WO2015039479A1 - 淀粉环保纸及其制备方法 - Google Patents

淀粉环保纸及其制备方法 Download PDF

Info

Publication number
WO2015039479A1
WO2015039479A1 PCT/CN2014/080776 CN2014080776W WO2015039479A1 WO 2015039479 A1 WO2015039479 A1 WO 2015039479A1 CN 2014080776 W CN2014080776 W CN 2014080776W WO 2015039479 A1 WO2015039479 A1 WO 2015039479A1
Authority
WO
WIPO (PCT)
Prior art keywords
raw material
polylactic acid
starch
paper
calcium carbonate
Prior art date
Application number
PCT/CN2014/080776
Other languages
English (en)
French (fr)
Inventor
郑文彬
纪永明
Original Assignee
郑文彬
纪永明
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by 郑文彬, 纪永明 filed Critical 郑文彬
Publication of WO2015039479A1 publication Critical patent/WO2015039479A1/zh

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L3/00—Compositions of starch, amylose or amylopectin or of their derivatives or degradation products
    • C08L3/02—Starch; Degradation products thereof, e.g. dextrin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/10—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of paper or cardboard
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/21—Macromolecular organic compounds of natural origin; Derivatives thereof
    • D21H17/24—Polysaccharides
    • D21H17/28—Starch
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/63—Inorganic compounds
    • D21H17/67—Water-insoluble compounds, e.g. fillers, pigments
    • D21H17/675—Oxides, hydroxides or carbonates
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
    • D21H27/30—Multi-ply
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/03—3 layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/40—Symmetrical or sandwich layers, e.g. ABA, ABCBA, ABCCBA
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
    • B32B2264/10—Inorganic particles
    • B32B2264/102—Oxide or hydroxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2554/00—Paper of special types, e.g. banknotes

