I 5 1 5TW^ DOC/Elvin/002 A7 B7 經濟部中央標準局員工消費合作社印製 五、發明説明(f ) 本發明是有關一種塑膠發泡材料及其製造方法,且特 別是有關一種苯乙烯系塑膠發泡材及其製造方法。 傳統上,塑膠材料以化學發泡劑、過氧化物爲架橋劑 來製造發泡材時,由於發泡的過程中,此塑膠材料必須能 經由過氧化物之架橋反應來穩定其泡孔結構,因此能使用 化學架橋發泡法來製造發泡材的塑膠種類就受到限制。可 用化學架橋發泡法來製造的塑膠種類,如聚乙烯(包括低 密度聚乙稀(Low Density PolyEthylene;LDPE )、高密度 聚乙稀(High Density PolyEthylene;HDPE )、線性低密度 聚乙嫌(Linear Low Density PolyEthylene;LLDPE ))、 乙稀-醋酸乙稀共聚合物(Ethylene Vinyl Acetate copolymer; EVA )和大部份的橡膠等,但是對於像苯乙烯 系的塑膠如聚苯乙烯(Polystyrene; PS )、丙烯腈-丁二烯 -苯乙稀共聚合物(Acrylonitrile-Butadiene-Styrene terpolymer ; ABS )、丙烯腈-苯乙烯共聚合物 (Acrylonitrile-Styrene copolymer ; AS )及丙嫌腈-苯乙 嫌-丙嫌酸醋共聚合物(Acrylonitrile-Styrene-Acrylate copolymer ; ASA )與工程塑膠如尼龍(Nylon )、聚碳 酸酯(Polycarbonate ; PC )、聚對酜酸乙烯酯(Poly Ethylene Terephthalate ; PET )、聚對联酸丁稀酉旨(Poly Butylene Terephthalate ; PBT)等,因爲這些塑膠無法以 過氧化物架橋,或是僅能部份架橋,故不能以此法獲得發 泡材。 因此在習知技藝中,密度大於〇.6g/cm1之苯乙烯系塑 (請先閲讀背面之注意事項再填寫本頁) -· 1 經濟部中央標準局貝工消費合作社印裝 1 5 1 5TW 7- .DOC/Elvin/002 A7 _B7_ 五、發明説明(z ) 膠結構發泡材,一般是以押出發泡或射出發泡製成板材, 雖然具有優良的尺寸精確性與耐熱性、高剛性與高硬度等 優點,但其缺點是不能製造成肉厚大且形狀複雜的產品, 且因爲苯乙烯系塑膠無法採用化學架橋發泡法,因此很難 得到低密度(<〇.2g/cm3 )發泡材。 因此本發明的主要目的就是提供一種利用化學架橋 發泡法製造苯乙烯系塑膠發泡材的方法,並提供一種具有 低密度、低收縮且兼具高剛性的苯乙烯系塑膠發泡材。 依據上述目的,本發明提供一種塑膠發泡材料及其製 造方法,係採用聚合物摻合的原理,將苯乙烯系塑膠的發 泡配方中,添加了可化學架橋發泡之聚烯烴類聚合物 (polyolefins )在熔融態均勻混合,並配合適當的相容劑 (compatibilizer),在熱壓模具中製備以化學架橋發泡形 成之苯乙烯系塑膠發泡材。此塑膠發泡材料,包括由下列 各成份所組成:I 5 1 5TW ^ DOC / Elvin / 002 A7 B7 Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs. 5. Description of the Invention (f) The present invention relates to a plastic foam material and a method for manufacturing the same, and more particularly to a styrene It is a plastic foam material and its manufacturing method. Traditionally, when a plastic material uses a chemical foaming agent and a peroxide as a bridging agent to manufacture a foaming material, since the foaming process, the plastic material must be able to stabilize its cell structure through the bridging reaction of the peroxide. Therefore, the types of plastics that can be used to make foamed materials using chemical bridge foaming are limited. Types of plastics that can be manufactured by chemical bridging foaming methods, such as polyethylene (including Low Density PolyEthylene (LDPE), High Density PolyEthylene (HDPE), linear low density polyethylene (HDPE) Linear Low Density PolyEthylene (LLDPE)), Ethylene Vinyl Acetate copolymer (EVA), and most of the rubber, etc., but for styrene-based plastics such as polystyrene (PS) ), Acrylonitrile-Butadiene-Styrene terpolymer (ABS), Acrylonitrile-Styrene copolymer (AS), and Acrylonitrile-Styrene copolymer (AS) -Acrylonitrile-Styrene-Acrylate copolymer (ASA) and engineering plastics such as Nylon, Polycarbonate (PC), Poly Ethylene Terephthalate (PET), Poly Butylene Terephthalate (PBT), etc., because these plastics cannot be bridged with peroxides or only partially bridged, so they cannot be bridged with