入聚丙 . 稀樹脂中’可製備限氧指數（L0I) 33〜37，且符合UL94-V0 標準的難燃性聚丙烯複材’但其機械性能不確定。Lv (2005) et al. used melamine ne ph〇Sphate as the acid source and gas source of intumescent flame retardant, pentaerythritol, dipentaerythrit〇1, and tripentaerythritol. Tripentaerythritol) is a carbon source mixed with polypropylene. In the thin resin, a flame retardant polypropylene composite material with a limit of oxygen index (L0I) of 33 to 37 and conforming to UL94-V0 can be prepared 'but its mechanical properties are uncertain.

Demir(2006)等人利用季戊四醇（pentaerythrit〇1)為 碳源，聚磷酸銨（ammonium polyph〇sphate)為酸源及氣源， 另外加入天然沸石當作促進劑，馬來酸酐接支的聚丙烯共 聚物當作相容劑，混合加入聚丙稀樹脂中，可製備限氧指 數（L0I ) 27~40，且抗張強度仍能維持在24〜28 MPa的難 燃性聚丙烯複材，但不確定其是否符合UL94-V0標準。 • Chiu(1998)等人利用季戊四醇（pentaerythrit〇i)為 碳源，聚磷酸銨（ammonium polyph〇sphate)為酸源，三聚 氰胺（fflelamine)為氣源，混合加入聚丙稀樹脂中，可製備 限氧扣數（L0I) 27〜38的難燃性聚丙烯複材，不過抗張強 度不佳，只点維持在14〜21 MPa，但不確定其是否符合 8 1320793 UL94-V0 標準。Demir (2006) and others use pentaerythritol (1) as a carbon source, ammonium polyph〇sphate as an acid source and gas source, and natural zeolite as a promoter, maleic anhydride-supported polypropylene. The copolymer is used as a compatibilizer and mixed into the polypropylene resin to prepare a flame retardant polypropylene composite material with a constant oxygen index (L0I) of 27 to 40 and a tensile strength of 24 to 28 MPa. Determine if it meets the UL94-V0 standard. • Chiu (1998) et al. used pentaerythrit〇i as the carbon source, ammonium polyph〇sphate as the acid source, and melamine as the gas source, which was mixed into the polypropylene resin to prepare oxygen-limited. The number of buckles (L0I) 27~38 is a flame retardant polypropylene composite, but the tensile strength is not good, only maintained at 14~21 MPa, but it is not sure whether it meets the 8 1320793 UL94-V0 standard.

Tang(2006)等人利用季戊四醇（pentaerythritol)為 碳源’聚填酸敍（ammonium polyphosphate)為酸源，三聚 氰胺磷酸（melamine phosphate)為氣源，另外以馬來酸酐 接支的聚丙烯共聚物當作抻容劑，混合加入聚丙烯與6_聚 醯胺（polyamide 6)複合材料中探討阻燃的相關性質，不 過文獻中並未測試試片的機械強度、限氧指數（L〇 I )，也 不確定其是否符合UL94-V0標準。Tang (2006) et al. used pentaerythritol as the carbon source to collect the ammonium polyphosphate as the acid source, melamine phosphate as the gas source, and the polypropylene copolymer supported by maleic anhydride. As a dry agent, mixed with polypropylene and 6_polyamide (polyamide 6) composite materials to explore the flame retardant properties, but the mechanical strength and oxygen limit index (L〇I) of the test piece were not tested in the literature. It is also uncertain whether it meets the UL94-V0 standard.

Almeras(2003)等人利用p〇iyamide 6為碳源，聚磷 酸銨（ammonium polyphosphate)為酸源，另外以滑石粉 (t a 1 c)及碳酸鈣作為添加劑，混合加入聚丙烯複合材料中 探討添加劑對阻燃效果的影響，可製備限氧指數（L〇I) 32、 抗張強度35 MPa，且符合UL94-V0標準的難燃性聚丙烯複 材。 综上所述，現有的膨脹型阻燃劑其配方組成大多過於 複雜，必須添加多種成分與大量試劑至高分子材料中才能 達到阻燃效果，其不但容易造成相容性的問題，增加使用 與製造成本，同時也難以兼顧複合材料的阻燃效果與機械 性能。 【發明内容】 有鑑於現有的難燃性複合材料難以兼顧阻燃效果與機 械丨生此，並且其所添加的阻燃劑配方組成複雜本發明之Almeras (2003) and others used p〇iyamide 6 as a carbon source, ammonium polyphosphate as an acid source, and talc powder (ta 1 c) and calcium carbonate as additives, mixed into polypropylene composites to discuss additives. For the effect of flame retardant effect, a flame retardant polypropylene composite material with a limited oxygen index (L〇I) 32, a tensile strength of 35 MPa, and a UL94-V0 standard can be prepared. In summary, the existing intumescent flame retardant composition is mostly too complex, and it is necessary to add a plurality of components and a large amount of reagents to the polymer material to achieve a flame retardant effect, which not only easily causes compatibility problems, but also increases use and manufacture. Cost, but also difficult to balance the flame retardant and mechanical properties of composite materials. SUMMARY OF THE INVENTION In view of the fact that the existing flame retardant composite material is difficult to achieve both the flame retardant effect and the mechanical hygiene, and the added flame retardant formulation composition is complicated by the present invention.