Definitions

  • the invention relates to a papermaking technique, in particular to a starch environmentally friendly paper. Background technique
  • the raw materials for papermaking are mainly plant fibers such as wood, straw, wheat straw, corn poles, bagasse, reed, hemp, bamboo and the like.
  • the production of paper can be roughly divided into two processes, pulping and papermaking. 1. Pulping: In the raw material China, some chemicals (such as lime or caustic soda) are cooked; or the raw materials are directly broken and ground by mechanical means; then washed to remove unnecessary components, and the fibers are retained to make a slurry. If bleaching is required, add the agent for bleaching. 2. Papermaking: The slurry is picked up by a grid or picked up, dehydrated, pressed and dried, and finally finished into paper.
  • the traditional paper industry is a light industry with large output, high water consumption and serious pollution.
  • the wastewater in the paper industry is discharged into the river without ineffective treatment, the organic matter in the wastewater is fermented, oxidized, decomposed, and the water is consumed by oxygen, causing the aquatic organisms such as fish and shellfish to die of oxygen; The fine fibers are suspended in the water, which easily block the fish carp and cause fish to die.
  • the bark, wood chips, grass clippings, rot, and pulp in the wastewater sink into the bottom of the river, and the riverbed is fouled. Poisonous odor; There are some substances in the wastewater that are not easy to be fermented and decomposed.
  • the object of the present invention is to provide a plant material which is not re-cut, does not use petrochemical products, does not produce air pollution, does not produce sewage, and utilizes annual reproducible plant raw materials and continuous calcium carbonate and natural auxiliaries to be polymerized.
  • the starch environmental protection paper produced by the method is a natural non-toxic, no heavy metal, no plasticizer, and can be 100% biodegradable.
  • the environmentally friendly materials can be used by all walks of life to achieve the goal of being environmentally friendly and not wasting resources.
  • the invention provides an environmentally friendly starch paper, which comprises: a three-layer composite structure comprising an upper polylactic acid polymer raw material, a middle layer masterbatch and a lower polylactic acid polymer raw material, wherein the thickness ratio of the three layers is 1: 8: 1, the papermaking master batch comprises the following mass percentage components:
  • Polylactic acid polymer raw material 20%;
  • the preparation method of the starch environmental protection paper is as follows:
  • Step 1 The granular starch raw material and the prepared polylactic acid polymer raw material and the calcium carbonate raw material are placed in an internal mixer at a mass ratio of 30%: 20%: 50%, at a high temperature of 130 degrees Celsius. Made into a masterbatch of papermaking after 90 minutes of hardening;
  • Step 2 The papermaking masterbatch is introduced into the casting machine by means of three layers of co-extrusion, wherein the upper and lower layers are made of a polylactic acid polymer raw material as a cover film layer, and the middle layer is simultaneously fed into the casting machine with a large amount of the papermaking master batch, the upper layer of polylactic acid
  • the ratio of the thickness of the polymer raw material, the middle layer masterbatch and the lower polylactic acid polymer material is 1:8:1, and then the film is cast at a temperature of 180 degrees, and then semi-cooled and then progressively made by dozens of rollers. Stretch straight, then enter the large-row oven, and slowly stretch it at a temperature of 8 ( ⁇ 110 °C), then enter dozens of rollers to make continuous cooling and shaping, flattening, and make Round roll of environmentally friendly paper;
  • Step 3 Put the prepared environmentally-friendly paper into the static elimination machine to remove the static electricity existing in the paper to obtain the desired environmentally friendly starch paper.
  • the starch raw material is prepared as follows: After the industrial starch is added to the glycerin, it is cooked at a high temperature of 120 to 160 degrees Celsius, catalyzed by heating, cooled, and then, after entering the internal mixer, is densely mixed at a temperature of 110 degrees Celsius. After the hour, the granules are further processed to obtain a granulated starch raw material; wherein the ratio of the industrial starch to the glycerin is 90%, and the glycerin accounts for 10%.
  • starch raw materials contribute to the special function of rapid cracking and biodegradation after use in the future when paper is produced.
  • the preparation method of the polylactic acid polymer raw material is as follows:
  • the polylactic acid and the additive are added to the reaction tank at a mass ratio of 1: 0. 05 ⁇ 0. 3 and then mixed, wherein the components of the additive are: glycerin, polylactic acid glycolic acid and licorice extract, Its ratio is 7:2:1 by mass ratio;
  • composition and ratio of the filler are as follows:
  • Amylose 4 ( ⁇ 55%; Calcium carbonate, mica powder or kaolin 40 ⁇ 55%;
  • the above-mentioned polylactic acid polymer raw material is taken as one of the main raw materials for the environmentally-friendly paper technology of the present invention, and the polylactic acid is subjected to a molecular structure of polylactic acid by a glyceride, and the molecular structure thereof is adjusted to the same. After the desired molecular weight, it is then chained, so that it can be used as a raw material for papermaking. This raw material can make it more extendable, stretchable and biodegradable in the manufacturing process of environmentally friendly starch paper.