Method foaming material is obtained. Therefore, in the know-how, styrene-based plastics with a density greater than 0.6 g / cm1 (please read the notes on the back before filling this page)-· 1 Printed by the Shellfish Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 1 5 1 5TW 7- .DOC / Elvin / 002 A7 _B7_ 5. Description of the Invention (z) The rubber structure foaming material is generally made of extruded foam or injection foam, although it has excellent dimensional accuracy, heat resistance and high rigidity. And high hardness, but its disadvantages are that it can not be made into products with large thickness and complex shapes, and because styrene-based plastics cannot use the chemical bridge foaming method, it is difficult to obtain low density (< 0.2 g / cm3 ) Foam material. Therefore, the main object of the present invention is to provide a method for manufacturing a styrene-based plastic foamed material by a chemical bridge foaming method, and to provide a styrene-based plastic foamed material having low density, low shrinkage, and high rigidity. According to the above purpose, the present invention provides a plastic foaming material and a method for manufacturing the same, using the principle of polymer blending, and adding a polyolefin polymer that can be chemically bridged and foamed to the foaming formula of a styrene plastic. (Polyolefins) are uniformly mixed in a molten state, and an appropriate compatibilizer is used to prepare a styrene-based plastic foamed material formed by chemical bridge foaming in a hot press mold. This plastic foam material consists of the following components:
a. 50至85份的苯乙烯系塑膠,例如ABS、AS、ASA 等。 b. 15至50份的聚烯烴類聚合物,例如LDPE、HDPE、 LLDPE、EVA、乙稀-丙嫌橡膠(Ethylene Propylene Monomer rubber ; ΕΡΜ )、乙烯-丙烯-二烯單體橡膠 (Ethylene Propylene Diene Monomer rubber ; EPDM )等。 c. 10至30份的相容劑,例如含有如氯、酸酐等官能基 之乙烯類聚合物或共聚合物或是苯乙烯·乙烯-丁烯-苯乙 嫌類共聚合物(Styrene-Ethylene-Butylene-Styrene co- 4 本紙張尺度適用中國國家標準(CNS ) Λ4規格(210X297公釐) (請先閲讀背面之注意事項再填寫本頁) I訂 ]5 1 5TWT- DOC/Eivin/002 A7 B7 五、發明説明(多) polymer ) ° d. l至10的化學發泡劑,例如偶氮類化學發泡劑。 (請先閲讀背面之注意事項再填寫本頁) e. l至2份的架橋劑’例如二異丙苯基過氧化物(以-cumyl peroxide )' 2,5-過氧三級丁基_2,5_二甲基己烷 (2,5-(ieri-butylperoxide)-2,5-dimethylhexane )等。 f. 〇至2份的發泡助劑’例如氧化鋅、尿素等。 g·其他添加劑,例如作爲加工助劑之硬脂酸鋅,或是 色料 '碳酸鈣及軟木屑(cork )等增量劑,或是白煙 (silica )、碳煙(carbon black )等補強劑。 而此塑膠發泡材料的製造方法,包括下列步驟: a. 將50至85份的苯乙烯系塑膠、15至5〇份的聚烴烯 類聚合物、10至30份的相容劑,在一混練機中以約13〇 艽到160 °C的溫度均勻混合,例如雙輥輪混練機(two-roll mill )或利拿混練機(kneader )。 b. 於此混練機中再加入1至10份的化學發泡劑與1至 2份的架橋劑以及0到2份之發泡助劑; c_將均勻混合後之前述各項原料壓出片,例如以雙輥 輪混練機出片; 經濟部中央揉準局貝工消費合作社印製 d·出片後置於一熱壓模具中以約160 °C到180 °C之溫 度,在約100Kg/cm2到250Kg/cm2的壓力下熱壓一適當時 間’例如約20分鐘到40分鐘;視模具厚度做修正。 藉以得到由化學架橋發泡法所形成之苯乙烯系塑膠 發泡材料。 _ 爲讓本發明之上述和其他目的、特徵、和優點能更明 5 本紙張尺度適用中國國家&準(CNS ) A4規格(210X297公釐) " " I 5 ! STV/J- .DOC/Elvin/002 A7 B7 經濟部中央樣準局貝工消费合作社印製 五、發明説明(午) 顯易懂,下文特舉一較佳實施例,並配合所附圖式,作詳 細說明如下: 圖式之簡單說明: 第1圖爲本發明第一實施例之壓縮曲線圖。 