主要目的在於提供"'種無i難燃性㈣烴類樹脂組成物， 其組成簡單，# + I 低成本’相容性佳，又不會降低材料機械性 9 能0 為達成前述之目的，本發明之無由難燃聚烯烴類樹脂 組f物係包括（1)100重量份之聚烯烴類樹脂；（2)15至45 重量份之酸源兼氣源；（3)1至30重量份之碳源；以及（4)1 至20重量份之相容性修飾劑；以上各成分構成百分百之 組成物》 本發明可達成的具體功效包括： 1·本發明之無自難燃聚烯烴類樹脂組成物除具有防 火難燃的特性外，燃燒時因不含鹵素，不會產生腐蝕性或 有毋性的氣體’此外燃燒時亦可抑制聚烯烴類塑膠產生滴 燃的現象，對於消防安全有相當具體的貢獻。 2·本發明之無函難燃聚烯烴類樹脂組成物除具有優 越的耐燃性外，其仍能維持聚烯烴類樹脂材料的機械強 度’並且成形加工容易’亦具有良好的耐水性、耐藥性以 及電絕緣性，相當適合運用於各式的產業上。 3 _本發明之無自難燃聚烯烴類樹脂組成物其配方簡 單，用料量也較一般阻燃劑少，具有成本與製造優勢，有 助於難燃聚烯烴類樹脂材料的推廣應用。 【實施方式】 本發明之較佳實施例係包括（1)100重量份之聚烯烴類 樹脂；（2)15至45重量份之酸源兼氣源；（3)1至30重量 份之碳源；以及（4)1至20重量份之相容性修飾劑；以上 各組成分構成百分百之組成物；其中， 前述之聚烯烴類樹脂係至少選自於一種以上之群組： 10 1320793 聚乙烯（PE)、低密度聚乙烯（LDPE)、線性低密度聚乙烯 (LLDPE)、高密度聚乙烯（HDPE)、聚丙烯（PP)。 前述之酸源兼氣源係至少選自於一種以上之群組··氮 填化合物（ammonium polyphosphate complex ’ PNP)、鱗 酸録（ammonium phosphate，AP)、聚填酸錄（ammonium polyphosphate ，APP)、三聚氛胺填酸（melamine phosphate ， MP)、三聚氰胺焦填酸（melamine pyrophosphate ， MPP) o 前述之碳源係至少選自於一種以上之群組：季戊四醇 (pentaerythri tol ， PER)、 雙季 戊四醇 (dipentaerythritol ， DPER)、三季戊四醇 (tripentaerythritol，TPER)、可膨脹性石墨（expandable graphite » EG) ° 前述之相容性促進（修飾）劑係至少選自於一種以上之 群組：馬來酸奸接支修飾之聚稀烴（maleic anhydride grafted polyolefins，PP-g-MA)類樹脂、壓克力酸接支 修飾之聚稀烴（acrylic acid grafted polyolefins，PP-g-AAc)類樹脂等共聚物。 下列實施例用於示範說明本發明，而不意欲以任何方 式限制本發明的範圍。 實施例一：PNP/PER/PP-g-MA/PP無自難燃聚丙烯樹脂 組成物 分別粹取 55~80wt% 聚丙稀（p〇iypr0pyiene 1320793 homopolymer，PP ’福聚股份有限公司產品），15~25^%氮 磷化合物（ammonium polyphosphate complex，PNP，美國 几S Chemical Inc.產品）’ 5~15wt% 季戊四醇 (pentaerythritol，PER，李長榮化學工業股份有限公司 產品）’以及0〜l〇wt%馬來酸酐接支修飾之聚丙稀相容劑 (maleic anhydride grafted polyproPyiene， pp_g_MA ，美 國DUPONT COMPANY產品），充分攪拌後，將混合均勻的試 料粉粒倒進恆溫180eC，轉速50 RPM之塑譜儀中，充份混 煉1 0分鐘。然後將混煉均勻之試料團塊以熱壓成型機在 溫度200°C，飽壓100 kgf/cm2 ’成型時間3〇秒的條件下， 產出150x50x3 mm之板狀試片’再以適當之試片成型機具 將此板狀试片製作成以下各項測試用的試片：ASTM4 號試片進行拉伸試驗’ ASTM D790標準抗折試片以進行抗 折試驗，ASTM D256缺口型試片以進行耐衝擊試驗，astm D2863 IV型試片進行氧氣指數試驗，讥94標準試片進行 耐燃試驗是否符合V0等級，以上配方及製程產出之試片 的實驗結果如表一所示。 PNP/PER/PP-g-MA/PP無自_聚丙賴脂組成物The main purpose is to provide a kind of non-flammable (four) hydrocarbon resin composition with a simple composition, # + I low cost, good compatibility, and no reduction in material mechanical properties. The non-flammable polyolefin resin group f of the present invention comprises (1) 100 parts by weight of a polyolefin resin; (2) 15 to 45 parts by weight of an acid source and a gas source; (3) 1 to 30 And a (4) 1 to 20 parts by weight of a compatibility modifier; the above components constitute a one hundred percent composition. In addition to the fire-resistant and flame-retardant properties, the flammable polyolefin resin composition does not contain halogens during combustion, and does not cause corrosive or damaging gases. In addition, it can suppress the occurrence of drenching of polyolefin plastics during combustion. There is a fairly specific contribution to fire safety. 2. The non-combustible polyolefin resin composition of the present invention, in addition to having excellent flame resistance, can maintain the mechanical strength of the polyolefin resin material and is easy to form and process, and has good water resistance and resistance. Sexuality and electrical insulation are quite suitable for use in various industries. 3 _ The non-flammable polyolefin resin composition of the present invention has a simple formula and a smaller amount of materials than the general flame retardant, and has cost and manufacturing advantages, and contributes to the promotion and application of the flame retardant polyolefin resin material. [Embodiment] The preferred embodiment of the present invention comprises (1) 100 parts by weight of a polyolefin resin; (2) 15 to 45 parts by weight of an acid source and a gas source; and (3) 1 to 30 parts by weight of carbon. And (4) 1 to 20 parts by weight of a compatibility modifier; the above components constitute a one hundred percent composition; wherein the polyolefin resin is at least selected from the group consisting of: 10 1320793 Polyethylene (PE), Low Density Polyethylene (LDPE), Linear Low Density Polyethylene (LLDPE), High Density Polyethylene (HDPE), Polypropylene (PP). The foregoing acid source and gas source are at least selected from the group consisting of: more than one group of ammonium polyphosphate complex 'PNPs, ampenium phosphate (AP), and ammonium polyphosphate (APP). Melamine phosphate (MP), melamine pyrophosphate (MPP) o The aforementioned carbon source is at least selected from the group consisting of: pentaerythri tol (PER), dipentaerythritol (dipentaerythritol, DPER), tripentaerythritol (TPER), expandable