CN101871182A - Thermoplasticity environmentally-friendly stone paper and preparation method - Google Patents
Thermoplasticity environmentally-friendly stone paper and preparation method Download PDFInfo
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Abstract
The invention discloses a thermoplasticity environmentally-friendly stone paper and a preparation method. The thermoplasticity environmentally-friendly stone paper comprises the following components in parts by weight: 80-90 parts of inorganic mineral powder, 3-5 parts of surface active ingredient, 2-3 parts of polymer monomer, 0.01-0.05 part of initiator and 5-15 parts of lubrication accessory ingredient, wherein the inorganic mineral powder is at least one of various inorganic mineral powders, such as wollastonite of which the grain diameter is 5-10 mu m, bentonite and the like; the surface active ingredient comprises at least one of anion surface active ingredient comprising inorganic acid ester; and the polymer monomer is one of methyl methacrylate, methyl acrylate, butyl acrylate and styrene. The thermoplasticity environmentally-friendly stone paper contains 90% of inorganic mineral powder, has favoarble thermoplasticity processing performance and can use the thermoplasticity processing equipment to carry out quick blow molding or calendaring and drawing shaping; and paper has obvious vertical and horizontal orientation, good deflection and strong rigidity, and appearance texture more approaches the traditional paper. The thermoplasticity environmentally-friendly stone paper is a novel environmentally-friendly paper.
Description
Technical field
The present invention relates to a kind of be the main body composition with the inorganic particle, be commonly called as the environment-friendly paper and the corresponding preparation method of " stone paper ", more specifically say it is a kind of environmentally-friendly stone paper and preparation method with thermoplastic processability.
Background technology
Because of containing " stone paper " that the inorganic particle composition is called, be a kind of new type of paper that comes from synthetic paper, adopt based on macromolecule resin, be auxiliary material with calcium carbonate, utilize the calendering process equipment to prepare synthetic paper.Because the synthetic paper raw material is based on resin, the content of calcium carbonate powder is less than 40%, and therefore not only cost is higher, and depends on oil, and its application and development are influenced by oil always.In recent years, this type of technology is obtaining the new breakthrough progress aspect the technology means, the content of calcium carbonate powder is improved constantly, and production cost significantly reduces, and progressively having formed with inorganic powder material calcium carbonate is the stone paper of main component.Because excellent properties such as stone paper waterproof, antifog, grease proofing, insect protected, high strength can be widely used in writing paper, printing paper, wrapping paper, atlas, notebook, paper bag, many fields such as cutlery box.In addition, because stone paper mainly is made up of inorganic powder material such as calcium carbonate and a spot of resin, add and adopt blowing or calendering man-hour, manufacturing process is not fallen trees fully, do not make water, not waste discharge, waste gas, need not add bleaching agent, strong acid, highly basic, can not pollute environment, cost also only is 1/2 of traditional paper pulp papermaking, so it not only helps and improve environmental problem, and meets the environmental protection and energy saving requirement, be fit to demands for development such as industrial structure transition, new forms of energy, new material, low-carbon economy, environmental protection, have the great development potentiality and the market demand.
Chinese patent publication number CN1378909A has proposed a kind of environmental protection paper, and the inorganic mineral powder of 56-80% and polyvinyl resin and the auxiliary agent of 43-18% are passed through extruder grain, and at O pattern interruption-forming tube film, blowing makes biaxial tension obtain environmental protection paper.This patent utilization coupling agent and dispersant have only been done surface treatment to the inorganic mineral powder, and mineral powder content can't further improve, and process equipment and technology have been done strict requirement, belong to special equipment, and the suitability for industrialized production investment is bigger.
Chinese patent publication number CN1651649 discloses a kind of preparation method of environment-friendly novel synthetic paper.This synthetic paper is that 30-50% polyolefin blends, 40-60% natural inorganic mineral powder and 5-10% auxiliary agent are made master batch, again master batch and polyolefin blend and auxiliary agent are mixed, through double screw extruder, the extrusion of T pattern head, two roller stretch forming equipment, make the environmental protection paper of different-thickness.Inorganic mineral powder mainly relies on coupling to fill in this environmental protection paper, and powder content needs to rely on a large amount of resins just can extrude, roll, stretch as backing material less than 60% in the processing.