第2圖爲本發明第二實施例之壓縮曲線圖。 第3圖爲本發明第三實施例之壓縮曲線圖。 第1表爲本發明中三實施例之成分組成表。 第2表爲本發明中三實施例之物性表。 第一實施例 取苯乙烯系塑膠之ABS塑膠65份、聚烯烴類聚合物 之EVA 35份,再配合相容劑15份,例如含有如氯、酸酐 等官能基之乙烯類聚合物或共聚合物或是苯乙烯-乙烯-丁 烯·苯乙烯類共聚合物、發泡劑2.3份,例如偶氮類化學發 泡劑、做架橋劑之過氧化物1份、做爲發泡助劑之氧化鋅 1份、做爲加工助劑之硬脂酸鋅1份,在混練機均勻混合, 例如雙輥輪混練機或利拿混練機,出片後於180 °C之熱壓 模具熱壓30分鐘,詳細的配方請參考第1表。由第2表的 物性結果顯示,添加可架橋發泡的EVA後,配合相容劑的 使用,可得到平整的發泡材,而密度可低至0.14g/cm3 ;第 1圖爲其壓縮曲線圖,壓縮強度約爲64Kgf。 第二實施仿 取苯乙烯系塑膠之ABS塑膠65份 '聚烯烴類聚合物 之LLDPE 35份,再配合相容劑15份,例如是含有如氯、 酸酐等官能基之乙烯類聚合物或共聚合物或是苯乙烯_乙 6 本紙張尺度適财關( CNS〉A4規格(210X297公釐) " 9. Hr n. -II - - I HI n n an n In (請先閲讀背面之注意事項再填寫本頁) 15l5TWp .DOC/Elvin/002 A7 15l5TWp .DOC/Elvin/002 A7 經濟部中央標準局員工消費合作社印裝 _ B7 ___ 五、發明説明(夕) 烯-丁烯-苯乙烯類共聚合物、發泡劑2份,例如偶氮類化 學發泡劑、做爲架橋劑之過氧化物0.8份、做爲發泡助劑 之氧化鋅1份、做爲加工助劑之硬脂酸鋅1份,在混練機 均勻混合,例如雙輥輪混練機或利拿混練機,出片後於180 艺之熱壓模具熱壓30分鐘,詳細的配方與物性請參考第1 表與第2表,第2圖爲其壓縮曲線圖,壓縮強度可達約 134Kgf。本實施例之特徵在於:雖然可提供架橋的LLDPE 成份僅佔35 %,但所得到的發泡材不僅未分層、密度低’ 而且Shore C硬度高達84,已逼近部份ABS結構發泡材的 硬度,但本實施例的密度僅其1/4,重量相當輕,充分顯 示本發明的優點。 第三實施例 取苯乙烯系塑膠之ABS塑膠65份、聚烯烴類聚合物 之LDPE 35份,再配合相容劑15份,例如是含有如氯、 酸酐等官能基之乙嫌類聚合物或共聚合物或是苯乙烯•乙 烯-丁烯-苯乙烯類共聚合物、發泡劑2份,例如偶氮類化 學發泡劑 '做爲架橋劑之過氧化物0.8份、做爲發泡助劑 之氧化鋅1份、做爲加工助劑之硬脂酸鋅1份,在混練機 均勻混合,例如雙輥輪混練機或利拿混練機,出片後於180 °(:之熱壓模具熱壓30分鐘,詳細的配方與物性請參考第1 表與第2表,shore C硬度高達84,密度僅有(M3 g/cm3, 第3圖爲其壓縮曲線圖,壓縮強度約74Kgf。 依據上述實施例,本發明之塑膠發泡材有以下的優 點: (請先閲讀背面之注意事項再填寫本頁)a. 50 to 85 parts of styrene plastic, such as ABS, AS, ASA, etc. b. 15 to 50 parts of polyolefin polymers, such as LDPE, HDPE, LLDPE, EVA, Ethylene Propylene Monomer rubber (EPM), Ethylene Propylene Diene monomer (Ethylene Propylene Diene) Monomer rubber; EPDM). c. 10 to 30 parts of compatibilizers, such as vinyl polymers or copolymers containing functional groups such as chlorine, anhydride, or styrene · ethylene-butene-styrene copolymers (Styrene-Ethylene -Butylene-Styrene co- 4 This paper size applies to Chinese National Standard (CNS) Λ4 specification (210X297 mm) (Please read the precautions on the back before filling this page) I order] 5 1 5TWT- DOC / Eivin / 002 A7 B7 V. Description of the invention (multiple) polymer) ° d. Chemical foaming agents from 1 to 10, such as azo chemical foaming agents. (Please read the precautions on the back before filling this page) e. 1 to 2 parts of the bridging agent 'such as dicumyl peroxide (as -cumyl peroxide)' 2,5-peroxy tertiary butyl_ 2,5_dimethylhexane (2,5- (ieri-butylperoxide) -2,5-dimethylhexane) and the like. f. 0 to 2 parts of a foaming aid 'such as zinc oxide, urea, and the like. g · Other additives, such as zinc stearate as a processing aid, or extenders such as pigments such as calcium carbonate and cork, or reinforcements such as silica and carbon black Agent. The method for manufacturing the plastic foaming material includes the following steps: a. 50 to 85 parts of a styrene-based plastic, 15 to 50 parts of a polyalkylene polymer, and 10 to 30 parts of a compatibilizer. A kneader is uniformly mixed