CN102011347A - Calcium silicate high-filling polymer modified paper - Google Patents
Calcium silicate high-filling polymer modified paper Download PDFInfo
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Abstract
The invention relates to calcium silicate high-filling polymer modified paper, which is compounded and formed by three layers of non-plant fiber calcium silicate substrates, wherein the first layer and the third layer are prepared from 2 to 6 percent of ethylene bis stearamide, 8 to 23 percent of high-density polyethylene, 3 to 9 percent of metallocene polyethylene, 0 to 1 percent of low-molecular polyethylene, 50 to 60 percent of activated calcium silicate, 10 to 25 percent of calcium silicate inorganic powder and 0 to 3 percent of addition agents, the first layer and the third layer accounts for 25 percent of the weight of the paper, the second layer is prepared from 50 to 60 percent of activated calcium silicate powder, 10 to 25 percent of calcium silicate, 2 to 9 percent of styrene-butadiene block copolymer, 7 to 21 percent of high-intensity polyethylene materials, 4 to 8 percent of linear low-intensity polyethylene and 0 to 3 percent of addition agents, and the second layer accounts for 50 percent of the weight of the paper. The modified paper has the same appearance, whiteness, sizing degree, opacity, strength, toughness and rigidity as plant fiber paper and has simple production processes, no bacteria and poison; and because the product is used for packing paper and can replace the traditional plastic packing paper, a great amount of petroleum can be saved.
Description
Technical field
The present invention relates to a kind of paper, particularly relate to calcium silicates (CaSiO
3XH
2O) high filled polymer is material modified, can be used for cultural paper, industrial paper, package paper, building decoration with paper and the special paper of using.
Background technology
It all is to adopt timber, reed, straw or bagasse to be main raw material with paper and the special paper that uses that present China is used for industry, culture, packing, building decoration.Along with improving constantly of rapid economy development and people's educational level, the scope of application of paper can be more and more wider, and use amount also can be increasing, and the performance and the quality of paper are also had higher requirement.The raw material that is used for papermaking at present mainly is a natural plant fibre, mainly contain the vegetable material of timber and reed and other high fibers, these materials are all deficient day by day, one ton of paper of every production need be with 2.6 tons of wood chips, quite what felling growth period was big tree 20 strains in 20 years, use about 200 tons of fresh water simultaneously, discharge a large amount of waste water simultaneously, waste residue, COD and multiple toxic harmful exhaust gas, the emission of some little factory is comprising dioxin, chloroform and a large amount of organic chlorides, dioxin, chloroform is a carcinogen, the structure that organic chloride can damage the ozone layer, damage the function that it filters solar ultraviolet, these have all caused great injury to the environment and the mankind.This phenomenon has caused the great attention of national government, and 2007-2008 just has a batch of traditional papermaking enterprises because the seriously polluted and transformation that is closed or stops production.China is populous, forest and water resource are all very limited, afforestation rate only is 16%, be lower than 28% of world average level, water consumption has only 15% of world average level per capita, because the critical shortage of the water resource and the forest reserves does not satisfy the demand of paper industry to raw material, therefore annual China all wants a large amount of paper of import, cardboard, paper pulp and waste paper, accounts for 66% of China's cardboard consumption figure.Contain a large amount of rubbish in the imported waste paper, the pollution that these are serious environment.Problem of environmental pollution, scarcity of resources problem, a large amount of imports of papermaking resource etc. are all multifactorly to become paper industry and the very strong driving force and the urgent task of new paper making raw material and technology are sought in material industry.
The subject matter that the string papermaking that people continued to use more than 2000 year exists is: (1) loss a large amount of forest reserves and water resources; (2) a large amount of organic chloride and the toxic gases of discharging, contaminated environment is destroyed the ecological balance, has brought serious harm for the people's living environment; (3) water absorption rate height, non-watertight protection against the tide has limited the scope of application; (4) be used to the paper packed non-watertight non-moistureproof, price is high; (5) complex process, power consumption is high.
Summary of the invention
The objective of the invention is; be to overcome the deficiencies in the prior art, provide a kind of non-plant fibre manufacturing the protection environment, save resource, nontoxic, waterproof and dampproof, mildew-resistant is fungi-proofing, anti-folding, mothproof, cost is low, printing performance well and the calcium silicates paper that can degrade fast.
