Summary of the invention
The objective of the invention is; Be to overcome the deficiency of 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 be made up of the bluk recombination of three layers of non-plant fibre calcium silicates paper substrate.Ground floor and the 3rd layer are to be prepared into by material mixing such as activated silicic acid calcium and calcium carbonate, high density polyethylene (HDPE), metallocene PE, ethylene group bis-stearamides EBS, low molecular polyethylenes; 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), LLDPE.
Above-mentioned activated silicic acid calcium and calcium carbonate granularity are 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, activated silicic acid calcium, calcium carbonate inorganic particle and auxiliary agent, 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 calcium silicates paper substrate body account for 25% of paper weight respectively.
Ethylene group bis-stearamides EBS has the polarity amide group; Can be good at combining with high density polyethylene (HDPE); Improve poly processing characteristics; Improve the absorbency of paper, therefore, make the high filled polymer modified paper of a kind of calcium silicates of the present invention have good writing quality and printing performance at ground floor and the 3rd layer of adding EBS of paper.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, so can be used as cultural paper, industrial paper, package paper, decoration and use with paper with paper and special with paper, advertisement.
Second layer non-plant fibre calcium silicates paper substrate body is to be become with the auxiliary agent raw material preparing by activated silicic acid calcium, styrene-butadiene block copolymer (SBS), LLDPE, high density polyethylene (HDPE), calcium carbonate; 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%; LLDPE (LLDPE) is 4-8%, and 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 1250-2500 order (5-10 μ m).
Above-mentioned auxiliary agent can select for use flexibilizer, lubricant, coupling agent, stuffing surface modification agent, anti-oxidant comprising: its molecular formula of aluminate coupling agent is (C
3H
7O) XAL (OCOR1) m (OCOR2) n (OAB) y, its molecular formula of silane coupler is C
1CH
2CH
2CH
2Si (OC
2H
5) 3, titanate coupling agent, antioxidant four (β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol ester (1010), its molecular formula is C
73H
108O
12, 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, has therefore improved the absorbency of paper, makes 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 721% high density polyethylene (HDPE); The LLDPE 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 through 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, and roll spacing is set automatically according to product requirement and is 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.
7, stretching is after after the HEAT SETTING apparatus processes, have the product size good stability, characteristics such as 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 sided corona treatment through corona treatment again after the cooling, can improve the surface tension of goods after the sided corona treatment and improve printing performance.
9, after last paper draws, curls through hauling machine, promptly get.
The applicant adopts advanced metallocene PE macromolecular material and macromolecular material and ethylene group bis-stearamides EBS, the styrene-butadiene block copolymer (SBS) that has a large amount of active groups; The processes moulding of embarking on journey such as the three-layer co-extruded trapezoidal head through having heat insulating function is extruded, calendering, curtain coating, adopt vanguard technology and technology such as stretching device stretches, embossing processing, cooling, sided corona treatment, rolling, produce that economy, environmental protection, nontoxic, good toughness, folding resistance are good, opaque, resistance to chemical attack, water-fast protection against the tide, TENSILE STRENGTH and the good environmental protection paper of tearing strength 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; Like 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 processed.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 and use 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, according to the technical requirement of 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, and research macromolecular structure and performance increase carboxyl, carbonyl and hydroxyl isoreactivity group on the macromolecular chain; Make the surface of paper have certain compatibility, the processing technology of research paper is through the structure of processing technology raising paper surface; 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.
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 that its molecular formula is C73H108O12 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 anti-oxidant (1010), 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%, LLDPE 3% and anti-oxidant 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 anti-oxidant 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%, LLDPE 8% and anti-oxidant 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 anti-oxidant 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%, LLDPE 6% and anti-oxidant 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) propionic acid) pentaerythritol ester (1010); 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% LLDPE (LLDPE); Add activated silicic acid calcium 45% and calcium carbonate powder 15%, add 7% styrene-butadiene block copolymer (SBS), 2% processing aid and modifier carry out the blend granulation; As second layer raw material, drop into second extruder.