The Chinese patent publication number CN1381347A provide a kind of high-strnegth low-cost synthetic polymer paper.This invention synthetic paper directly passes through the mixing processing of mixing roll in order to reduce cost with 100 parts of polymer, 2.5-250 part powder, 3-40 part modification agent and all kinds of lubricating auxiliary agent.Owing to used a large amount of inside and outside lubricant agents, only as a kind of filler, its content is the highest about 60%, so cost is still higher relatively in system for powder.
By above-mentioned patent analyses, inorganic particles such as calcium carbonate are processed into thin paper open, generally select for use granularity at micron-sized powder.Because the surface energy height of micron-sized powder particle is in the thermodynamic instability state, very easily reunite, the surface hydrophilic oleophobic, polarity is very high, is difficult to disperse in organic media, and is poor with the adhesion of resin binder, easily forms boundary defect.All adopt coupling technology that powder is carried out simple surfaces in the above-mentioned patent and handle, inorganic particle content about 60%, is up to 80% usually in the stone paper, and powder is to exist with the form of filling, and needs to rely on a large amount of resins as backing material, and cost is higher.And processing characteristics is relatively poor, and high to the equipment requirement in the production, the production investment is huge, can not stretch fast, and production capacity is low, and the Substance height can not draw thin, has hindered its large-scale production and application.In addition, can't carry out uniformly, the paper poor rigidity, lack the paper sense in length and breadth to stretch orientation.
And to prepare the environmentally-friendly stone paper of real meaning, must guarantee inorganic particle content such as calcium carbonate more than 80%, and have good processing and forming.Therefore, inorganic particle has only been done coupling and has been filled the development that can not satisfy stone paper far away.In order to overcome above deficiency, must carry out complete plastics processing to inorganic particles such as calcium carbonate, improve the content of inorganic particle in stone paper, make simultaneously himself to can be good at processing and forming.
Summary of the invention
At above-mentioned situation, the present invention at first will provide a kind of environmentally-friendly stone paper that can have good thermoplastic processability, and on this basis, the present invention further also will provide a kind of preparation method of this thermoplasticity environmentally-friendly stone paper.
Thermoplasticity environmentally-friendly stone paper of the present invention, it contains inorganic mineral powder and organic principle in forming equally, and the weight portion composition form of each composition is:
80～90 parts of inorganic mineral powders,
3～5 parts of surface active ingredients,
2～3 parts of polymer monomers,
0.01～0.05 part of initator,
5～15 parts of lubricating auxiliary agent,
Wherein, said inorganic mineral powder is at least a in the wollastonite, bentonite, calcite in powder, kaolin, titanium dioxide, diatomite, talcum powder, precipitated calcium carbonate of particle diameter 5～10 μ m (being equivalent to 1250 orders～2500).
Said surface active ingredient is to comprise at least a in the anion surfactant of inorganic acid ester, as zirconate, titanate esters, aluminic acid ester, amino polybasic alcohol ester, phosphate, stearic acid and derivative thereof etc.Wherein, said zirconate can be the positive tetrapropyl zirconate of existing report/use; Said titanate esters can be selected as isopropoxy titanate esters, fluoroacetic acid chelate group titanate esters, ethylene glycol chelate group titanate esters, pyrophosphoric acid type monoalkoxytitanates etc.; Said aluminic acid ester can be aluminium isopropoxide acid esters etc.; Said amino polybasic alcohol ester can be selected as stearic acid amido sorbitol ester, laurate amido sorbitol ester, palmitic acid amido sorbitol ester etc.; Said phosphate can be selected in phosphatase 11 2 alcohol esters, phosphatase 11 4 alcohol esters, phosphatase 11 6 alcohol esters, phosphatase 11 8 alcohol esters etc.; Said stearic acid and derivative thereof can be stearic acid, and as multi-form derivatives such as zinc stearate, calcium stearate, odium stearate or stearic amides.Wherein preferred surface active ingredient is a phosphate.Owing in these surface active ingredient structures the group of hydrophilic is arranged all, thereby can reduce the surface energy of inorganic particle composition, avoid reuniting, increase the split activity, be beneficial to the processing of postorder.As the hydrophilic radical in zirconate, titanate esters, aluminic acid ester, amino polybasic alcohol ester, the phosphate equimolecular, can with the free proton generation chemical reaction of inorganic powder surface, its oil factor and water absorption rate are reduced, active increasing.The suitable appropriateness of the consumption of surface active ingredient, very few activation effect is not good, excessively then can easily reunite again because of reversing.