  • the calcium carbonate raw material is prepared as follows: First, after the calcium carbonate is ground to a fineness of 800 mesh to 1000 mesh, natural salad oil, polylactic acid, and stearic acid slip agent are added, and then placed in an internal mixer with 150 The high temperature of Celsius is mixed and then shirred into a granulated calcium carbonate raw material; the amount of each raw material is in the mass ratio: 82% of calcium carbonate, 5% of natural salad oil, 10% of polylactic acid, hard Fatty acid slipper 3%.
  • the above-mentioned calcium carbonate raw material has the effect of making the product better written and achieving a better hand feeling after being made into paper.
  • the environmentally-friendly starch paper prepared by the invention has a thin layer of polylactic acid on the upper and lower sides, which is equivalent to a laminating film in a general paper cup (the conventional laminating film is a layer of tantalum material),
  • the conventional laminating film is a layer of tantalum material
  • our environmentally friendly paper does not have the problem of using plastic, that is to say, there is no problem of plasticizer.
  • the function is to reduce the specific gravity and reduce the density, which is comparable to the density and specific gravity of the original paper.
  • the environmentally-friendly paper products described in this patent are in use, such as water (such as water cups), oil (such as hamburger boxes, French fries paper bags), no need to make any liquid paper, so there will be no use when used.
  • water such as water cups
  • oil such as hamburger boxes, French fries paper bags
  • the starch is made from industrial starch (90% by mass), glycerin (10% by mass), high temperature (120 degrees to 160 degrees), cooking (catalyst without heating, catalyzed by heating), After cooling, after entering the internal mixer, it is made to be granulated after being kneaded at a temperature of 110 ° C for one hour, and after cooling, it is waited for the next stage. This material helps to achieve special functions for rapid cracking and biolysis after use in the future.
  • Polylactic acid polymer raw material After the molecular structure of polylactic acid is broken by glyceride, the molecular structure is adjusted to the desired molecular weight, and then it is chained to become the desired raw material. . This material can make it more stretchable, stretchable and biodegradable during the manufacturing process.
  • the polylactic acid polymer raw material is prepared as follows:
  • the polylactic acid and the additive are added to the reaction tank at a mass ratio of 1: 0. 05 ⁇ 0. 3 and then mixed, wherein the components of the additive are: glycerin, polylactic acid glycolic acid and licorice extract, Its ratio is 7:2:1 by mass ratio;
  • composition and ratio of the filler are as follows:
  • Amylose 4 ( ⁇ 55%
  • Calcium carbonate raw materials It is an inorganic substance, a natural mineral that is neither toxic, no heavy metal, and has no plasticizer. It returns to the natural land after use. The effect of this material enables the product to be better written after being made into paper. Get a better feel.
  • the preparation method is as follows: First, calcium carbonate (82% by mass) is ground to the required fineness (800 mesh to 1000 mesh), natural salad oil (5% by mass) and a little poly Lactic acid (10% by mass) and stearic acid slip (3% by mass) are placed in an internal mixer and fixed at a high temperature of 150 degrees, and then sifted into a snail machine to form granules. spare.
  • Step 1 using the starch raw material (30% by mass), adding the prepared polylactic acid polymer raw material (20% by mass) and calcium carbonate raw material (50% by mass) ), according to the product required to be put into the machine in a certain proportion, at a high temperature of 130 degrees, after 90 minutes of compact manufacturing into a masterbatch.
  • the masterbatch to be prepared is a three-layer co-extruded double-spinning-based casting machine; the upper and lower layers are made of pure polylactic acid polymer raw material as a cover layer (two layers of pure polylactic acid) Similar to the laminating machine, the coating forms a protective film on the middle layer of the masterbatch.
  • the middle layer uses a large amount of papermaking masterbatch (the upper layer of polylactic acid polymer raw material, the middle layer of the masterbatch, the lower polylactic acid polymer raw material, the thickness ratio For 1: 8: 1), enter the snail machine at the same time, cast into a film at a temperature of 180 degrees, and then, after semi-cooling, make progressive straight stretching by dozens of rollers, and then enter the large row.
  • the oven is slowly stretched at a temperature of 8 ( ⁇ 110 degrees), and then enters dozens of rollers for continuous cooling and shaping, flattening, and becomes a circular roll of environmentally friendly paper.
  • the thickness can be used according to the requirements.
  • the paper is used for control in re-stretching.
  • the density and weight of the paper will be comparable to the weight and density of ordinary paper due to the biaxial stretching of these machines.
  • Step 3 Put the prepared environmentally-friendly paper into another machine (static elimination machine).
  • the purpose of this machine is to remove the static electricity existing in the paper, so that it can be used for subsequent printing and dyeing. At this point, the environmentally friendly paper has been manufactured.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Biological Depolymerization Polymers (AREA)
  • Paper (AREA)