The technical scheme that adopts is:
The high filled polymer modified paper of a kind of calcium silicates, its technical essential are to constitute by three layers of non-plant fibre calcium silicates matrix is compound.Ground floor is to be mixed with materials such as calcium carbonate, high density polyethylene (HDPE), metallocene PE, ethylene group bis-stearamides EBS, low molecular polyethylenes by activated silicic acid calcium with the 3rd layer, have good ink absorption, odor-absorbing, metallocene PE has good flexibility, toughness and elasticity.The second layer is mixed with the high density polyethylene (HDPE) raw material by activated silicic acid calcium, styrene-butadiene block copolymer (SBS), linear low density polyethylene.
Above-mentioned activated silicic acid calcium granularity is the 1250-2500 order.
Calcium silicates activation: be to adopt silane coupler or aluminate coupling agent, processing method: earlier the pH value is stirred preheating and drying under 110-130 ℃ of condition for the calcium silicates between the 7-9 in high-speed mixer, remove the aluminate coupling agent and the 0.3-0.6% silane coupler that drop into 0.6-1.0% behind the moisture in batches or once, stir about (detection activation grade) back discharging in 15 minutes, rapid cooling promptly is prepared into the activated silicic acid calcium packing material after the activation.
Above-mentioned each layer interpolation has the auxiliary agent of difference in functionality according to user's needs, and its total amount is 0-3%.
Three layers of concrete batching of non-plant fibre calcium silicates paper substrate body are:
Ground floor and the 3rd layer of non-plant fibre calcium silicates paper substrate body are to be prepared into by ethylene group bis-stearamides EBS, high density polyethylene (HDPE), metallocene PE, low molecular polyethylene and activated silicic acid calcium, and its percentage by weight is: ethylene group bis-stearamides (EBS) 2-6%, high density polyethylene (HDPE) 8-23%, metallocene PE 3-9%, low molecular polyethylene 0-1%, activated silicic acid calcium 50-60% and calcium carbonate inorganic particle 10-25%, auxiliary agent 0-3%.
Ground floor and the 3rd layer of non-plant fibre paper substrate body account for 25% of paper weight respectively.
Ethylene group bis-stearamides EBS has the polarity amide group, can be good at and the high density polyethylene (HDPE) combination, improve poly processing characteristics, improve the absorbency of paper, therefore, ground floor and the 3rd layer of adding EBS at paper makes the high filled polymer modified paper of a kind of calcium silicates of the present invention have good writing quality and printing performance.The metallocene PE flexibility is good, therefore add the toughness that metallocene PE has improved the high filled polymer modified paper of a kind of calcium silicates of the present invention the ground floor of paper and the 3rd layer, trace is folded in folding, calcium silicates, calcium carbonate join and can make paper produce a large amount of micropores in the paper, increase absorbency and the printing and the paper sense of material, therefore can be used as cultural paper, industrial paper, package paper, decoration with paper, advertisement with paper and specially use with paper.
Second layer non-plant fibre calcium silicates paper substrate body is to be become with the high density polyethylene (HDPE) raw material preparing by activated silicic acid calcium, styrene-butadiene block copolymer (SBS), linear low density polyethylene, its batching is 50-60% for activated silicic acid calcium powder body by weight percentage, calcium carbonate is 10-25%, styrene-butadiene block copolymer is that 2-9%, high-density polyethylene material are 7-21%, linear low density polyethylene (LLDPE) is 4-8%, auxiliary agent and modifier are 0-3%, and the second layer accounts for 50% of paper gross weight.
Above-mentioned activated silicic acid calcium and calcium carbonate powder, particle diameter are 1250-2500 order (5-10 μ m).
Above-mentioned auxiliary agent can select for use flexibilizer, lubricant, coupling agent, stuffing surface modification agent, antioxidant comprising: its molecular formula of aluminate coupling agent is (C3H7O) XAL (OCOR1) m (OCOR2) n (OAB) y, its molecular formula of silane coupler is ClCH2CH2CH2Si (OC2H5) 3, titanate coupling agent, antioxidant four (β-(3, the 5-di-tert-butyl-hydroxy phenyl) pentaerythritol ester (1010) propionic acid), its molecular formula is C73H108O12, lubricant is a low molecular polyethylene, aliphatic acid etc.