Said polymer monomer is a kind of in methyl methacrylate, methyl acrylate, butyl acrylate, the styrene, and by initiated polymerization, these polymer monomers can form has thermoplastic polymer.According to the different handling characteristics and the needs of production paper, can select different polymer monomers.As, the resistance to water of resultant paper is poor slightly during polymer monomers such as use methyl acrylate, butyl acrylate, but its absorbency is better; The resistance to water of the paper of producing is good when selecting monomers such as styrene for use, but ink absorption is poor slightly.Wherein be preferably styrene monomer, the versatility of the paper of producing is stronger.
Said initator can adopt the normal various initators that use in the present plastic processing industry, as peroxide initiators such as normally used dibenzoyl peroxide, cumyl peroxide, di-t-butyl peroxides, or azo-compound initator such as azodiisobutyronitrile, azo two eyeball in different heptan etc.For adding fast response, can under proper temperature, carry out polymerization, the polymerization temperature during as the use peroxide initiator can be 60 ℃～80 ℃, and the polymerization-stable when using azo initiator generally can be 80 ℃～100 ℃.
Said lubricating auxiliary agent generally can be in polyethylene, polypropylene, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, metallocene PE, metallocene polypropylene, polycaprolactone, poly butylene succinate, poly terephthalic acid adipic acid butanediol copolymer, poly butyric ester, poly-hydroxyl valerate, the poly (propylene carbonate) at least a.
The preparation of the above-mentioned thermoplasticity environmentally-friendly stone paper of the present invention, can be undertaken by following mode:
1 ' after said inorganic mineral powder and surface active ingredient fully mixed, add said polymer monomer and fully mix, add lubricating auxiliary agent again and mix;
2 ' said mixture material and said initator are added twin-screw reaction extrusion equipment, under 60 ℃～200 ℃ temperature conditions, carry out polymerisation and extruding pelletization, obtain thermoplastic granulates;
3 ' utilize thermoplastic to blow paper equipment or rolling equipment, will go up the step thermoplastic granulates and directly be processed into the sheet environmentally-friendly stone paper.
Reunite for avoiding the superfine little powder material of granularity, the married operation in above-mentioned the 1st ' step, can adopt powder mixing mixing plant, as L-100/200, W-100/200, high speed stirring mixers such as L-300/600, W-300/600 commonly used, it is generally carried out under the surface active ingredient fusing point (for example being higher than its fusing point gets final product for 20 ℃-40 ℃) and finishes, so that can better full and uniformly mix to use being not less than.When said polymer monomer and mixing of materials, also good to adopt even spray pattern to be incorporated as, help to realize the full and uniform mixing of each material component equally.Test shows that when adopting mixing device to mix, the inorganic mineral powder can preferably stir with mixing of surface active ingredient under the speed of 100-900rpm; When continuation mixed with polymer monomer, preferred mixing speed generally can be 1000-1500rpm.
Twin-screw response type extrusion equipment, preferred parallel dual-screw extrusion equipment, but the characteristics of aspects such as can having constant temperature devolatilization, high pressure, shear by force, reaction is continuous, particularly has big screw slenderness ratio (for example draw ratio was greater than 52: 1 o'clock), can guarantee that material has sufficiently long reaction time in screw rod, be a kind of polymer monomer the finished polymerization of excellent performance and the continuous reaction apparatus of extruding pelletization.Wherein, a kind of preferred operations condition when adopting the said equipment can be main-machine screw rotating speed 100-300rpm, and each is distinguished temperature and is controlled at: a district 60-80 ℃; Two district 100-140 ℃; Three district 145-170 ℃; Four district 170-200 ℃; Five district 170-150 ℃.
Extrude the thermoplastic granulates that obtains by the twin-screw extrusion equipment, can select for use single or multiple lift to blow paper forming device such as F-600 type, F-800 type, F-1000 type, in 165-220 ℃ of scope, make the thermoplastic granulates Flashmelt, utilize rotary die head convection cell in length and breadth to dispersion, form tubular paper through compressed air, utilize multistage air cooling equipment fast cooling and carry out in length and breadth to stretching.For guaranteeing paper formation, adopt air-cushion type guiding steel rider and horizontally taking type film nip rolls rotary steering, the doubling position can be cut open and carry out double and batch, batching apparatus adopts torque motor, stability of rotation, the electrodeless adjusting of rotary speed can keep the tension force that suits, and rolling is neat.Perhaps adopt at calendering stretcher 3F800 type, 4F1000 type, 5L1200 type calendering formation (extrusion temperature 165-220 ℃), by obtaining the environmentally-friendly stone paper that extends in 0.05～0.2mm different-thickness plane to stretching in length and breadth.
