CN115403842A

CN115403842A - Printable polymer sheet and application thereof

Info

Publication number: CN115403842A
Application number: CN202110596129.3A
Authority: CN
Inventors: 叶孔萌
Original assignee: Jiangsu Qingyun New Material Technology Co ltd
Current assignee: Jiangsu Qingyun New Material Technology Co ltd
Priority date: 2021-05-27
Filing date: 2021-05-30
Publication date: 2022-11-29

Abstract

The invention relates to a polymer sheet with printability and application thereof, wherein the raw material of the polymer sheet is mainly polyethylene, and the gram weight of the polymer sheet is 46-76 g/m ² (ii) a The strength of the positive printing surface is more than 3.4m/s; the strength of the reverse printing surface is more than 2.8m/s; the smoothness is 25-50 seconds; the burst index is 6-12 kPa.m ² (ii) in terms of/g. The application utilizes the addition of inorganic matters to improve the printability of the sheet, and simultaneously utilizes the high toughness of the PBT to improve the technical problem that the polyethylene sheet has insufficient toughness to cause poor printability; the polymer sheet prepared by flash evaporation has excellent waterproof and air permeability, and can isolate chemical liquid, dry and wet particlesAnd the physical properties of the product are not affected after the product is immersed in water. Therefore, the paper can be used as high-grade paper such as various book paper, ground blueprint, coin paper and the like, for manufacturing outdoor maps, military charts, outdoor posters, flags and the like, is not afraid of wind and rain, and is an ideal material for use in severe environments.

Description

Printable polymer sheet and application thereof

[ technical field ] A

The invention relates to the technical field of flash spinning, in particular to a printable polymer sheet and application thereof.

[ background ] A method for producing a semiconductor device

The flash evaporation spinning superfine fiber is prepared through dissolving fiber forming polymer at high temperature and high pressure to prepare homogeneous spinning solution in certain concentration, feeding the homogeneous spinning solution into low pressure chamber under the action of high pressure, incomplete phase separation owing to slight pressure reduction, fast passing the spinning solution through the spinning holes, fast expanding at the spinning holes, fast phase separation of the solvent into vapor and polymer, and formation of supersonic vapor flow. Then, the high-speed solvent airflow impact force is used to send the superfine fiber clusters into a rotary dispersion plate, and the superfine fiber clusters are blocked by the rotary dispersion plate and change the direction to move towards a lower conveyor belt. And finally, applying an electrostatic field to the superfine fiber plexifilamentary yarns by a corona discharge method to enable the superfine fiber plexifilamentary yarns to carry the same type of electrostatic charges to repel each other and scatter in the stretching process, stacking and lapping the split reticular superfine fiber plexifilamentary yarns by a swinging device to meet the design requirements of products, and bonding and reinforcing the obtained fiber nets in different modes to obtain flash evaporation sheets with different styles. At present, the flash evaporation sheet has the technical problem that the flash evaporation sheet is high in strength and difficult to print, and the flash evaporation sheet is improved through raw materials and processes. For flash sheet patents, the applicant is mostly dupont; some patents are listed below to analyze the characteristics of DuPont, i.e., the product is defined by physical parameters.

Chinese patent publication No. CN112423978A relates to a conformable polyethylene fabric and articles made therefrom, the sheet having a width of at least 10mm and a plurality of punctures, wherein each puncture is separated from each other puncture by a distance of at least 1mm, and wherein the fabric has an average sound velocity of more than 2500 m/s.

Chinese patent publication No. CN109070534B relates to a composite ballistic resistant laminate comprising a plurality of cross-plied sheets, each cross-plied sheet further comprising (i) first and second fibrous or non-fibrous ultra-high molecular weight polyethylene layers and (ii) first and second thermoplastic adhesive layers, each adhesive layer having a basis weight of no greater than 5gsm, wherein the thermoplastic adhesive has a zero shear rate viscosity of at least 1500Pa-s as measured by astm d4440, and wherein (a) the polyethylene layers and thermoplastic adhesive layers alternate within the sheet, (B) greater than 50% of the polyethylene layers are arranged such that the orientation of the first polyethylene layer is offset relative to the orientation of the second polyethylene layer, and (c) the plurality of cross-plied sheets form a stack that does not suffer a pressure loss of greater than 8 bar within the first minute of compaction under the test method when subjected to compaction at a pressure of 255 bar and a temperature of 132 ℃.

Chinese patent publication No. CN106574401B relates to flash spun plexifilamentary strands and sheet materials, including flash spun plexifilamentary fiber strands comprising fibers having a total crystallinity index of less than or equal to 55%, and having a BET surface area of less than or equal to 12m2/g, an extrusion value of greater than or equal to 0.9mm/g, wherein the fiber strands comprise primarily fibers formed from homopolymers of ethylene; wherein the fiber strand comprises predominantly the fibers, the fibers are formed from high density polyethylene and have a monoclinic structure and an orthorhombic structure as determined by X-ray characteristics, and the monoclinic structure has a crystallinity index higher than 1%; the sheet is produced by a flash spinning process using a spin agent medium comprising a mixture of i) and ii) below, wherein: i) Is dichloromethane or trans-1, 2-dichloroethylene; and ii) is 2, 3-dihydrodecafluoropentane 1,1,1,2,2,3,3,4,4,5,5,6,6-tridecafluorohexane 1,1,1,2,2,2,3,3,4,4,5,5,6,6-dodecafluorohexane or a hydrofluoroether.