The preparation method of the high filled polymer modified paper of a kind of calcium silicates comprises the steps:
1, in ground floor and three-ply paper total weight percent: get high density polyethylene (HDPE) 8-23%, the Paris white of metallocene PE 3-9%, ethylene group bis-stearamides (EBS) 2-6%, auxiliary agent 0-3% and low molecular polyethylene 0-1%, 50-60%, calcium silicates, 10-25% is put into mixer and is carried out batch mixing, batch mixing 10-15 minute, the batch mixer rotating speed was 80 rev/mins;
2, the raw material that mixes is dropped into double screw extruder, carry out extruding pelletization, extruding pelletization becomes modified master after making nonpolar vistanex and the ethylene group bis-stearamides EBS that has multiple functional group carrying out graft modification, this masterbatch has certain polarity, therefore improved the absorbency of paper, made material that printing performance preferably arranged.
3, the pellet of making is the raw material of ground floor paper and three-ply paper, puts into respectively in first extruder and the 3rd extruder.
4, take by weighing the high density polyethylene (HDPE) of 7-21%, the linear low density polyethylene of 4-8% (LLDPE), activated silicic acid calcium 50-60% and calcium carbonate powder 10-25%, the styrene-butadiene block copolymer of 2-9% (SBS), the auxiliary agent of 1-3% and modifier carry out the blend granulation, as second layer raw material, drop into second extruder.
5, adopt first extruder, second extruder, the 3rd extruder to carry out three layers of composite co-extruding and go out technology, extrude the back and be shaped to sheet material by trapezoidal head, carry out moulding through the substrate forming device of forming by multiple roll again, shaped device is furnished with phoenix cutter and roller constant temperature cooling system, automatic lifting, roll spacing are set automatically according to product requirement and are regulated.
6, adopt the multiple roll stretching device, the multiple spot stretching technique stretches, and multiple spot stretches can guarantee that the product lateral shrinkage is low, and longitudinal stretching can require to select draw ratio according to properties of product, stretching device is made up of the heating roller by more than 20, adopts the transmission of twin-stage variable-frequency motor.
Characteristics such as 7, stretching is after after the HEAT SETTING device handles, have the product size good stability, and surface smoothness and printing performance are good.Heat setting temperature is controlled at 100-120 ℃.
8, the high filled polymer modification of the calcium silicates paper after the stretching cools off through two rollers that are connected with cold water, and chilling temperature is controlled at 5-10 ℃.Carry out corona treatment through corona treatment again after the cooling, can improve the surface tension of goods after the corona treatment and improve printing performance.
9, after last paper draws, curls by hauling machine, promptly.
The applicant adopts advanced metallocene PE macromolecular material and macromolecular material and the ethylene group bis-stearamides EBS that has a large amount of active groups, styrene-butadiene block copolymer (SBS), extrude by three-layer co-extruded trapezoidal head with heat insulating function, calendering, the processes moulding of embarking on journey such as curtain coating, adopt stretching device to stretch, embossing is handled, cooling, corona treatment, vanguard technology and technology such as rolling produce economy, environmental protection, nontoxic, good toughness, folding resistance is good, opaque, resistance to chemical attack, water-fast protection against the tide, the environmental protection paper that TENSILE STRENGTH and tearing strength are good with recycle.Can partly replace the string paper that the mankind continued to use more than 2000 year.
Compared with prior art, the invention has the beneficial effects as follows: the composition of raw materials of the high filled polymer modified paper of a kind of calcium silicates does not adopt traditional paper making raw material---the natural plant fibre class, as wood pulp, straw pulp and secondary stock etc., but be matrix with high molecular polymers such as high density polyethylene (HDPE) (HDPE), metallocene PE (mPE), styrene-butadiene block copolymer (SBS) and ethylene group bis-stearamides EBS, fill a large amount of activated silicic acid calcium materials, add a spot of activated calcium carbonate again and the novel environment friendly paper made.Product has following characteristics:
1, have the outward appearance the same with the string paper, performance indications such as whiteness, degree of sizing, absorbency, opaque, intensity, toughness and rigidity, these performance indications partly are better than traditional fibre paper.It also has the characteristics that are different from traditional fibre paper, and resistance to chemical attack, water-fast protection against the tide are mothproof, do not produce distortion, and DIMENSIONAL STABILITY is good etc.