For making paper adapt to different demands at aspects such as gloss, whiteness, printing performances, can also further adopt intaglio plate reticulate pattern coating machine to be coated with, be coated with a coating at paper surface, obtain having the paper of specific use, as can be used for the senior paper of using of aspects such as illustrated supplement, brochure, magazine.
Scanning electron microscopic observation shows, in the structure of the above-mentioned environmentally-friendly stone paper of the present invention, said inorganic particle has become a kind of micrograined texture by polymer overmold (as shown in Figure 1), thereby the application of inorganic powder material in stone paper filled by traditional simple coupling, become a kind of functional component among the present invention.Show that by the DSC collection of illustrative plates is also clear papermaking material of the present invention can have good thermoplastic processability in 165.2-220.5 ℃ of scope.
Be appreciated that thus inorganic particle is mainly filled by coupling in the present stone paper, the low and processing difficulties of inorganic particle content in the paper, equipment requires high, and investment is big, and production capacity is low, causes cost higher relatively owing to contain a large amount of resins.Environmentally-friendly stone paper of the present invention is at the defective of present stone paper, by material composition and the processing of twin-screw reaction extrusion equipment of selecting suitable type, make the polymer monomer of inorganic particle microparticle surfaces in the twin-screw extrusion equipment, form polymer shell behind the initiated polymerization, inorganic particle coated fully carried out the thermoplastification processing, thereby make inorganic particle have good thermoplastic processability.The consumption of inorganic particle composition in environmentally-friendly stone paper brought up to 90%, further reduced cost, but do not influence its processing characteristics because of the raising of inorganic particle content.Therefore though the form of employed inorganic particle raw material itself, specification etc. be there is no too much requirement; but owing to had good thermoplastic processability; thereby can on the thermoplastic process equipment, carry out sheet processing easily; especially can carry out quick traction stretches; production capacity significantly improves; can prepare thin thickness and quantitative low paper, break through the stone paper process equipment to invest the low restriction of big production capacity, promote stone paper large-scale production and application.Simultaneously, because good thermoplastic processability, can have in blowing paper or calendering paper process significantly in length and breadth to orientation, paper sheet stiffness is good, rigidity is strong, and appearance tactile impression more approaches conventional paper, realizes stone papermaking truly.
Below in conjunction with the specific embodiment of accompanying drawing illustrated embodiment, foregoing of the present invention is described in further detail again.But this should be interpreted as that the scope of the above-mentioned theme of the present invention only limits to following example.Do not breaking away under the above-mentioned technological thought situation of the present invention, various replacements or change according to ordinary skill knowledge and customary means are made all should comprise within the scope of the invention.
Description of drawings
Fig. 1 is the sem photograph of the particles coated structure that the polymer overmold inorganic particle is become in the thermoplasticity environmentally-friendly stone paper of the present invention.
Fig. 2 is the DSC collection of illustrative plates of the inorganic particle of particles coated structure shown in Figure 1.
The specific embodiment
1) L-100/200 type mixing and blending machine being warming up to 80 ℃ of constant temperature, is that 1250 purpose bentonites, 3kg stearic acid add mixer with the 85kg granularity, and stirring reaction is 10 minutes under the mixing speed of 400rpm;
2) mixing speed is increased to 1500rpm, slowly evenly adds 2kg styrene, high-speed stirred 10 minutes makes styrene monomer evenly be coated in the bentonite microparticle surfaces;
3) bentonite that will finish coating is delivered in the cold mixer, adds the stirring of 5kg polypropylene and is cooled to below 50 ℃, adds the 0.05kg azodiisobutyronitrile then and mixes.
4) above compound is sent into parallel dual-screw extruding machine (screw slenderness ratio is greater than 52: 1) extruding pelletization, main-machine screw rotating speed 200rpm, each is distinguished temperature and is controlled at: 80 ℃ in a district; 100 ℃ in two districts; 165 ℃ in three districts; 195 ℃ in four districts; 170 ℃ in five districts obtain a kind of thermoplastic particle that has.
5) will more than the thermoplastic granulates that obtains on the 3F800 calender, roll drawing and forming and obtain the environmentally-friendly stone paper that thickness is 0.08mm.The physical property test result contrast of this routine stone paper and other different paper is as shown in table 1.