Abstract

一种环保淀粉纸，其包括上层聚乳酸聚合物原料、中层造纸母粒和下层聚乳酸聚合物原料的三层复合结构，三层的厚度比例为1：8：1，其中，造纸母粒包括如下质量百分比的组分：淀粉原料：30%；聚乳酸聚合物原料：20%；碳酸钙原料：50%。所述环保淀粉纸通过不使用重金属和塑化剂的环境友好的方式制造，是完全可降解的。

Description

说 明 书 淀粉环保纸及其制备方法 技术领域
本发明涉及一种造纸技术， 尤其是一种淀粉环保纸。 背景技术
现有的造纸技术中， 造纸的原料主要是植物纤维， 如木材、 稻草、 麦草、 玉 米杆、 甘蔗渣、 芦苇、 麻、 竹等。 纸的生产大体上可分为两个过程， 即制浆和造 纸。 1、 制浆： 在原料中国入一些化学药品 （如石灰或烧碱等） 进行蒸煮； 或者 将原料直接用机械打碎、 研磨； 然后洗涤， 去除不必要成分， 保留纤维， 制成浆 料。 需要漂白的， 再加入药剂进行漂白。 2、 造纸： 把浆料用网格或捞起， 脱水 压搾干燥， 最后整理成纸。
因此， 传统的造纸工业是一个产量大、 用水多、 污染严重的轻工业。 如： 造 纸工业中的废水若未经不效处理而排入江河中， 废水中的有机物质发酵、 氧化、 分解， 消耗水是的氧气， 使鱼类、 贝类等水生生物缺氧致死； 一些细小的纤维悬 浮在水中， 容易堵塞鱼鳃， 也造成鱼类死亡； 废水中的树皮屑、 木屑、 草屑、 腐 草、 腐浆等沉入水底， 淤塞河床， 在缓慢发酵中， 不断产生毒臭气； 废水中还有 一些不容易发酵、 分解的物质， 悬浮在水中， 吸收光线， 减少阳光透入河水， 妨 碍水生植物的光合作用；另外还会带有一些致癌、致畸、致突变的有毒有害物质。 另外， 造纸工业排放的一些固体废物如腐烂浆料， 浆渣、 树皮、 碎木片、 草根、 煤灰渣等， 占用场地， 发酵变质， 放出臭气， 下雨时， 还流出有毒臭水， 污染地 面水和地下水源。 同时，在造纸的生产过程中锅炉燃煤产生的废气和烟尘及机械 的噪声也影响工作人员和附近居民健康。 发明内容
本发明的目的在于提供一种采用不砍树、 不用石化产品、不制造空污、 不产 生污水， 而是利用年年可再生产的植物原料和取之不断的碳酸钙和天然助剂， 经 聚合后再用专用生产设备所生产出来的淀粉环保纸及其制备方法，采用该方法所 生产出来的淀粉环保纸是一种天然无毒， 无重金属， 无塑化剂， 可 100%为生物 可分解的环保材料， 可供应各行各业所用， 而达到既环保又不浪费资源的目的。
本发明提供了一种环保淀粉纸， 其特征在于： 包括上层聚乳酸聚合物原料、 中层造纸母粒和下层聚乳酸聚合物原料的三层复合结构，所述三层的厚度比例为 1： 8： 1， 所述造纸母粒包括如下质量百分比的组分：
淀粉原料： 30%;
聚乳酸聚合物原料： 20%;
碳酸钙原料： 50%。
所述淀粉环保纸的制备方法如下：
步骤一、将颗粒状的淀粉原料加上制好的聚乳酸聚合物原料和碳酸钙原料按 质量比为 30%: 20%： 50%的比例放入密炼机中， 以 130摄氏度的高温， 经 90分 钟密炼制造成为造纸母粒；
步骤二、将造纸母粒用三层共挤的方式进入流延机， 其中上、 下层用聚乳酸 聚合物原料做覆盖膜层， 中层用大量的造纸母粒同时进入流延机， 上层聚乳酸聚 合物原料、 中层造纸母粒和下层聚乳酸聚合物原料的厚度比例为 1 : 8： 1， 再以 180度的温度流延成膜状， 然后经半冷却后再由数十支滚轮做渐进式直向拉伸， 而后再进入大排式烘箱， 以 8(Γ110摄氏度的温度， 慢慢做横向拉伸， 出来后再 进入数十支滚轮做连绩式冷却和定型、 压平， 制成为圆卷式的环保纸；