2, production technology is simple, and energy-saving and water-saving reduces organic chloride and discharge of harmful gases, and no discharging wastes does not contain string, has protected the forest reserves, preserves the ecological environment.
3, aseptic nontoxic, have good biologically inert, can be widely used in food, drug packaging and building decoration paper, enlarged the scope of application of paper.
4, save petroleum resources, because product is used for package paper, therefore alternative present plastic package material can save a large amount of oil.
Principle of the present invention is: any macromolecular material all can not have the desired all properties characteristics of product simultaneously concurrently, only take special structure design and unique technical recipe design, form the intersection sandwich, make full use of the characteristics that each layer film has, make the material of each layer bring into play its function separately, and the different advantages that various material possessed are concentrated in together, take complementary method just can reach utility function.The present invention is on the basis of the multiple macromolecular material character of choose reasonable, technical requirement according to the high filled polymer modification of a kind of calcium silicates paper, according to the close compatibility principle of macromolecular material and the structure-activity relationship of macromolecular material, high molecular polymer is carried out modification and grafting, research macromolecular structure and performance, increase carboxyl on the macromolecular chain, carbonyl and hydroxyl isoreactivity group, make the surface of paper have certain compatibility, the processing technology of research paper, improve the structure of paper surface by processing technology, make paper surface form a large amount of spaces, improve the absorbency of paper, improve printing performance and writing quality, design and synthesize the non-toxic high molecular material modifier and the nucleator that are fit to the various functions of this project, improve the compatibility of activated silicic acid calcium powder body and polyolefin macromolecular material, improve strength of paper and folding resistance, improve the water proofing property and the pliability of paper, improve the writing property and the printing of paper.Prepare and have the combination property that the string paper is had.
Description of drawings
Fig. 1-Fig. 4 is three-layer co-extruded calcium silicates paper structure figure, and its ground floor and the 3rd layer are for improving writing quality and printing ergosphere, and the intermediate layer is for gaining in strength and the deflection layer.Fig. 1 is 80% three-layer co-extruded calcium silicates paper structure figure for activated silicic acid calcium and calcium carbonate content, Fig. 2 is that activated silicic acid calcium and calcium carbonate content are 72% three-layer co-extruded calcium silicates paper structure figure, Fig. 3 is that activated silicic acid calcium and calcium carbonate content are 65% three-layer co-extruded calcium silicates paper structure figure, and Fig. 4 is that activated silicic acid calcium and calcium carbonate content are 60% three-layer co-extruded calcium silicates paper structure figure.Label 1 is a ground floor, and 2 is the intermediate layer, and 3 is the 3rd layer.
The specific embodiment
Embodiment one
The high filled polymer modified paper of a kind of calcium silicates, by three layers of non-plant fibre calcium silicates, calcium carbonate and macromolecular material is matrix, constitute through three extruder coextru-laminations, first and the 3rd layer of non-plant fibre calcium silicates paper substrate body raw material is by ethylene group stearic bicine diester ammonia 2%, high density polyethylene (HDPE) 8%, metallocene PE 9%, activated silicic acid calcium 58%, calcium carbonate 21%, low molecular polyethylene 1% and antioxidant (1010), its molecular formula is C73H108O12, and 1% forms; Second layer paper material is made up of activated silicic acid calcium 60%, calcium carbonate 23%, stupid ethene-butadiene block copolymer 5%, high density polyethylene (HDPE) 8%, linear low density polyethylene 3% and antioxidant 1%; Above-mentioned ground floor and the 3rd layer account for 25% of paper weight respectively.