The physical property test result contrast of table 1 embodiment 1 stone paper and different paper product
| Test event | Tradition art printing paper (GB/T 10335.1-2005) | Contrast stone paper (CN1378909A document) | Stone paper of the present invention |
| Inorganic particle content | ??- | ??70％ | ??85％ |
| Paper sheet thickness (mm) | ??- | ??0.082 | ??0.08 |
| Quantitative (g.m -2) | ??80 | ??64.1 | ??60 |
| Whiteness (%) | ??- | ??80.5 | ??85.6 |
| Smoothness (s) | ??≥400 | ??- | ??600 |
| Opacity (%) | ??≥88 | ??95.7 | ??98 |
| Folding strength (inferior) | ??- | ??- | ??≥5000 |
| Glossiness (%) | ??≥50 | ??- | ??65 |
| Tensile strength (kN/m) | ??- | ??0.79 | ??1.3 |
| Printing | Excellent | Generally | Excellent |
By the contrast of table 1 test result as can be seen, paper of the present invention is better than the similar stone paper of traditional fine arts paper and CN1378909A bibliographical information fully.The printing performance of stone paper of the present invention is good, is suitable for propagating paper such as picture album, atlas, placard, front cover fully.
Embodiment 2
1) the W-100/200 mixing and blending machine is warming up to 120 ℃ of constant temperature, with the 70kg granularity is that 2000 order precipitated calcium carbonates, 10kg granularity are 2500 order titanium dioxide, the different tridecanol phosphate of 1kg, 3kg aluminic acid ester adding mixer, and stirring reaction is 5 minutes under the mixing speed of 900rpm;
2) mixing speed is increased to 1200rpm, slowly evenly adds the 2.5kg methyl methacrylate, high-speed stirred 10 minutes makes methyl methacrylate monomer evenly be coated in the bentonite microparticle surfaces;
3) powder that will finish coating is delivered in the cold mixer, and adding 8kg high density polyethylene (HDPE), 2kg ethylene-vinyl acetate copolymer continue stirring and be cooled to below 50 ℃, add the 0.01kg cumyl peroxide and mix.
4) above compound is sent into extruding pelletization on the parallel dual-screw extruding machine, screw slenderness ratio is greater than 52: 1, screw speed 300rpm, and each is distinguished temperature and is controlled at: 70 ℃ in a district; 130 ℃ in two districts; 150 ℃ in three districts; 175 ℃ in four districts; 150 ℃ in five districts obtain a kind of thermoplastic particle that has.
5) thermoplastic granulates that obtains more than the general blows at F-800 and carries out the blowing stretching on the paper unit, obtains the thin property environmentally-friendly stone paper that thickness is 0.04mm by the control stretching hauling speed.The physical property test result contrast of this routine stone paper and other different paper is as shown in table 2.
The comparing result of table 2 shows that paper of the present invention is better than traditional letterpress paper and stone paper fully, and paper printing characteristic of the present invention is good, and is thin and light weight is suitable for typing paper, kent, rice paper, writing paper, drawing paper, folio paper etc.
The physical property test result contrast of table 2 embodiment 2 stone paper and different paper product
| Test event | Letterpress paper (GB/T3524-1999) | Contrast stone paper (CN1378909A document) | Stone paper of the present invention |
| Inorganic particle content | ??- | ??60％ | ??80％ |
| Paper sheet thickness (mm) | ??- | ??0.052 | ??0.04 |
| Quantitative (g.m -2) | ??52 | ??44.9 | ??43 |
| Whiteness (%) | ??≥65 | ??79.2 | ??85.2 |
| Smoothness (s) | ??≥35 | ??- | ??350 |
| Opacity (%) | ??≥80 | ??90.8 | ??95 |
| Folding strength (inferior) | ??≥5 | ??- | ??≥5000 |
| Glossiness (%) | ??- | ??- | ??54 |
| Tensile strength (kN/m) | ??- | ??0.71 | ??1.1 |
| Printing | Excellent | Generally | Excellent |
Embodiment 3
1) the L-300/600 mixing and blending machine is warming up to 100 ℃ of constant temperature, with the 25kg granularity is that 1250 purpose wollastonites in powder, 60kg granularity are 1250 purpose calcite in powder, 0.5kg titanate esters, 3kg zirconate, 0.5kg amino polybasic alcohol ester (JL-G02 amino polybasic alcohol ester, Nanjing Jin Laiwang company produces) add mixer, stirring reaction is 8 minutes under the mixing speed of 500rpm;
2) mixing speed is increased to 1500rpm, slowly evenly adds the 2.5kg methyl acrylate, high-speed stirred 10 minutes makes monomer evenly be coated in microparticle surfaces;
3) particulate that will finish coating is delivered in the cold mixer, and adding 4kg polycaprolactone, 4kg ethylene-acrylic acid copolymer continue stirring and be cooled to below 50 ℃, add the 0.01kg dibenzoyl peroxide and mix.