步骤三、将做好的环保纸张再进入静电消除机，将存在于纸张内之静电除去， 得到所需的环保淀粉纸。
所述淀粉原料的制法如下： 将工业用淀粉加入甘油后， 经 120 〜160摄氏度 高温蒸煮、 以加热方式催化， 再冷却后， 再进入密炼机后， 在 110摄氏度的温度 下密炼一小时后再制成颗粒， 经冷却后得到颗粒状的淀粉原料； 其中工业用淀粉 与甘油的配比按质量比为： 工业用淀粉占 90%， 甘油占 10%。
上述的淀粉原料有助于将来制成纸张时，在使用后达到快速裂解与生物分解 的特殊功能。
所述聚乳酸聚合物原料的制法如下：
( 1 ) 将聚乳酸与添加剂按质量比 1 ： 0. 05〜0. 3的比例加入反应槽混合后进 行改质， 其中添加剂的组分为： 甘油、 聚乳酸甘醇酸和甘草提取液， 其配比按质 量比为 7 : 2 : 1；
( 2 ) 将改质后的聚乳酸与填充料混合搅匀， 再经造粒机造出完全生物降解 的聚乳酸聚合物颗粒， 所述聚乳酸与填充料的配比按质量比为： 聚乳酸占 40〜80%， ±真充料占 20〜60%。
所述填充料的具体成分及配比按质量比如下：
直链淀粉 4(Γ55%; 碳酸钙、 云母粉或高岭土 40〜55%；
甘油 0. 75〜3%；
乙二醇 0. 75〜3%；
环氧大豆油 2〜8%；
山梨酸 1〜4%；
尿素 0. 25〜1%；
偶联剂 0. θΓθ. 015%；
甲壳素 0. 01%；
枯草菌 0. 01%ο
上述的聚乳酸聚合物原料取作为本发明的制造环保纸技术的主要原料之一， 所述聚乳酸在通过甘油酯把聚乳酸之高分子结构将之断链后，将其分子结构调至 所需的分子量后， 再将之结链， 如此即可成为造纸所需的原料。本原料在环保淀 粉纸的制造过程能使其更有延展、 拉伸之功能和达到生物分解之功效。
所述碳酸钙原料制法如下： 首先， 将碳酸钙磨成细度为 800目〜 1000目后， 加入天然色拉油、聚乳酸、和硬脂酸滑剂后， 放入密炼机中用 150摄氏度的高温 加以密炼， 而后再入螺杵机制成颗粒状的碳酸钙原料； 其中各原料的用量按质量 比为： 碳酸钙用量为 82%， 天然色拉油 5%， 聚乳酸 10%， 硬脂酸滑剂 3%。
上述碳酸钙原料的功效是能使本产品在制成纸张后，更好书写并取得更好的 手感。
与现有的普通纸张相比，本发明所制备的环保淀粉纸中， 由于上下有薄层的 聚乳酸， 相当于一般的纸杯中的淋膜 (传统的淋膜为一层 ΡΕ材质）， 具有与淋膜 相同的功能； 本产品做成水杯后一样不漏水， 其淋膜部份， 我们的环保纸却没有 使用塑料的问题， 也就是说没有塑化剂的问题。 同时， 由于本专利所述的环保纸 张， 经双轴拉伸后， 功能在于比重减轻、 密度减低， 和原本纸浆制成纸的密度、 比重不相上下， 但本产品用于书写时， 不但有原木纸浆做成的手感， 将环保纸书 写后， 浸泡水中然后擦干， 其字体不但不会被水所侵蚀和溶解， 及模糊不清； 铅 笔书写时， 橡皮擦也可擦掉。 另外， 本专利所述的环保纸张产品在使用中， 如遇 有水 (如水杯）， 油（如汉堡盒、 薯条纸袋）， 不需再做任何液体的纸张， 所以在使 用时不会有任何毒素， 重金属及塑化剂的产生， 是一种真正的环保纸张。 具体实施方式 下面通过具体的实施例来进一步介绍本发明所述的环保淀粉纸。
一、 原料的取得与用法：