Embodiment two
The high filled polymer modified paper of a kind of calcium silicates, by three layers of non-plant fibre calcium silicates, calcium carbonate and macromolecular material is matrix, constitute through three extruder coextru-laminations, first and the 3rd layer of non-plant fibre calcium silicates paper substrate body raw material is made up of ethylene group stearic bicine diester ammonia 5%, high density polyethylene (HDPE) 18%, metallocene PE 3%, activated silicic acid calcium 52%, calcium carbonate 19%, low molecular polyethylene 1% and antioxidant 2%; Second layer paper material is C73H108O12 by activated silicic acid calcium 58.5%, calcium carbonate 16%, stupid ethene-butadiene block copolymer 2%, high density polyethylene (HDPE) 15%, linear low density polyethylene 8% and antioxidant 0.5% (1010) its molecular formula, forms;
Embodiment three
The high filled polymer modified paper of a kind of calcium silicates, by three layers of non-plant fibre calcium silicates, calcium carbonate and macromolecular material is matrix, constitute through three extruder coextru-laminations, first and the 3rd layer of non-plant fibre calcium silicates paper substrate body raw material is made up of ethylene group stearic bicine diester ammonia 6%, high density polyethylene (HDPE) 20%, metallocene PE 5%, activated silicic acid calcium 51%, calcium carbonate 14% low molecular polyethylene 1% and antioxidant 3%; Second layer paper material is made up of activated silicic acid calcium 50%, calcium carbonate 16%, stupid ethene-butadiene block copolymer 9%, high density polyethylene (HDPE) 18%, linear low density polyethylene 6% and antioxidant 1%;
Embodiment four
The preparation method of the high filled polymer modified paper of a kind of calcium silicates comprises following processing step:
1, with high density polyethylene (HDPE) 40%, metallocene PE 43%, ethylene group bis-stearamides EBS15%, 1% antioxidant four (β-(3, the 5-di-tert-butyl-hydroxy phenyl) pentaerythritol ester (1010) propionic acid), its molecular formula is C73H108O12, and raw materials such as 1% low molecular polyethylene are put into high-speed mixer and carried out batch mixing.
2, the raw material that mixes is dropped into double screw extruder, extruding pelletization becomes modified master after making nonpolar vistanex and the ethylene group bis-stearamides EBS that has multiple functional group carrying out graft modification, this masterbatch has certain polarity, therefore improved the absorbency of paper, made material that printing performance preferably arranged.
3, take by weighing 40% modified master, add activated silicic acid calcium 40% and calcium carbonate powder 20%, mix the raw material of back, drop into first extruder and the 3rd extruder as ground floor and the 3rd layer.
4, take by weighing 21% high density polyethylene (HDPE), 10% linear low density polyethylene (LLDPE), add activated silicic acid calcium 45% and calcium carbonate powder 15%, the styrene-butadiene block copolymer (SBS) of adding 7%, 2% processing aid and modifier carry out the blend granulation, as second layer raw material, drop into second extruder.
Claims (2)
1. high filled polymer modified paper of calcium silicates is characterized in that being constituting by three layers of non-plant fibre calcium silicates matrix is compound; Ground floor is to be mixed with calcium carbonate, high density polyethylene (HDPE), metallocene PE, ethylene group bis-stearamides, low molecular polyethylene by activated silicic acid calcium with the 3rd layer, and the second layer is mixed with by activated silicic acid calcium, styrene-butadiene block copolymer and high density polyethylene (HDPE) raw material;
Above-mentioned activated silicic acid calcium grain and calcium carbonate degree are the 1250-2500 order;
Calcium silicates and calcium carbonate activation: be to adopt silane coupler or aluminate coupling agent, processing method: earlier the pH value is stirred preheating and drying under 110-130 ℃ of condition for the calcium silicates between the 7-9 in high-speed mixer, remove the aluminate coupling agent and the 0.3-0.6% silane coupler that drop into 0.6-1.0% behind the moisture in batches or once, stir about (detection activation grade) back discharging in 15 minutes, rapid cooling promptly is prepared into the activated silicic acid calcium packing material after the activation;
Above-mentioned each layer interpolation has the auxiliary agent of difference in functionality according to user's needs, and its total amount is 0-3%;
Three layers of concrete batching of non-plant fibre calcium silicates paper substrate body are:
Ground floor and the 3rd layer of non-plant fibre calcium silicates paper substrate body are to be prepared into by ethylene group bis-stearamides, high density polyethylene (HDPE), metallocene PE, low molecular polyethylene and activated silicic acid calcium body, and its percentage by weight is: ethylene group bis-stearamides 2-6%, high density polyethylene (HDPE) 823%, metallocene PE 3-9%, low molecular polyethylene 0-1%, activated silicic acid calcium 50-60% and calcium carbonate inorganic particle 10-25%, auxiliary agent 0-3%;
Ground floor and the 3rd layer of non-plant fibre paper matrix account for 25% of paper weight respectively;
Second layer non-plant fibre calcium silicates paper substrate body is to be become by activated silicic acid calcium, styrene-butadiene block copolymer, high density polyethylene (HDPE) and auxiliary agent raw material preparing, its batching is 50-60% for activated silicic acid calcium powder body by weight percentage, calcium carbonate is 10-25%, styrene-butadiene block copolymer 2-9%, high-density polyethylene material are 7-21%, linear low density polyethylene 4-8%, auxiliary agent is 0-3%, and the second layer accounts for 50% of paper gross weight;
Above-mentioned activated silicic acid calcium and calcium carbonate powder, particle diameter are the 1250-2500 order;
Above-mentioned auxiliary agent can be selected flexibilizer, lubricant, coupling agent, stuffing surface modification agent or antioxidant for use, comprising: its molecular formula of aluminate coupling agent is (C3H7O) XAL (OCOR1) m (OCOR2) n (OAB) y, its molecular formula of silane coupler is ClCH2CH2CH2Si (OC2H5) 3, antioxidant four (β-(3, the 5-di-tert-butyl-hydroxy phenyl) pentaerythritol ester (1010) propionic acid), its molecular formula is C73H108O12, and lubricant is a low-molecular polypropylene, fatty acid.