graphite (EG) ° The aforementioned compatibility promoting (modifying) agent is selected from at least one group: male traitor Copolymers of maleic anhydride grafted polyolefins (PP-g-MA) resin and acrylic acid grafted polyolefins (PP-g-AAc) resin . The following examples are intended to illustrate the invention and are not intended to limit the scope of the invention in any way. Example 1: PNP/PER/PP-g-MA/PP non-flammable polypropylene resin composition was obtained from 55~80wt% polypropylene (p〇iypr0pyiene 1320793 homopolymer, PP 'Fuju Co., Ltd.), 15~25^% nitrogen phosphate compound (PNP, US S Chemical Inc.) '5~15wt% pentaerythritol (PER, product of Li Changrong Chemical Industry Co., Ltd.)' and 0~l〇wt % maleic anhydride grafted polypro-Pyiene (pp_g_MA, US DUPONT COMPANY product), after thorough mixing, the uniformly mixed sample powder is poured into a constant temperature 180eC, the rotational speed of 50 RPM Medium, fully mixed for 10 minutes. Then, the sample piece which is uniformly kneaded is produced in a hot press molding machine at a temperature of 200 ° C, a pressure of 100 kgf / cm 2 'forming time of 3 sec seconds, and a 150 x 50 x 3 mm plate test piece is produced. Test piece forming machine This test piece was made into the following test pieces: ASTM No. 4 test piece for tensile test ' ASTM D790 standard anti-fold test piece for bending test, ASTM D256 notched test piece For the impact resistance test, the astm D2863 type IV test piece was tested for oxygen index, and the 讥94 standard test piece was tested for compliance with the V0 level. The test results of the test pieces produced by the above formula and process are shown in Table 1. PNP/PER/PP-g-MA/PP without self-polypropylene lysate composition

表一 12 1320793 8 25 10 0 65 21.6 51.4 2.7 31.3 34.5 V0 9 25 15 5 55 23.1 53.1 3.0 21.7 36.5 V0 10 20 5 10 65 32.4 67.1 2.5 25.9 31.9 V0 實施例二：PNP/EG/PP-g-MA/PP無鹵難燃聚丙烯樹脂 組成物 分別秤取 57~85wt% 聚丙烯（polypropylene homopolymer，PP，福聚股份有限公司產品），1 5~25wt%氮 填化合物（ammonium polyphosphate complex，PNP，美國 JLS Chemical Inc.產品），5〜15wt%可膨脹性石墨 (expandable graphite，EG，日本 Tomoe Engineering Co.，Table 1 12 1320793 8 25 10 0 65 21.6 51.4 2.7 31.3 34.5 V0 9 25 15 5 55 23.1 53.1 3.0 21.7 36.5 V0 10 20 5 10 65 32.4 67.1 2.5 25.9 31.9 V0 Example 2: PNP/EG/PP-g-MA /PP halogen-free flame-retardant polypropylene resin composition is separately weighed 57~85wt% polypropylene (polypropylene homopolymer, PP, Fuju Co., Ltd.), 15~25wt% nitrogen-filled compound (ammonium polyphosphate complex, PNP, USA) JLS Chemical Inc., 5~15wt% expandable graphite (EG, Japan Tomoe Engineering Co.,

Ltd.產品）’以及〇〜6wt%馬來酸Sf接支修飾之聚丙稀相容 劑（maleic anhydride grafted polypropylene » PP-g-MA > 美國DUPONT COMPANY產品），充分攪拌後，將混合均勻的 試料粉粒倒進恆溫180°C，轉速50 RPM之塑譜儀中，充份 混煉10分鐘。然後將混煉均勻之試料團塊以熱壓成型機 在溫度200°C，飽壓100 kgf/cm2，成型時間30秒的條件 下’產出150χ50χ3 mm之板狀試片’再以適當之試片成型 機具將此板狀試片製作成以下各項測試用的試片：astm 加38 4號試片進行拉伸試驗，aSTM D790標準抗折試片以 進行抗折試驗，ASTM D2 56缺口型試片以進行耐衝擊試驗， ASTM D2863 IV型試片進行氧氣指數試驗，UL 94標準試 片進行对燃試驗是否符合V0等級，以上配方及製程產出 之試片的實驗結果如表二所示。 表二PNP/EG/PP-g-MA/PP無_難燃聚丙烯樹脂組成物 13 1320793 PP-g- ΜΑ 抗折強度 (MPa) 實驗編號 PNP (wt%) EG (wt%) PP (wt%) 抗拉強度 (MPa) 抗折碰衝擊強度 限氧指數 (%) UL94判定 (wt%) (GPa) (J/m) 1 15 5 0 85 28.9 53.3 2.1 52.8 21.8 V0 2 15 10 3 72 31.4 53.8 2.1 47.2 21.8 V0 3 15 15 6 64 31.2 56.0 2.7 42.5 28.3 V0 4 20 5 3 77 26.3 58.9 2.3 38.3 22.8 V0 5 20 10 6 64 31.5 56.5 2.5 42.4 24.3 V0 6 20 15 0 65 28.0 53.5 2.9 46.6 27.3 V0 7 25 5 6 69 30.8 58.5 2.5 32.6 24.3 V0 8 25 10 0 65 24.7 50.1 2.7 38.6 28.3 V0 9 25 15 3 57 28.0 52.5 2.9 28.2 26.8 V0 10 20 15 6 59 30.9 57.8 2.9 38.5 27.8 V0 實施例三：MPP/PER/PP-g-MA/PP無函難燃聚丙稀樹脂 組成物 分別秤取 55〜65wt%聚丙烯（polypr〇pylene homopolymer ’ PP，福聚股份有限公司產品），2〇〜25wt%三 聚氰胺焦磷酸（melamine pyrophosphate，MPP，美國几兮Ltd. product) 'and 〇 ~ 6wt% maleic acid Sf graft modified polypropylene (PP-g-MA > US DUPONT COMPANY products), fully mixed, will be evenly mixed The sample powder was poured into a plastic spectrometer with a constant temperature of 180 ° C and a rotational speed of 50 RPM, and the mixture was thoroughly mixed for 10 minutes. Then, the sample mixture which is uniformly kneaded is subjected to a hot press molding machine at a temperature of 200 ° C, a saturated pressure of 100 kgf / cm 2 , and a molding time of 30 seconds to produce a plate test piece of 150 χ 50 χ 3 mm. Sheet forming machine This test piece was made into the following test pieces: astm plus 38 4 test piece for tensile test, aSTM D790 standard anti-fold test piece for bending test, ASTM D2 56 notch type