at a temperature of about 130 to 160 ° C, such as a two-roll mill or a kneader. b. Add 1 to 10 parts of chemical foaming agent, 1 to 2 parts of bridging agent, and 0 to 2 parts of foaming aid to this kneader; c_ Extrude the aforementioned raw materials after uniform mixing For example, a double-roller kneading machine is used to produce the film; the Central Ministry of Economic Affairs prints d · after printing and puts it in a hot-press mold at a temperature of about 160 ° C to 180 ° C. Hot pressing under a pressure of 100Kg / cm2 to 250Kg / cm2 for an appropriate time 'for example, about 20 minutes to 40 minutes; depending on the thickness of the mold to make corrections. Thereby, a styrene-based plastic foamed material formed by a chemical bridge foaming method is obtained. _ In order to make the above and other objects, features, and advantages of the present invention clearer 5 paper sizes are applicable to China's national & standard (CNS) A4 specifications (210X297 mm) " " I 5! STV / J-. DOC / Elvin / 002 A7 B7 Printed by Shellfish Consumer Cooperative of the Central Samples Bureau of the Ministry of Economic Affairs 5. Description of the Invention (L) It is easy to understand. The following is a detailed description of a preferred embodiment and the accompanying drawings. : Brief description of the drawings: Fig. 1 is a compression curve diagram of the first embodiment of the present invention. Fig. 2 is a compression curve diagram of the second embodiment of the present invention. FIG. 3 is a compression curve diagram of the third embodiment of the present invention. Table 1 is a component composition table of the three embodiments of the present invention. Table 2 is a physical property table of the three embodiments of the present invention. In the first embodiment, 65 parts of styrene-based plastic ABS plastic and 35 parts of EVA of polyolefin-based polymer are added, and 15 parts of compatibilizer are blended, such as an ethylene-based polymer or copolymer containing functional groups such as chlorine and acid anhydride. Or styrene-ethylene-butene · styrene copolymer, 2.3 parts of foaming agent, such as azo-based chemical foaming agent, 1 part of peroxide as a bridging agent, and foaming auxiliary 1 part of zinc oxide, 1 part of zinc stearate as a processing aid, evenly mixed on a kneading machine, such as a twin-roller kneader or a lina kneader, and hot-pressed at 180 ° C in a hot-pressing mold after the tablet is released. Min. For detailed recipe, please refer to Table 1. The physical property results in Table 2 show that after adding EVA that can be bridged and foamed, the use of a compatibilizer can obtain a flat foam material with a density as low as 0.14 g / cm3; Figure 1 shows its compression curve. Figure, the compression strength is about 64Kgf. The second implementation