4) above compound is sent into extruding pelletization on the parallel dual-screw extruding machine, screw slenderness ratio is greater than 52: 1, screw speed 250rpm, and each is distinguished temperature and is controlled at: 80 ℃ in a district; 140 ℃ in two districts; 165 ℃ in three districts; 200 ℃ in four districts; 170 ℃ in five districts obtain a kind of thermoplastic particle that has.The particles coated even structure that the polymer overmold inorganic particle is become is complete, shown in Figure 1 as ESEM.The result that resulting thermoplastic granulates is carried out DSC test shows that this material can have good thermoplastic processability in 165.2 ℃～220.5 ℃ scopes as shown in Figure 2.
5) thermoplastic granulates that obtains more than the general blows at F-1000 and carries out the blowing stretching on the paper machine, and control traction draw speed obtains the environmentally-friendly stone paper that thickness is 0.08mm, 0.1mm, 0.12mm at 200-100r/min.Handle by the coating of intaglio plate coating machine, obtain the high-grade paper of alternative traditional art paper.Physical property test result contrast to the different size stone paper product of preparation is as shown in table 3.
Table 3 result shows, the surface smoothing of each specification stone paper of the present invention, good luster, no dry linting, print clear true to nature, be applicable to products propaganda volume, wall calendar, placard, etc. use paper.
The physical property test result contrast of table 3 different size stone paper of the present invention product
| Paper sheet thickness | ??0.08mm | ??0.1mm | ??0.12mm |
| Quantitative (g.m -2) | ??80 | ??100 | ??125 |
| Whiteness (%) | ??85 | ??82 | ??79 |
| Smoothness (s) | ??650 | ??680 | ??700 |
| Opacity (%) | ??87 | ??90 | ??93 |
| Folding strength (inferior) | ??≥4000 | ??≥4000 | ??≥4000 |
| Glossiness (%) | ??65 | ??67 | ??65 |
| Tensile strength (kN/m) | ??1.8 | ??2.1 | ??2.3 |
| Printing | Excellent | Excellent | Excellent |
Embodiment 4
1) the W-300/600 mixing and blending machine is warming up to 100 ℃ of constant temperature, with the 40kg granularity is 2500 purpose titanium dioxides, 46kg talcum powder, 3kg zincic acid ester, 1kg phosphate (road, Nanjing the Ninghua worker provide the DN-27 phosphate), 0.5kg zinc stearate adding mixer, and stirring reaction is 5 minutes under the mixing speed of 100rpm;
2) mixing speed is increased to 1000rpm, slowly evenly adds the 2kg butyl acrylate, high-speed stirred 10 minutes makes Butyl Acrylate Monomer evenly be coated in microparticle surfaces;
3) particulate that will finish coating is delivered in the cold mixer, and adding 9kgF600 high density polyethylene (HDPE), 1kg poly butylene succinate continue stirring and be cooled to below 50 ℃, add the 0.04kg di-t-butyl peroxide and mix.
4) above compound is sent into extruding pelletization on the parallel dual-screw extruding machine, screw slenderness ratio is greater than 52: 1, screw speed 220rpm, and each is distinguished temperature and is controlled at: 70 ℃ in a district; 120 ℃ in two districts; 165 ℃ in three districts; 170 ℃ in four districts; 160 ℃ in five districts obtain a kind of thermoplastic particle that has.
5) thermoplastic granulates that obtains more than the general obtains the thin property environmentally-friendly stone paper that thickness is 0.07mm, 0.075mm, 0.08mm carry out the blowing stretching on the paper machine with blowing of embodiment 3 by control stretching speed.Physical property test result contrast to the different size stone paper product of preparation is as shown in table 4.
Table 4 result shows that the paper printing characteristic of different size stone paper of the present invention is good, can be suitable for hectographic printing.