The test piece is subjected to the impact test, the ASTM D2863 type IV test piece is subjected to the oxygen index test, and the UL 94 standard test piece is subjected to the test of the V0 level. The test results of the test pieces produced by the above formula and the process are shown in Table 2. . Table 2 PNP/EG/PP-g-MA/PP without _ flame retardant polypropylene resin composition 13 1320793 PP-g- ΜΑ flexural strength (MPa) Experiment number PNP (wt%) EG (wt%) PP (wt %) Tensile strength (MPa) Anti-collision impact strength Oxygen index (%) UL94 judgement (wt%) (GPa) (J/m) 1 15 5 0 85 28.9 53.3 2.1 52.8 21.8 V0 2 15 10 3 72 31.4 53.8 2.1 47.2 21.8 V0 3 15 15 6 64 31.2 56.0 2.7 42.5 28.3 V0 4 20 5 3 77 26.3 58.9 2.3 38.3 22.8 V0 5 20 10 6 64 31.5 56.5 2.5 42.4 24.3 V0 6 20 15 0 65 28.0 53.5 2.9 46.6 27.3 V0 7 25 5 6 69 30.8 58.5 2.5 32.6 24.3 V0 8 25 10 0 65 24.7 50.1 2.7 38.6 28.3 V0 9 25 15 3 57 28.0 52.5 2.9 28.2 26.8 V0 10 20 15 6 59 30.9 57.8 2.9 38.5 27.8 V0 Example 3: MPP/PER /PP-g-MA/PP uncomfortable flame-retardant polypropylene resin composition weighing 55~65wt% polypropylene (polypr〇pylene homopolymer 'PP, Fuju Co., Ltd.), 2〇~25wt% melamine pyrophosphate (melamine pyrophosphate, MPP, a few US

Chemical Inc·產品），l〇〜15wt%季戊四醇 (pentaerythritol ’ PER ’李長榮化學工業股份有限公司 產品），以及0〜10w«馬來酸酐接支修飾之聚丙稀相容劑 (maleic anhydride grafted p〇lypropylene’ pp_gMA ，美 國DUPONT COMPANY產品），充分攪拌後，將混合均勻的試 料粉粒倒進恆溫180°C，轉速50 rpm之塑譜儀中充份混 煉10分鐘。然後將混煉均勻之試料團塊以熱壓成型2 = 溫度200°C，飽壓100 kgf/cm2，成也丨昧 取型時間30秒的條件下， 產出15〇χ5〇χ3隨之板狀試片，再以適當之試片成型機1 將此板狀試片製作成以下各項測試用的試片：咖_“ 14 1320793 號試片進行拉伸試驗，ASTM D790標準抗折試片以進行抗 折試驗，ASTM D256缺口型試片以進行耐衝擊試驗，ASTM D2863 IV型試片進行氧氣指數試驗，UL 94標準試片進行 耐燃試驗是否符合V0等級，以上配方及製程產出之試片 的實驗結果如表三所示。 表三 MPP/PER/PP-g-MA/PP無_難燃聚丙烯樹脂組成物 實驗編號 MPP (wt%) PER (wt%) PP-g- MA (wt%) PP (wt%) 抗拉強度 (MPa) 抗折強度 (MPa) 抗折模數 (GPa) 衝擊強度 (J/m) 限氧指數 (%) UL94判定 1 20 10 10 60 30.5 57.1 2.8 28.1 23.5 V0 2 20 15 0 65 27.1 50.4 2.8 28.0 27.6 V0 3 25 10 0 65 29.1 55.5 2.9 25.2 25.6 V0 4 25 15 5 55 27.9 53.8 3.2 19.7 29.5 V0 5 25 10 10 55 31.7 57.4 2.9 21.6 25.0 V0 實施例四：MPP/EG/PP-g-MA/PP無函難燃聚丙烯樹脂 組成物 分別秤取 55~65wt% 聚丙稀（polypropylene homopolymer，PP，福聚股份有限公司產品），15~25wt%三 聚氰胺焦填酸（melamine pyrophosphate，MPP，美國 JLS Chemical Inc.產品〉，10〜15wt%可膨脹性石墨（expandable graphite，EG，日本 Tomoe Engineering Co.，Ltd.產品）， 以及0〜10wt96馬來酸酐接支修飾之聚丙烯相容劑（maleic anhydride grafted polypropylene，PP-g-MA，美國 DUPONT COMPANY產品），充分攪拌後，將混合均勻的試料粉粒倒進 恆溫180°C，轉速50 RPM之塑譜儀中，充份混煉10分鐘。 然後將混煉均勻之試料團塊以熱壓成型機在溫度200°C， 15 1320793 飽壓100kgf/cm2,成型時間30秒的條件下，產出15〇χ5〇χ3 mm之板狀試片，再以適當之試片成型機具將此板狀試片製 作成以下各項測試用的試片：ASTM D638 4號試片進行拉 伸試驗，ASTM D790標準抗折試片以進行抗折試驗，ASTM D256缺口型試片以進行耐衝擊試驗，ASTM D2863 IV型試 片進行氧氣指數試驗，UL 94標準試片進行耐燃試驗是否 符合V0等級，以上配方及製程產出之試片的實驗結果如 表四所示。 表四 MPP/EG/PP-g-MA/PP無i難燃聚丙烯樹脂組成物 實驗編號 MPP fwt%) EG (wt%) PP-g- MA Cwt%) PP (wt%) 抗拉強度 (MPa) 抗折強度 (MPa) 抗折纖 (GPa) 衝擊強度 (J/m) 限氧指數 (%) UL94判定 1 15 15 10 60 25.7 48.5 2.4 31.8 26.6 V0 2 20 15 0 65 22.7 42.9 2.7 36.0 25.5 V0 3 25 10 0 65 20.9 41.1 2.3 34.2 23.5 V0 4 25 15 5 55 20.7 40.1 2.8 24.6 28.5 V0 5 20 15 10 55 25.6 47.1 2.8 27.7 27.0 V0 實施例五：APP/PER/PP-g-MA/PP無i難燃聚丙烯樹脂 組成物 分別种取 55〜65wt%聚丙烯 （polypropylene homopolymer，PP，福聚股份有限公司產品），20~25wt%聚 碟酸敍（ammonium polyphosphate，APP ’ 美國 JLS Chemical Inc.產品），5〜15wt%季戊四醇（pentaerythritol，PER， 李長榮化學工業股份有限公司產品），以及〇〜l〇wt%馬來酸 酐接支修飾之聚丙烯相容劑（maleic anhydride grafted polypropylene，PP-g-MA，美國 DUPONT COMPANY 產品），充 16 見拌後，將混合均勻的試料粉粒倒進恆溫18 Ο π，轉速 5〇/ΡΜ之塑譜儀中’充份混煉1G分鐘。紐將混煉均勻 之试料團塊以熱壓成型機在溫度20(TC，飽壓100kgf/cm2， 成型時間30秒的條件下，產出15〇χ5〇χ3咖之板狀試片， 再以適當之試片成型機具將此板狀試片製作成以下各項測 試用的試片· ASTM D638 4號試片進行拉伸試驗，ASTM D790 標準抗折試片以進行抗折試驗，ASTM D256缺口型試片以 進行耐衝擊試驗，ASTM D2863 IV型試片進行氧氣指數試 驗’ UL 94標準試片進行耐燃試驗是否符合v〇等級，以上 配方及製程產出之試片的實驗結果如表五所示。 表五APP/PER/PP-g-MA/PP無自難燃聚丙烯樹脂組成物 實驗編號 APP (wt%) PER Cwt%) PP-g- MA (wt%) PP (wt%) 抗拉強度 (MPa) 抗折強度 (MPa) 抗折模數 (GPa) 衝擊強度 (J/m) 限氧指數 (%) UL94判定 1 20 10 10 60 23.8 51.2 2.2 34.9 27.5 V0 2 20 15 0 65 23.4 49.6 2.7 28.2 31.5 V0 3 25 5 10 60 26.9 54.3 2.6 32.7 26.5 V0 4 25 10 0 65 23.7 49.7 2.7 36.4 35.5 V0 5 25 15 5 55 24.8 49.9 2.9 24.4 31.5 V0 6 25 10 5 60 26.9 54.3 2.8 29.6 32.5 V0 實施例六：APP/EG/PP-g-MA/PP無自難燃聚丙烯樹脂 組成物 分別科·取 55~65wt% 聚丙稀（polypropylene homopolymer，PP，福聚股份有限公司產品），15〜25wt%聚 填酸兹（ammonium polyphosphate ’ APP ’ 美國 JLS Chemical Inc.產品），5〜15wt%可膨脹性石墨（expandable graphi te， EG，日本 Tomoe Engineering Co.