is based on 65 parts of ABS plastic of styrene plastic, 35 parts of LLDPE of polyolefin polymer, and 15 parts of compatibilizer, such as vinyl polymers or copolymers containing functional groups such as chlorine and acid anhydride. Polymer or styrene_B 6 This paper is suitable for paper size (CNS> A4 size (210X297mm) " 9. Hr n. -II--I HI nn an n In (Please read the notes on the back first (Fill in this page again) 15l5TWp .DOC / Elvin / 002 A7 15l5TWp .DOC / Elvin / 002 A7 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs _ B7 ___ V. Description of the invention (Even) olefin-butene-styrene 2 parts of polymer and foaming agent, such as azo chemical blowing agent, 0.8 part of peroxide as bridging agent, 1 part of zinc oxide as foaming aid, and stearic acid as processing aid 1 part of zinc, evenly mixed in a kneading machine, such as a double-roller kneading machine or a Lina kneading machine. After the film is released, it is hot-pressed for 30 minutes in a 180-pressure hot-pressing mold. For detailed recipes and physical properties, please refer to Table 1 and Table 2. Table 2 is the compression curve diagram, and the compression strength can reach about 134Kgf. This embodiment is characterized in that although it can be improved The LLDPE composition for the bridge only accounts for 35%, but the obtained foamed material not only has no layering and low density, but also has a Shore C hardness of 84, which is close to the hardness of some ABS structural foamed materials, but the density of this embodiment Only 1/4 of it is quite light and fully shows the advantages of the present invention. The third embodiment takes 65 parts of styrene plastic ABS plastic, 35 parts of polyolefin polymer LDPE, and 15 parts of compatibilizer. For example, ethylene polymer or copolymer containing functional groups such as chlorine and acid anhydride, or styrene-ethylene-butene-styrene copolymer, foaming agent, such as azo chemical foam Agent '0.8 parts peroxide as bridging agent, 1 part zinc oxide as foaming aid, 1 part zinc stearate as processing aid, uniformly mixed in a kneading machine, such as a two-roller kneading machine Or Lina mixer, hot-pressed at 180 ° (: hot-pressing mold for 30 minutes after the film is released. For detailed formula and physical properties, please refer to Table 1 and Table 2. Shore C hardness is as high as 84, density is only (M3 g / cm3, Figure 3 is its compression curve diagram, and the compression strength is about 74Kgf. According to the above embodiment, the present invention Mingzhi Plastic Foam has the following advantages: (Please read the precautions on the back before filling this page)