2. the preparation method of the high filled polymer modified paper of a kind of calcium silicates according to claim 1 is characterized in that comprising the steps:
1., in ground floor and three-ply paper total weight percent: get high density polyethylene (HDPE) 8-23%, metallocene PE 3-9%, ethylene group bis-stearamides 2-6%, auxiliary agent 0-3% and low molecular polyethylene 0-1%, activated silicic acid calcium 50-60% and calcium carbonate powder 10-25% put into mixer and carry out batch mixing, batch mixing 10-15 minute, the batch mixer rotating speed was 80 rev/mins;
2., the raw material that mixes is dropped into double screw extruder, extruding pelletization becomes modified master after making nonpolar vistanex and the ethylene group bis-stearamides that has multiple functional group being carried out graft modification;
Take by weighing 25% raw material of gross weight, put into respectively in first extruder and the 3rd extruder as ground floor paper and three-ply paper 3., respectively;
4., take by weighing the high density polyethylene (HDPE) of 7-21%, the linear low density polyethylene of 4-8%, activated silicic acid calcium 50-60% and calcium carbonate powder 10-25%, the styrene-butadiene block copolymer of 2-9%, the processing aid of 1-3% carries out the blend granulation, as second layer raw material, drop into second extruder;
5., adopt first extruder, second extruder, the 3rd extruder to carry out three layers of composite co-extruding and go out technology, extrude the back and be shaped to sheet material by trapezoidal head, carry out moulding through the substrate forming device of forming by multiple roll again, stretch through multiple spot, HEAT SETTING is handled again, cooling, after the corona treatment, promptly.
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| CN103333369A (en) * | 2013-05-17 | 2013-10-02 | 大唐国际发电股份有限公司高铝煤炭资源开发利用研发中心 | Preparation method of calcium silicate master batch |
| CN103333369B (en) * | 2013-05-17 | 2015-05-20 | 大唐国际发电股份有限公司高铝煤炭资源开发利用研发中心 | Preparation method of calcium silicate master batch |
| CN104194404A (en) * | 2014-08-20 | 2014-12-10 | 大唐国际发电股份有限公司高铝煤炭资源开发利用研发中心 | Active calcium silicate, and preparation method and application thereof |
| CN113290965A (en) * | 2021-04-26 | 2021-08-24 | 特耐王汇立塑料制品无锡有限公司 | High-filling easy-printing logistics packaging material and preparation method thereof |
| JP7113579B1 (en) | 2022-05-24 | 2022-08-05 | 株式会社Tbm | LAMINATED SHEET AND FOOD PACKAGING CONTAINER |
| WO2023228549A1 (en) * | 2022-05-24 | 2023-11-30 | 株式会社Tbm | Laminate sheet and food packaging container |
| JP2023172715A (en) * | 2022-05-24 | 2023-12-06 | 株式会社Tbm | Laminate sheet, and food packaging container |
| JP7248359B1 (en) * | 2022-12-28 | 2023-03-29 | 株式会社Tbm | LAMINATED SHEET AND FOOD PACKAGING CONTAINER |
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