，Ltd·產品），以及 〇~l〇wt% 17Chemical Inc.), l〇~15wt% pentaerythritol (pentaerythritol 'PER) product, and 0~10w «maleic anhydride grafted p... Lypropylene' pp_gMA (US DUPONT COMPANY product), after fully stirring, the uniformly mixed sample powder is poured into a plastic spectrometer with a constant temperature of 180 ° C and a rotation speed of 50 rpm for 10 minutes. Then, the kneaded sample block is hot-pressed 2 = temperature 200 ° C, saturated pressure 100 kgf / cm 2 , and the yield time is 30 seconds, yielding 15 〇χ 5 〇χ 3 with the board The test piece is prepared by the appropriate test piece forming machine 1 into the test piece for the following tests: coffee _ "14 1320793 test piece for tensile test, ASTM D790 standard anti-fold test piece For the bending test, ASTM D256 notched test piece for impact test, ASTM D2863 type IV test piece for oxygen index test, UL 94 standard test piece for flame resistance test for V0 level, the above formula and process output test The experimental results of the tablets are shown in Table 3. Table 3 MPP/PER/PP-g-MA/PP without _ flame retardant polypropylene resin composition Experiment No. MPP (wt%) PER (wt%) PP-g-MA ( Gt%) PP (wt%) Tensile strength (MPa) Flexural strength (MPa) Flexural modulus (GPa) Impact strength (J/m) Oxygen limit index (%) UL94 judgement 1 20 10 10 60 30.5 57.1 2.8 28.1 23.5 V0 2 20 15 0 65 27.1 50.4 2.8 28.0 27.6 V0 3 25 10 0 65 29.1 55.5 2.9 25.2 25.6 V0 4 25 15 5 55 27.9 53.8 3.2 19.7 29.5 V0 5 25 10 10 55 31.7 57.4 2.9 21.6 25.0 V0 Example 4: MPP/EG/PP-g-MA/PP uncomfortable flame-retardant polypropylene resin composition is weighed 55~65wt% polypropylene (polypropylene homopolymer, PP, Fuju Co., Ltd.) Product), 15~25wt% melamine pyrophosphate (MPP, JLS Chemical Inc., USA), 10~15wt% expandable graphite (EG, Japan Tomoe Engineering Co., Ltd.) And 0~10wt96 maleic anhydride grafted polypropylene (PP-g-MA, DUPONT COMPANY, USA), after fully stirring, the uniformly mixed sample powder is poured into a constant temperature of 180°. C, in a 50 RPM plastic spectrometer, fully knead for 10 minutes. Then mix the sample with uniform kneading at a temperature of 200 ° C, 15 1320793, 100 kgf / cm 2, molding time 30 seconds Under the conditions, a 15 〇χ 5 〇χ 3 mm plate test piece was produced, and the test piece was made into the test piece for the following test using an appropriate test piece forming tool: ASTM D638 No. 4 test piece Tensile test, ASTM D790 Quasi-folding test piece for bending test, ASTM D256 notched test piece for impact test, ASTM D2863 type IV test piece for oxygen index test, UL 94 test piece for flame resistance test conforms to V0 level, the above formula and The experimental results of the test pieces produced by the process are shown in Table 4. Table 4 MPP/EG/PP-g-MA/PP without i-flammable polypropylene resin composition Experiment No. MPP fwt%) EG (wt%) PP-g- MA Cwt%) PP (wt%) Tensile strength ( MPa) Flexural strength (MPa) Anti-fibrillation (GPa) Impact strength (J/m) Oxygen limit index (%) UL94 judgement 1 15 15 10 60 25.7 48.5 2.4 31.8 26.6 V0 2 20 15 0 65 22.7 42.9 2.7 36.0 25.5 V0 3 25 10 0 65 20.9 41.1 2.3 34.2 23.5 V0 4 25 15 5 55 20.7 40.1 2.8 24.6 28.5 V0 5 20 15 10 55 25.6 47.1 2.8 27.7 27.0 V0 Example 5: APP/PER/PP-g-MA/PP i flame retardant polypropylene resin composition is separately taken from 55~65wt% polypropylene (polypropylene homopolymer, PP, Fuju Co., Ltd.), 20~25wt% ammonium polyphosphate, APP 'JLS Chemical Inc. Product), 5~15wt% pentaerythritol (PER, product of Li Changrong Chemical Industry Co., Ltd.), and 〇~l〇wt% maleic anhydride grafted polypropylene (maleic anhydride grafted polypropylene, PP- g-MA, US DUPONT COMPANY product), fill 16 After mixing, pour the mixed sample powder into Temperature 18 Ο plastic spectrometer π, speed 5〇 / ΡΜ in the 'fully kneaded 1G minutes. The sample will be uniformly mixed with a hot-pressing machine at a temperature of 20 (TC, a saturated pressure of 100 kgf/cm2, and a molding time of 30 seconds to produce a plate test piece of 15〇χ5〇χ3 coffee, and then This plate-shaped test piece was prepared into the following test pieces by a suitable test piece forming tool. ASTM D638 No. 4 test piece was subjected to a tensile test, and ASTM D790 standard anti-fold test piece was subjected to a bending test, ASTM D256. The notched test piece is subjected to the impact test, and the ASTM D2863 IV test piece is subjected to the oxygen index test. The UL 94 test piece is tested for compliance with the v〇 grade. The test results of the above formula and the test piece produced by the process are shown in Table 5. Table 5. APP/PER/PP-g-MA/PP non-flammable polypropylene resin composition experiment number APP (wt%) PER Cwt%) PP-g- MA (wt%) PP (wt%) Tensile strength (MPa) Flexural strength (MPa) Flexural modulus (GPa) Impact strength (J/m) Oxygen limit index (%) UL94 judgement 1 20 10 10 60 23.8 51.2 2.2 34.9 27.5 V0 2 20 15 0 65 23.4 49.6 2.7 28.2 31.5 V0 3 25 5 10 60 26.9 54.3 2.6 32.7 26.5 V0 4 25 10 0 65 23.7 49.7 2.7 36.4 35.5 V0 5 25 15 5 55 24.8 49.9 2.9 2 4.4 31.5 V0 6 25 10 5 60 26.9 54.3 2.8 29.6 32.5 V0 Example 6: APP/EG/PP-g-MA/PP non-flammable polypropylene resin composition respectively, take 55~65wt% polypropylene (polypropylene) Homopolymer, PP, Fuju Co., Ltd.), 15~25wt% of aggregate polyphosphate 'APP 'JLS Chemical Inc., USA, 5~15wt% expandable graphite (expandable graphi te, EG, Japan) Tomoe Engineering Co., Ltd. product), and 〇~l〇wt% 17

馬來酸酐接支修飾之聚丙烯相容劑（maleic anhydride grafted p〇lypropylene，pp_g_MA，美國 Μρ〇Ντ c〇MpANY 產品），充分攪拌後，將混合均勻的試料粉粒倒進恆溫18〇 C，轉速50 RPM之塑譜儀中，充份混煉丨〇分鐘。然後將 混煉均勻之試料團塊以熱壓成型機在溫度2〇〇。〇，飽壓ι〇〇 kgf/cm2 ’成型時間3〇秒的條件下，產出15〇χ5〇χ3 _之 板狀試片，再以適當之試片成型機具將此板狀試片製作成 以下各項測試用的試片：ASTM D638 4號試片進行拉伸試 驗，ASTM D790標準抗折試片以進行抗折試驗，ASTM D256 缺口型試片以進行耐衝擊試驗，ASTM D2863 IV型試片進 灯氧氣指數試驗，UL 94標準試片進行耐燃試驗是否符合 V0等級，以上配方及製程產出之試片的實驗結果如表六所 〇 表六APP/EG/PP-g-MA/PP無自難燃聚丙烯樹脂組成物 實驗編號 APP (wt%) EG (wt%) PP-g- MA (wt%) PP (wt%) 抗拉触 (MPa) 抗折強度 (MPa) 抗折模數 (GPa) 衝擊強度 (J/m) 限氧指數 (%) UL94判定 1 15 15 10 60 30.7 54.0 2.8 31.4 27.5 V0 2 20 15 0 65 25.2 50.8 2.7 42.6 25.5 νπ 3 25 5 10 60 29.9 54.4 2.4 27.8 24.5 V0 4 25 10 0 65 23.5 47.9 2.5 39.4 23.5 V0 5 25 15 5 55 26.2 49.4 3.0 29.4 25.5 V0 6 15 15 10 60 30.8 53.1 2.7 31.3 27.7 V0 比較例一：未添加無鹵難燃劑之聚丙烯樹脂 秤取 100wt%l 丙稀（p〇lypr〇pyiene h〇m〇p〇iymer，pp， 福聚股份有限公司產品），不添加任何無齒難燃劑，充分 授拌後’將混合均勻的試料粉粒倒進怪溫18 〇 ，轉速5 〇 18 1320793 RPM之塑譜儀中，充份混煉1 〇分鐘。然後將混煉均勻之試 料團塊以熱壓成型機在溫度20ITC，飽壓1〇〇 kgf/cm2，成 型時間30秒的條件下’產出15〇x5〇x3 mm之板狀試片， 再以適當之試片成型機具將此板狀試片製作成以下各項測 試用的試片：ASTM D638 4號試片進行拉伸試驗，ASTM D790 標準抗折試片以進行抗折試驗，ASTM D256缺口型試片以 進行对衝擊試驗’ ASTM D2863 IV型試片進行氧氣指數試 驗’ UL 94標準試片進行耐燃試驗是否符合v〇等級，以上 配方及製程產出之試片的實驗結果如表七所示。The maleic anhydride grafted p〇lypropylene (pp_g_MA, US Μρ〇Ντ c〇MpANY product) is fully stirred, and the uniformly mixed sample powder is poured into a constant temperature of 18 〇C. In a 50 RPM plastic spectrometer, mix thoroughly for 丨〇 minutes. The homogenized sample pellets were then kneaded at a temperature of 2 Torr. 〇, saturated ι〇〇kgf/cm2 'formation time 3 〇 seconds, yield 15 〇χ 5 〇χ 3 _ plate test piece, and then make the plate test piece with appropriate test piece forming machine Test pieces for the following tests: ASTM D638 No. 4 test piece for tensile test, ASTM D790 standard anti-fold test piece for bending test, ASTM D256 notched test piece for impact test, ASTM D2863 Type IV test The film enters the lamp oxygen index test, the UL 94 standard test piece is tested for compliance with the V0 level. The test results of the above formula and the test piece produced by the test are shown in Table 6. Table 6 APP/EG/PP-g-MA/PP Non-flammable polypropylene resin composition test No. APP (wt%) EG (wt%) PP-g- MA (wt%) PP (wt%) tensile contact (MPa) flexural strength (MPa) anti-folding mold Number (GPa) Impact strength (J/m) Oxygen limit index (%) UL94 judgement 1 15 15 10 60 30.7 54.0 2.8 31.4 27.5 V0 2 20 15 0 65 25.2 50.8 2.7 42.6 25.5 νπ 3 25 5 10 60 29.9 54.4 2.4 27.8 24.5 V0 4 25 10 0 65 23.5 47.9 2.5 39.4 23.5 V0 5 25 15 5 55 26.2 49.4 3.0 29.4 25.5 V0 6 15 15 10 60 30.8 53.1 2.7 31.3 27.7 V0 Comparative example : Polypropylene resin without added halogen-free flame retardant is 100% by weight of propylene (p〇lypr〇pyiene h〇m〇p〇iymer, pp, Fuju Co., Ltd.), without adding any toothless flame retardant After the agent is fully mixed, 'pour the mixed sample powder into the strange temperature 18 〇, the speed of 5 〇18 1320793 RPM in the spectrometer, fully mix for 1 〇 minutes. Then, the sample piece which is uniformly kneaded is produced by a hot press molding machine at a temperature of 20 ITC, a pressure of 1 〇〇 kgf/cm 2 , and a molding time of 30 seconds to produce a plate test piece of 15 〇 x 5 〇 x 3 mm. This plate-shaped test piece was prepared into the following test pieces by a suitable test piece forming machine: ASTM D638 No. 4 test piece for tensile test, ASTM D790 standard anti-fold test piece for bending test, ASTM D256 The notched test piece is used for the impact test 'ASTM D2863 IV test piece for oxygen index test' UL 94 standard test piece for flame resistance test conforms to the v〇 grade. The test results of the above formula and process output test piece are shown in Table 7. Shown.