本紙張尺度適用中國國家;CNS ) A4規格(210X297公嫠Γ " ^ 15I5TW^.DOC/Elvin/002 A7 B7 五、發明説明(6) 1. 可在熱壓模具中以化學架橋發泡法製造苯乙烯系塑 膠發泡材。 2. 密度低,範圍可達0.1〜0.5g/cm3。 3. 硬度達Shore C 70以上。 4. 壓縮強度可達60Kg以上。 5. 經實驗可在70 °C的烘箱中放置72小時以上不會收 縮變形。 因此經由本發明所製作之塑膠發泡材,將可在有需質 輕且硬度大之高溫環境下應用,如建材(人造木材、耐熱 之隔音、隔熱材)、運動器材與運輸器材等。 雖然本發明已以一較佳實施例揭露如上,然其並非用 以限定本發明,任何熟習此技藝者,在不脫離本發明之精 神和範圍內,當可作各種之更動與潤飾,因此本發明之保 護範圍當視後附之申請專利範圍所界定者爲準。 I III 1 _ - I - I 1 _ I - (請先閲讀背面之注意事項再填寫本頁) 經濟部中央標準局員工消費合作社印製 8 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) 第1表、本發明中三個實施例之成分組成表 第一實施例 第二實施例 第三實施例 ABS 65 ABS 65 ABS 65 EVA 35 LLDPE 35 LDPE 35 相容劑 15 相容劑 15 相容劑 15 氧化鋅 1 氧化鋅 1 氧化鋅 1 硬脂酸鋅 1 硬脂酸鋅 1 硬脂酸鋅 1 發泡劑 2.3 發泡劑 2 發泡劑 2 過氧化物 0.8 過氧化物 0.8 過氧化物 0.8 第2表、本發明中三個實施例之物性表 第一實施例 第二實施例 第三實施例 相容性 不分層 不分層 不分層 密度(g/cm3) 0.14 0.18 0.13 硬度(Shore C) 74 84 78 壓縮強度(Kgf) 64 134 74This paper size is applicable to China; CNS) A4 size (210X297mm) ^ 15I5TW ^ .DOC / Elvin / 002 A7 B7 V. Description of the invention (6) 1. It can be used in the hot-pressing mold by chemical bridge foaming method Manufacture of styrenic plastic foam material. 2. Low density, range up to 0.1 ~ 0.5g / cm3. 3. Hardness up to Shore C 70 or more. 4. Compressive strength up to 60Kg or more. 5. Tested at 70 ° C will not shrink and deform if left in the oven for more than 72 hours. Therefore, the plastic foam material produced by the present invention can be applied in high-temperature environments that require light weight and high hardness, such as building materials (artificial wood, heat-resistant sound insulation). , Insulation materials), sports equipment and transportation equipment, etc. Although the present invention has been disclosed as above with a preferred embodiment, it is not intended to limit the present invention. Any person skilled in the art will not depart from the spirit and scope of the present invention. In addition, various modifications and retouching can be made, so the scope of protection of the present invention shall be determined by the scope of the attached patent application. I III 1 _-I-I 1 _ I-(Please read the note on the back first Please fill in this page for matters) Central Bureau of Standards, Ministry of Economic Affairs Printed by Employee Consumer Cooperatives 8 This paper size is in accordance with Chinese National Standard (CNS) A4 (210X297 mm) Table 1, Composition Table of the Three Embodiments of the Invention First Embodiment Second Embodiment Third Embodiment ABS 65 ABS 65 ABS 65 EVA 35 LLDPE 35 LDPE 35 Compatibility agent 15 Compatibility agent 15 Compatibility agent 15 Zinc oxide 1 Zinc oxide 1 Zinc oxide 1 Zinc stearate 1 Zinc stearate 1 Zinc stearate 1 Foaming Agent 2.3 Foaming agent 2 Foaming agent 2 Peroxide 0.8 Peroxide 0.8 Peroxide 0.8 Table 2 and the physical properties of the three embodiments of the present invention The first embodiment, the second embodiment and the third embodiment are compatible Non-stratified non-stratified non-stratified density (g / cm3) 0.14 0.18 0.13 Hardness (Shore C) 74 84 78 Compressive strength (Kgf) 64 134 74