The physical property test result contrast of table 4 different size stone paper of the present invention product
| Paper sheet thickness | ??0.07mm | ??0.075mm | ??0.08mm |
| Quantitative (g.m -2) | ??60 | ??65 | ??70 |
| Whiteness (%) | ??87 | ??85 | ??84 |
| Smoothness (s) | ??100 | ??80 | ??75 |
| Opacity (%) | ??85 | ??86 | ??92 |
| Folding strength (inferior) | ??≥5000 | ??≥5000 | ??≥5000 |
| Glossiness (%) | ??50 | ??60 | ??62 |
| Tensile strength (kN/m) | ??1.3 | ??1.5 | ??1.9 |
| Printing | Excellent | Excellent | Excellent |
Embodiment 5
1) the L-300/600 mixing and blending machine is warming up to 90 ℃ of constant temperature, with the 50kg granularity is that 1250 purpose diatomite, 38kg granularity are 300 purpose calcite in powder, 2kg phosphate, 1kg stearic amide, 0.2kg ethylene glycol chelate group titanate esters adding mixer, and stirring reaction is 5 minutes under the mixing speed of 400rpm;
2) mixing speed is increased to 1000rpm, slowly evenly adds the 2kg methyl methacrylate, high-speed stirred 8 minutes makes monomer evenly be coated in microparticle surfaces;
3) particulate that will finish coating is delivered in the cold mixer, and adding 6kg poly (propylene carbonate), 3kg metallocene polypropylene stir and be cooled to below 50 ℃, add the 0.01kg dibenzoyl peroxide and mix.
4) above compound is sent into extruding pelletization on the parallel dual-screw extruding machine, screw slenderness ratio is greater than 52: 1, screw speed 250rpm, and each is distinguished temperature and is controlled at: 80 ℃ in a district; 140 ℃ in two districts; 170 ℃ in three districts; 195 ℃ in four districts; 170 ℃ in five districts obtain a kind of thermoplastic particle that has.
5) thermoplastic granulates that obtains more than the general rolls stretching on 5L1200 type extrusion calendaring machine, obtains the environmentally-friendly stone paper that thickness is 0.1mm, 0.15m, 0.2mm, alternative Traditional Packing paper.Physical property test result contrast to the different size stone paper product of preparation is as shown in table 5.
The physical property test result contrast of table 5 different size stone paper of the present invention product
| Paper sheet thickness | ??0.1mm | ??0.15mm | ??0.2mm |
| Quantitative (g.m -2) | ??100 | ??135 | ??185 |
| Whiteness (%) | ??86 | ??84 | ??82 |
| Paper sheet thickness | ??0.1mm | ??0.15mm | ??0.2mm |
| Smoothness (s) | ??432 | ??540 | ??650 |
| Opacity (%) | ??95 | ??98 | ??98 |
| Folding strength (inferior) | ??≥2000 | ??≥1000 | ??≥750 |
| Glossiness (%) | ??43 | ??48 | ??52 |
| Deflection (mN.m) | ??2.6 | ??2.8 | ??3.7 |
| Printing | Excellent | Excellent | Excellent |
Table 5 result shows, the surface smoothing of each specification stone paper of the present invention, and good luster, well-pressed degree prints clear true to naturely well, is applicable to all kinds of high-grade package papers.
Embodiment 6
1) the L-300/600 mixing and blending machine is warming up to 100 ℃ of constant temperature, with the 60kg granularity is that 2500 purpose talcum powder, 30kg granularity are 2500 purpose titanium dioxides (chemical company of Xinhua provides), 0.5kg zinc stearate, 2kg aluminium isopropoxide acid esters, 0.5kg isopropoxy titanate esters adding mixer, and stirring reaction is 5 minutes under the mixing speed of 500rpm;
2) mixing speed is increased to 1300rpm, slowly evenly adds 3kg styrene, high-speed stirred 10 minutes makes monomer evenly be coated in microparticle surfaces;
3) particulate that will finish coating is delivered in the cold mixer, adds the 7kg high density polyethylene (HDPE), the 3kg ethylene-vinyl acetate copolymer stirs and is cooled to below 50 ℃, adds 0.04kg azo two eyeball in different heptan and mixes.
4) above compound is sent into extruding pelletization on the parallel dual-screw extruding machine, screw slenderness ratio is greater than 52: 1, screw speed 250rpm, and each is distinguished temperature and is controlled at: 80 ℃ in a district; 140 ℃ in two districts; 165 ℃ in three districts; 190 ℃ in four districts; 170 ℃ in five districts obtain a kind of thermoplastic particle that has.
5) thermoplastic granulates that obtains more than the general blows at F-600 and carries out the blowing stretching on the paper machine, control traction draw speed is obtaining the environmentally-friendly stone paper that thickness is 0.05mm, 0.08mm, 0.10mm, handle by the coating of intaglio plate coating machine then, the physical property test result contrast of the different size stone paper product of preparation is as shown in table 6.