-- —~| iQ.u Invalid 比較例一係為未添加無齒難燃劑之聚丙烯樹脂，由表 七UL 94耐燃試驗的判定結果可知其無法達到難燃的v〇 標準（Invalid)，亦即其不具有難燃性。而相較於本發明 各實施例的UL 94耐燃試驗的判定結果均可達到v〇標準， f實施例的限氧指數亦均較比較例一為高’顯示本^明所 提出的無齒難燃性聚烯烴類樹脂組成物確實具有難燃的效 果。此外，對照各實施例與比較例一的機械性能測試結果， 顯示本發明各實施例雖然添加了 _定比例的無自難：劑： 但機械性能相較於比較例—並未顯著下降，因此本發明所 :出的無齒難燃性聚稀烴類樹脂組成物可以同時 性質與機械性能。 ·'，、 19 1320793 比較例二：市售商用無齒難燃聚丙烯樹脂組成物 表八為部份目前市售商用之無齒難燃聚丙烯樹脂組成 物的相關性質比較表。 表八 市售商用無南難燃聚丙烯樹脂組成物 實驗編號 抗拉強度 抗折強度 抗折模數 衝擊強度 限氧指數 UL94判定 (MPa) (MPa) CGPa) (J/m) (%) HFFR 1 30.0 48.0 1.9 27.0 —— V0 HFFR2 30.0 48.0 1.9 37.0 — V0 HFFR3 22.8 42.1 2.4 26.7 —— V0 HFFR4 25.0 35.0 2.9 25.0 — V0 HFFR5 24.1 38.6 1.9 26.7 —— V0 HFFR6 28.0 45.0 2.0 30.0 —— V0 HFFR7 24.0 _ 2.0 25.0 30.0 V0 說明= [HFFR 1] 30% Exolit® AP-750 + 70% PP Profax® 6524, MFI=4, homopolymer 耐燃劑商品名:Ex〇lit® AP-750 供應商:Clariant International Ltd 聚丙稀商品名:PP Profax® 6524: 供應商:台灣福聚股份有限公司Taiwan Polypropylene Co.，LTD [HFFR 2] 20% CN-2616 + 80% PP Profax® 6524, MFI=4, homopolymer 耐燃劑商品名:CN-2616 供應商:Great Lakes Chemical Corporation 聚丙烯商品名:PP Profax® 6524: 供應商:台灣福聚股份有限公司Taiwan Polypropylene Co., LTD [HFFR 3] RTP Company RTP 151 Polypropylene (PP) Non Halogen Flame Retardant - UL94 V-0 耐燃劑商品名:RTP 151 供應商:RTP Company [HFFR 4] Singapore Polymer Corporation SINPOLENE Flame Retardant Polypropylene 耐燃劑商品名:MFP 220A2 供應商：Singapore Polymer Corporation Pte Ltd [HFFR 5] Asahi Thermofil Polypropylene P6-9900-0570 Unfilled, Flame Retardant, Heat Stabilized 耐燃劑商品名:P6-9900-0570 供應商:Asahi KASEI Corporation [HFFR 6] A. Schulman, Inc. POLYFLAM FRPP 1360, Non-Halogenated Homopolymer Polypropylene 耐燃劑商品名:POLYFLAM™ RPP 1360 供應商:A. Schulman» Inc [HFFR 7] GICHEM GIPLENE DX06/V0F Polypropylene - Flame Retardant 耐燃劑商品名:GICHEM GIPLENE DXO6/V0F Polypropylene 供應商:Giplast S.A. 比較例二為市售商用無鹵難燃聚丙烯樹脂組成物，由 20 ^20793 各實施例與比較例二的比較結果可以發現，本發明具有不 遊於市售商用組成物的機械性質，尤其在抗折強度與抗折 模數方面較大多數市售商用組成物為佳，顯示本發 鹵難燃性聚烯烴類樹脂組成物的確擁 ”，、 械性質，具有相當大的商業潛力》 異的難燃性與機 【圖式簡單說明】 無 【主要元件符號說明】 無 21---~| iQ.u Invalid Comparative example 1 is a polypropylene resin without a tooth-free flame retardant. It can be seen from the judgment result of the UL 94 flame-resistant test in Table 7 that it cannot reach the flame retardant V〇 standard (Invalid). That is, it is not flame retardant. The determination results of the UL 94 flame resistance test of the embodiments of the present invention can reach the v〇 standard, and the oxygen limiting index of the f embodiment is also higher than that of the comparative example. The flammable polyolefin resin composition does have a flame retardant effect. In addition, comparing the mechanical property test results of the respective examples and the comparative example 1, it is shown that although the embodiment of the present invention adds a ratio of no self-difficulties: the mechanical properties are not significantly decreased compared to the comparative examples, The toothless flame-retardant polyolefin resin composition of the present invention can have both simultaneous properties and mechanical properties. ·', 19 1320793 Comparative Example 2: Commercially available non-toothed flame-retardant polypropylene resin composition Table 8 is a comparison table of the relevant properties of some commercially available non-toothed flame-retardant polypropylene resin compositions. Table 8 Commercially available non-refractory polypropylene resin composition No. Experimental number Tensile strength Flexural strength Fracture modulus Impact strength Oxygen index UL94 judgment (MPa) (MPa) CGPa) (J/m) (%) HFFR 1 30.0 48.0 1.9 27.0 —— V0 HFFR2 30.0 48.0 1.9 37.0 — V0 HFFR3 22.8 42.1 2.4 26.7 —— V0 HFFR4 25.0 35.0 2.9 25.0 — V0 HFFR5 24.1 38.6 1.9 26.7 —— V0 HFFR6 28.0 45.0 2.0 30.0 —— V0 HFFR7 24.0 _ 2.0 25.0 30.0 V0 Description = [HFFR 1] 30% Exolit® AP-750 + 70% PP Profax® 6524, MFI=4, homopolymer Flame Retardant Trade Name: Ex〇lit® AP-750 Supplier: Clariant International Ltd Polypropylene Name: PP Profax® 6524: Supplier: Taiwan Polypropylene Co., Ltd. [HFFR 2] 20% CN-2616 + 80% PP Profax® 6524, MFI=4, homopolymer Flame Retardant Trade Name: CN -2616 Supplier: Great Lakes Chemical Corporation Polypropylene Trade Name: PP Profax® 6524: Supplier: Taiwan Polypropylene Co., LTD [HFFR 3] RTP Company RTP 151 Polypropylene (PP) Non Halogen Flame Retarda Nt - UL94 V-0 Flame Retardant Trade Name: RTP 151 Supplier: RTP Company [HFFR 4] Singapore Polymer Corporation SINPOLENE Flame Retardant Polypropylene Flame Retardant Trade Name: MFP 220A2 Supplier: Singapore Polymer Corporation Pte Ltd [HFFR 5] Asahi Thermofil Polypropylene P6-9900-0570 