(一)淀粉原料：
首先， 淀粉是采用工业用淀粉 (按质量比占 90%)加入甘油（按质量比占 10%) 后高温（120度〜 160度)蒸煮、 催化 (不加催化剂， 以加热方式催化）， 再冷却后， 再进入密炼机后，在 110度的温度下密炼一小时后再制成颗粒， 经冷却后再等下 一阶段。此材料有助于将来制成纸张时，在使用后达到快速裂解与生物分解的特 殊功能。
(二） 聚乳酸聚合物原料： 用甘油酯把聚乳酸之高分子结构将之断链后， 将 其分子结构调至所需的分子量后， 再将之结链， 即可成为所需的原料。本原料在 产品之制造过程能使其更有延展、 拉伸之功能和达到生物分解之功效。
所述聚乳酸聚合物原料制法如下：
( 1 ) 将聚乳酸与添加剂按质量比 1 ： 0. 05〜0. 3的比例加入反应槽混合后进 行改质， 其中添加剂的组分为： 甘油、 聚乳酸甘醇酸和甘草提取液， 其配比按质 量比为 7 : 2 : 1；
( 2 ) 将改质后的聚乳酸与填充料混合搅匀， 再经造粒机造出完全生物降解 的聚乳酸聚合物颗粒， 所述聚乳酸与填充料的配比按质量比为： 聚乳酸占 40〜80%， ±真充料占 20〜60%；
所述填充料的具体成分及配比按质量比如下：
直链淀粉 4(Γ55%;
碳酸钙、 云母粉或高岭土 4(Γ55%;
甘油 0. 75〜3%；
乙二醇 0. 75〜3%；
环氧大豆油 2〜8%；
山梨酸 1〜4%；
尿素 0. 25〜1%；
偶联剂 0. θΓθ. 015%；
甲壳素 0. 01%；
枯草菌 0. 01%ο
(三） 碳酸钙原料： 为无机物， 既无毒、 再无重金属、 无塑化剂的天然矿物 质， 使用后回归自然大地。此材料之功效能使本产品在制成纸张后， 更好书写并 取得更好的手感。
其制法如下： 首先， 碳酸钙 （按质量比用量为 82%) 磨成所需的细度 (800目 〜1000目），加入天然色拉油（按质量比用量为 5%)和少许的聚乳酸 (按质量比用量 为 10%)和硬脂酸滑剂（按质量比用量为 3%)后， 放入密炼机中用 150度的高温加 以密练， 而后再入螺杵机制成颗粒备用。
二、 所述环保淀粉纸的制备方法：
步骤一、用制成颗粒之淀粉原料 (按质量比用量为 30%)加上制好的聚乳酸聚 合物原料 (按质量比用量为 20%)和碳酸钙原料 (按质量比用量为 50%)， 视产品所 需用一定比例放入 密练机中， 以 130度之高温， 经 90分钟密练制造成为造纸母 粒。
步骤二.将做好的母粒， 用三层共挤的双螺杵为基础之流延机械； 上、 下层 用纯制好的聚乳酸聚合物原料做覆盖膜层 (上下两层纯聚乳酸类似淋膜机做法， 淋膜在中层的造纸母粒上形成覆盖保护膜），中层用大量的造纸母粒 (上层聚乳酸 聚合物原料、 中层造纸母粒、 下层聚乳酸聚合物原料， 厚度比例为 1 : 8： 1)， 同时进入螺杵机， 以 180度的温度流延成膜状，然后经半冷却后再由数十支滚轮 做渐进式直向拉伸， 而后再进入大排式烘箱， 以 8(Γ110度的温度， 慢慢做横向 拉伸， 出来后再进入数十支滚轮做连绩式冷却和定型、压平， 成为圆卷式的环保 纸。 其厚度可根据要用的纸张用途， 再拉伸中做控制。 其密度、 重量也会因经过 这些机器的双轴拉伸后， 将和一般纸用的厚度及密度与克重不相上下。
步骤三.将做好的环保纸张再进入另一部机器 (静电消除机）， 此机器的用途， 是将把存在于纸张内之静电除去， 以便后续使用之印刷、 染色时不受静电影向， 至此环保纸张已制造完成。