The physical property test result contrast of table 6 different size stone paper of the present invention product
| Paper sheet thickness | ??0.05mm | ??0.08mm | ??0.10mm |
| Quantitative (g.m -2) | ??50 | ??75 | ??80 |
| Whiteness (%) | ??82 | ??82 | ??85 |
| Smoothness (s) | ??150 | ??120 | ??80 |
| Opacity (%) | ??93 | ??90 | ??93 |
| Paper sheet thickness | ??0.05mm | ??0.08mm | ??0.10mm |
| Folding strength (inferior) | ??≥4000 | ??≥4000 | ??≥4000 |
| Glossiness (%) | ??15 | ??21 | ??20 |
| Tensile strength (kN/m) | ??1.6 | ??2.2 | ??2.7 |
| Printing | Excellent | Excellent | Excellent |
Table 6 result shows, each specification stone paper of the present invention smoothly moderate, and good strength, alternative tradition is write, printing.
Claims (10)
1. thermoplasticity environmentally-friendly stone paper contains inorganic mineral powder and organic principle, it is characterized in that its weight portion consists of:
80～90 parts of inorganic mineral powders,
3～5 parts of surface active ingredients,
2～3 parts of polymer monomers,
0.01～0.05 part of initator,
5～15 parts of lubricating auxiliary agent,
Wherein, at least a in the said inorganic mineral powder wollastonite that is particle diameter 5～10 μ m, bentonite, calcite in powder, kaolin, titanium dioxide, diatomite, talcum powder, the precipitated calcium carbonate; Said surface active ingredient is to comprise at least a in the anion surfactant of inorganic acid ester; Said polymer monomer is a kind of in methyl methacrylate, methyl acrylate, butyl acrylate, the styrene; Said initator is peroxide or azo-compound; Said lubricating auxiliary agent is at least a in polyethylene, polypropylene, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, metallocene PE, metallocene polypropylene, polycaprolactone, poly butylene succinate, poly terephthalic acid adipic acid butanediol copolymer, poly butyric ester, poly-hydroxyl valerate, the poly (propylene carbonate) etc.
2. thermoplasticity environmentally-friendly stone paper as claimed in claim 1 is characterized in that said surface active ingredient is a phosphate.
3. thermoplasticity environmentally-friendly stone paper as claimed in claim 1 is characterized in that said polymer monomer is a styrene monomer.
4. thermoplasticity environmentally-friendly stone paper as claimed in claim 1 is characterized in that said peroxide initiator is dibenzoyl peroxide, cumyl peroxide, di-t-butyl peroxide.
5. thermoplasticity environmentally-friendly stone paper as claimed in claim 1 is characterized in that said azo-compound initator is azodiisobutyronitrile, azo two eyeball in different heptan.
6. the method for preparing the described thermoplasticity environmentally-friendly stone paper of claim 1 is characterized in that being undertaken by following mode:
1 ' after said inorganic mineral powder and surface active ingredient fully mixed, add said polymer monomer and fully mix, add lubricating auxiliary agent again and mix;
2 ' said mixture material and said initator are added twin-screw reaction extrusion equipment, under 60 ℃～200 ℃ temperature conditions, carry out polymerisation and extruding pelletization, obtain thermoplastic granulates;
3 ' utilize thermoplastic to blow paper equipment or rolling equipment, will go up the step thermoplastic granulates and directly be processed into the sheet environmentally-friendly stone paper.
7. preparation method as claimed in claim 6, it is characterized in that said the 1st ' in mixing of materials, in mixer, use under the heating condition of surface active ingredient melting temperature and carry out in being not less than.
8. preparation method as claimed in claim 6, it is characterized in that the 1st ' in adopt even spray pattern to add when said polymer monomer and mixing of materials.
9. preparation method as claimed in claim 6 is characterized in that said twin-screw reaction extrusion equipment is a screw slenderness ratio greater than 52: 1 parallel dual-screw extruding machine.
10. preparation method as claimed in claim 9 is characterized in that the reaction extrusion condition of mixed material in the said twin-screw reaction extrusion equipment is: screw speed 100-300rpm, and each distinguishes operating temperature: a district 60-80 ℃; Two district 100-140 ℃; Three district 145-170 ℃; Four district 170-200 ℃; Five district 170-150 ℃.
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Application publication date: 20101027 |