Unfilled, Flame Retardant, Heat Stabilized Commodity name: P6-9900-0570 Supplier: Asahi KASEI Corporation [HFFR 6] A. Schulman, Inc. POLYFLAM FRPP 1360, Non-Halogenated Homopolymer Polypropylene Product Name: POLYFLAMTM RPP 1360 Supplier: A. Schulman» Inc [HFFR 7] GICHEM GIPLENE DX06/V0F Polypropylene - Flame Retardant Flame Retardant Trade Name: GICHEM GIPLENE DXO6/V0F Polypropylene Supplier: Giplast SA Comparative Example 2 is commercially available Commercial halogen-free flame-retardant polypropylene resin composition, from 20 ^ 20793 comparison results of the examples and comparative example 2, it can be found that the present invention has mechanical properties not to be commercially available, especially in flexural strength and resistance. The number of folds is better than most commercially available commercial compositions, indicating that the halogen is flame retardant. Polyolefin resin composition does have "," mechanical properties, and considerable commercial potential." Different flame retardancy and machine. [Simplified description] None [Main component symbol description] None 21

Claims (1)

1320793 十、申請專利範圍： 1 · 一種無鹵難燃聚烯烴類樹脂組成物，其係包括： (1) 100重量份之聚烯烴類樹脂； (2) 15至45重量份之酸源兼氣源，係至少選自於 一種以上之群組：氮填化合物、填酸錢、聚鱗酸敍、三聚 氰胺磷酸及三聚氰胺焦磷酸； (3) 1至30重量份之碳源，係至少選自於一種以上 之群組：季戊四醇、雙季戊四醇、三季戊四醇及可膨脹性 石墨；以及 (4) 1至20重量份之相容性修飾劑，其係至少選自 於一種以上之群組：馬來酸酐接支修飾之聚烯烴類樹脂及 壓克力酸接支修飾之聚烯烴類樹脂； 以上各組成分構成百分百之組成物。 2·如申請專利範圍第1項所述之無由難燃聚稀烴類 樹脂組成物’其中的聚烯烴類樹脂係至少選自一種以上之 群組：聚乙烯、低密度聚乙烯 '線性低密度聚乙稀、高密 度聚乙烯及聚丙烯。 3·如申請專利範圍第1項所述之無鹵難燃聚稀烴類 樹脂組成物，其中的聚烯烴類樹脂係為聚丙烯。 4 ·如申凊專利範圍第3項所述之無鹵難燃聚稀煙卖員 樹脂組成物，其中的酸源兼氣源係至少選自於_種以上< 群組：氮磷化合物、聚磷酸銨及三聚氰胺焦碟酸。 5·如申請專利範圍第4項所述之無齒難燃聚歸經類 樹脂組成物，其中的碳源係至少選自於一種以上之群会 22 1320793 季戊四醇及可膨脹性石墨。 6.如申請專利範圍第5項所述之無鹵難燃聚浠烴類 樹脂組成物’其中的相容性修飾劑係為馬來酸酐接支修飾 之聚丙烯樹脂。 7 ·如申請專利範圍第1項所述之無鹵難燃聚烯烴類 樹脂組成物’其中的酸源兼氣源係至少選自於一種以上之 群組：氮鱗化合物、聚填酸錢及三聚氰胺焦填酸〇 8. 如申請專利範圍第1項所述之無豳難燃聚烯烴類 樹脂組成物，其中的碳源係至少選自於一種以上之群組： 季戊四醇及可膨脹性石墨。 9. 如申請專利範圍第1項所述之無鹵難燃聚烯烴類 樹脂組成物，其中的相容性修飾劑係為馬來酸酐接支修飾 之聚丙烯樹脂。 Η"一、圓式： 無 231320793 X. Patent application scope: 1 · A halogen-free flame-retardant polyolefin resin composition comprising: (1) 100 parts by weight of a polyolefin resin; (2) 15 to 45 parts by weight of an acid source and a gas The source is at least selected from the group consisting of: a nitrogen-filled compound, an acid-filled acid, a polysulfate, a melamine phosphate, and a melamine pyrophosphate; (3) 1 to 30 parts by weight of a carbon source, at least selected from the group consisting of More than one group: pentaerythritol, dipentaerythritol, tripentaerythritol, and expandable graphite; and (4) 1 to 20 parts by weight of a compatibility modifier selected from at least one group: maleic anhydride The polyolefin resin modified with the modified polyolefin and the polyolefin resin modified with the acrylic acid; the above components constitute a one hundred percent composition. 2. The non-flammable polyolefin resin composition as described in claim 1, wherein the polyolefin resin is at least selected from the group consisting of polyethylene and low density polyethylene. Density polyethylene, high density polyethylene and polypropylene. 3. The halogen-free flame-retardant polyolefin resin composition according to claim 1, wherein the polyolefin resin is polypropylene. 4. The halogen-free flame-retardant poly-smoke-selling resin composition according to claim 3, wherein the acid source and the gas source are at least selected from the group consisting of < Ammonium polyphosphate and melamine coke acid. 5. The toothless flame retardant polyacetal resin composition of claim 4, wherein the carbon source is at least selected from the group consisting of more than one group 22 1320793 pentaerythritol and expandable graphite. 6. The halogen-free flame-retardant polysulfonated hydrocarbon resin composition as described in claim 5, wherein the compatibility modifier is a maleic anhydride-modified polypropylene resin. 7. The halogen-free flame-retardant polyolefin resin composition as described in claim 1, wherein the acid source and the gas source are at least selected from the group consisting of nitrogen scale compounds, poly-alkali and The melamine-based flammable resin composition according to claim 1, wherein the carbon source is at least selected from the group consisting of pentaerythritol and expandable graphite. 9. The halogen-free flame-retardant polyolefin-based resin composition according to claim 1, wherein the compatibility modifier is a maleic anhydride-modified polypropylene resin. Η"一,圆式: 无 23