Claims

权 利 要 求 书
1. 一种环保淀粉纸， 其特征在于： 包括上层聚乳酸聚合物原料、 中层造纸母粒 和下层聚乳酸聚合物原料的三层复合结构， 所述三层的厚度比例为 1 : 8： 1， 所 述造纸母粒包括如下质量百分比的组分：
淀粉原料： 30%;
聚乳酸聚合物原料： 20%;
碳酸钙原料： 50%。
2. 根据权利要求 1所述的环保淀粉纸， 其特征在于： 所述淀粉环保纸的制备方 法如下：
步骤一、将颗粒状的淀粉原料加上制好的聚乳酸聚合物原料和碳酸钙原料按 质量比为 30%: 20%： 50%的比例放入密炼机中， 以 130摄氏度的高温， 经 90分 钟密炼制造成为造纸母粒；
步骤二、将造纸母粒用三层共挤的方式进入流延机， 其中上、 下层用聚乳酸 聚合物原料做覆盖膜层， 中层用大量的造纸母粒同时进入流延机， 上层聚乳酸、 中层造纸母粒和下层聚乳酸的厚度比例为 1 : 8： 1； 再以 180度的温度流延成膜 状，然后经半冷却后再由数十支滚轮做渐进式直向拉伸，而后再进入大排式烘箱， 以 8(Γ110摄氏度的温度， 慢慢做横向拉伸， 出来后再进入数十支滚轮做连绩式 冷却和定型、 压平， 制成为圆卷式的环保纸；
步骤三、将做好的环保纸张再进入静电消除机，将存在于纸张内的静电除去， 得到所需的环保淀粉纸。
3. 根据权利要求 1所述的环保淀粉纸，其特征在于： 所述淀粉原料的制法如下: 将工业用淀粉加入甘油后， 经 120 〜160摄氏度高温蒸煮、 以加热方式催化， 再 冷却后， 再进入密炼机后， 在 110摄氏度的温度下密炼一小时后再制成颗粒， 经 冷却后得到颗粒状的淀粉原料； 其中工业用淀粉与甘油的配比按质量比为： 工业 用淀粉占 90%， 甘油占 10%。
4. 根据权利要求 1所述的环保淀粉纸， 其特征在于：
所述聚乳酸聚合物原料的制法如下：
( 1 ) 将聚乳酸与添加剂按质量比 1 ： 0. 05〜0. 3的比例加入反应槽混合后进 行改质， 其中添加剂的组分为： 甘油、 聚乳酸甘醇酸和甘草提取液， 其配比按质 量比为 7 : 2 : 1；
( 2 ) 将改质后的聚乳酸与填充料混合搅匀， 再经造粒机造出完全生物降解 的聚乳酸聚合物颗粒， 所述聚乳酸与填充料的配比按质量比为： 聚乳酸占 40〜80%， ±真充料占 20〜60%。
所述填充料的具体成分及配比按
直链淀粉 4(Γ55%;
碳酸钙、 云母粉或高岭土 4(Γ55%;
甘油 0· 75〜3%；
乙二醇 0. 75〜3%；
环氧大豆油 2〜8%；
山梨酸 广 4%;
尿素 0. 25〜1%
偶联剂 0. 0Γ0. 015%；
甲壳素 0. 01%;
枯草菌 0. 01%。
5. 根据权利要求 1所述的环保淀粉纸，其特征在于： 所述碳酸钙原料制法如下: 首先， 将碳酸钙磨成细度为 800目〜 1000目后， 加入天然色拉油、 聚乳酸、 和硬 脂酸滑剂后，放入密炼机中用 150摄氏度的高温加以密炼， 而后再入螺杵机制成 颗粒状的碳酸钙原料； 其中各原料的用量按质量比为： 碳酸钙用量为 82%， 天然 色拉油 5%， 聚乳酸 10%， 硬脂酸滑剂 3%。
PCT/CN2014/080776 2013-09-22 2014-06-25 淀粉环保纸及其制备方法 WO2015039479A1 (zh)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201310432760.5A CN103588995B (zh) 2013-09-22 2013-09-22 淀粉环保纸及其制备方法
CN201310432760.5 2013-09-22

Publications (1)

Publication Number Publication Date
WO2015039479A1 true WO2015039479A1 (zh) 2015-03-26

Family

ID=50079332

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2014/080776 WO2015039479A1 (zh) 2013-09-22 2014-06-25 淀粉环保纸及其制备方法

Country Status (2)

Country Link
CN (1) CN103588995B (zh)
WO (1) WO2015039479A1 (zh)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103588995B (zh) * 2013-09-22 2016-03-30 郑文彬 淀粉环保纸及其制备方法
CN107031153B (zh) * 2017-03-30 2019-08-13 齐庆德 一种可生物降解的多层共挤出材料的制备方法
CN110132787B (zh) * 2019-06-04 2021-11-05 山鹰华南纸业有限公司 一种造纸用石灰石粉的检测方法
CN110387773A (zh) * 2019-06-24 2019-10-29 东莞职业技术学院 一种新型环保纸张及其制备工艺

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100669502B1 (ko) * 2005-11-24 2007-01-16 도선제 생분해성 소재 및 이를 이용한 용기
CN1974203A (zh) * 2001-10-19 2007-06-06 宝洁公司 多层层压薄膜和减少环境污染的方法
CN101157792A (zh) * 2007-09-20 2008-04-09 浙江海正生物材料股份有限公司 一种可完全生物降解的聚乳酸复合材料及其制备方法
CN101312830A (zh) * 2005-11-23 2008-11-26 特里奥凡德国有限公司及两合公司 具有良好抗静电性质的pla膜
CN102120841A (zh) * 2010-12-27 2011-07-13 华东理工大学 一种可降解合成纸材料及其制备方法
US20110172326A1 (en) * 2010-01-08 2011-07-14 Paul Weismann Biodegradable polymer composition with calcium carbonate and methods and products using same
CN102796357A (zh) * 2011-05-23 2012-11-28 郑文彬 完全生物降解农膜的制备方法
WO2013017431A1 (de) * 2011-07-29 2013-02-07 Basf Se Biologisch abbaubare polyesterfolie
CN103588995A (zh) * 2013-09-22 2014-02-19 郑文彬 淀粉环保纸及其制备方法

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006160810A (ja) * 2004-12-03 2006-06-22 Toray Ind Inc ポリ乳酸改質用錠剤およびそれを用いたポリ乳酸繊維の製造方法
CN101914294B (zh) * 2010-08-26 2012-08-29 成都新柯力化工科技有限公司 一种仿纸生物降解树脂及制备方法
CN102444056B (zh) * 2010-10-12 2016-08-10 龙盟环保纸（集团）有限公司 五层可分解或降解的环保纸及其制造方法
CN103059527B (zh) * 2012-05-08 2015-05-13 纪永明 聚乳酸植物纤维复合可分解材料

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1974203A (zh) * 2001-10-19 2007-06-06 宝洁公司 多层层压薄膜和减少环境污染的方法
CN101312830A (zh) * 2005-11-23 2008-11-26 特里奥凡德国有限公司及两合公司 具有良好抗静电性质的pla膜
KR100669502B1 (ko) * 2005-11-24 2007-01-16 도선제 생분해성 소재 및 이를 이용한 용기
CN101157792A (zh) * 2007-09-20 2008-04-09 浙江海正生物材料股份有限公司 一种可完全生物降解的聚乳酸复合材料及其制备方法
US20110172326A1 (en) * 2010-01-08 2011-07-14 Paul Weismann Biodegradable polymer composition with calcium carbonate and methods and products using same
CN102120841A (zh) * 2010-12-27 2011-07-13 华东理工大学 一种可降解合成纸材料及其制备方法
CN102796357A (zh) * 2011-05-23 2012-11-28 郑文彬 完全生物降解农膜的制备方法
WO2013017431A1 (de) * 2011-07-29 2013-02-07 Basf Se Biologisch abbaubare polyesterfolie
CN103588995A (zh) * 2013-09-22 2014-02-19 郑文彬 淀粉环保纸及其制备方法

Also Published As

Publication number Publication date
CN103588995B (zh) 2016-03-30
CN103588995A (zh) 2014-02-19

Similar Documents

Publication Publication Date Title
de Azevedo et al. Possibilities for the application of agro-industrial wastes in cementitious materials: A brief review of the Brazilian perspective
Phonphuak et al. Types of waste, properties, and durability of pore-forming waste-based fired masonry bricks
KR101539224B1 (ko) 바이오메스 고형연료의 제조방법
KR101293642B1 (ko) 하수 슬러지를 이용한 고형연료 및 그의 제조방법
CN102675712B (zh) 生物降解塑料及其生产方法
WO2015039479A1 (zh) 淀粉环保纸及其制备方法
KR100735543B1 (ko) 음식물쓰레기와 폐합성수지를 이용한 고체연료의제조방법과 그 장치
CN105368520A (zh) 生物质成型颗粒燃料的制备方法
KR20110005104A (ko) 탄화 고체연료 및 그 제조방법
CN102898670B (zh) 一种可生物降解的环保纸及其制备方法
CN103332763A (zh) 柚子皮的新用途
CN106116508A (zh) 一种利用市政污泥为造孔剂生产防堵烧结透水砖的方法
CN105176620A (zh) 一种氧气助燃型生物质成型燃料的制备方法
CN105018172A (zh) 一种助燃型生物质成型燃料的制备方法
TW201641288A (zh) 聚乳酸環保紙及其製造方法
CN103205023A (zh) 一种竹粉/白炭黑复合补强淀粉基可降解塑料的制备方法
CN105695029A (zh) 生物质成型燃料及其制作方法
Kumar et al. Tea byproducts biorefinery for bioenergy recovery and value-added products development: A step towards environmental sustainability
CN107189473A (zh) 一种环保材料防水阻燃板材及其制备方法
CN101485894A (zh) 一种无灰型环保香及其制造方法
CN103819749A (zh) 一种可降解食品包装材料的制备方法
CN115160683A (zh) 一种环保可降解发泡鞋底及其制备方法
KR102369274B1 (ko) 패각 분말을 포함하는 조성물 및 그 제조방법
KR20170110061A (ko) 지방산을 함유한 커피분말의 지방산 제어 기술 및 이를 포함하는 바이오 소재
CN107698273A (zh) 一种利用疏浚淤泥和市政污泥制作烧结透水砖的方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 14845205

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 14845205

Country of ref document: EP

Kind code of ref document: A1