Chinese patent publication No. CN107073872B relates to a flame retardant thermal liner comprising a nonwoven sheet comprising nanofibers of a synthetic polymer having an limiting oxygen index of at least 21, a mean flow pore of 10 microns or less, a thickness air permeability of 25 to 6000 cubic feet per minute-microns (12 to 2880 cubic meters per square meter per minute-microns), and an average thickness T1; and a thermally stable flame resistant fabric attached to the outer surface of the nonwoven sheet, the fabric having an average thickness T2; a surface of the thermally stable fabric is in contact with a surface of the nonwoven sheet; wherein T1 and T2 are selected such that the ratio of T1 to T2 is less than 0.75. The application relates to a flame retardant composite fabric comprising the flame retardant thermal liner and a garment comprising the flame retardant composite fabric.

Chinese patent publication No. CN109803818A relates to a package comprising a sealed contact area with a nonwoven having a bonding surface with an embossed embossing pattern; a package for providing an enclosed interior environment capable of being sterilized, and a breathable fibrous nonwoven sheet structure useful in such structures, wherein the nonwoven sheet structure has: at least one surface having a pre-sealed, embossed pattern of impressions; and a particle barrier penetration of less than 10%, a gurley hill porosity of 40 seconds or less, and a moisture vapor transmission rate of 3500g/m 2/day or more.

Chinese patent publication No. CN109154138A relates to a composite material comprising a nonwoven vapor permeable sheet, a composite laminate comprising at least one water vapor permeable nonwoven sheet having first and second surfaces and a fluorinated polymer coating on the first surface of the sheet, wherein (i) the fluorinated polymer coating is present in an amount such that the total fluorine content of the coated nonwoven sheet is from 0.05gsm to no greater than 0.4gsm, and (ii) the composite laminate exhibits a retained hydrohead of water after exposure to wet wood when tested according to test method a of at least 60%.

Chinese patent publication No. CN104159734B relates to a breathable product cover product for protection of bulk transport and cold chain applications, comprising a product to be protected and a protective cover sheet covering the product to be protected, wherein said cover sheet comprises at least one layer made of a highly reflective moisture permeable substrate having an outer side and an inner side, wherein said high reflection means reflection of more than 65% of visible light, said inner side being closest to the protected product and at least one metal layer adjacent to said inner side of said moisture permeable substrate to achieve a suitable emissivity by high reflection and low convection to provide thermal insulation while providing a controlled moisture vapor transmission rate, wherein said suitable emissivity means an emissivity of less than 0.35.

Chinese patent publication No. CN104969381B relates to a separator medium for an electrochemical cell, a separator medium for an electrochemical cell comprising at least one nonwoven sheet comprising polymeric fibers, wherein the nonwoven sheet has a surface area of 0.5 to 1.5m2/g, a maximum pore size equal to or greater than 2.5 times the mean flow pore size and greater than 11 times the minimum pore size, wherein the separator medium is obtained by a process comprising the steps of: flash spinning a solution of 12 to 24 wt% polyethylene in a spin agent at a spinning temperature of 205 to 220 ℃ to form plexifilamentary fiber bundles and collecting the plexifilamentary fiber bundles into an unbonded web, wherein the spin agent consists of a mixture of n-pentane and cyclopentane; uniaxially stretching the unbonded web in the machine direction between heated stretching rolls having a temperature between 124 ℃ and 154 ℃ and positioned between 5cm and 30cm apart, and stretching between 3% and 25% to form a stretched web; and bonding the stretched web between heated bonding rolls having a temperature between 124 ℃ and 154 ℃ to form a nonwoven sheet, wherein the nonwoven sheet has 0.5 to about 1.5m ² A surface area per gram, and the method further comprises sulfonating the nonwoven sheet after bonding the stretched web.

Chinese patent publication No. CN 10555555528A multilayer polymer sheet and lightweight laminates made therefrom a laminate comprising a multilayer polymer sheet and at least one additional layer; wherein the multilayer polymeric sheet comprises two outer layers and comprises an inner layer, wherein the two outer layers are positioned on either side of the inner layer; wherein the inner layer comprises an ethylene vinyl acetate composition; and wherein the two outer layers are the same or different and comprise an ionomer composition; the ionomer composition comprises an ionomer; and the ionomer is the product of neutralizing an acid copolymer; wherein the acid copolymer comprises copolymerized repeat units derived from an olefin, about 0.1 to about 30 wt% of copolymerized repeat units derived from a β -ethylenically unsaturated carboxylic acid having 3 to 8 carbon atoms, and optionally about 2 to about 25 wt% of copolymerized repeat units derived from an ester of an ethylenically unsaturated carboxylic acid, the ester having 4 to 12 carbon atoms; and the ethylenically unsaturated carboxylic acid and ethylenically unsaturated carboxylic acid are the same or different; wherein the weight percentages are based on the total weight of the acid copolymer and the sum of the weight percentages of copolymerized residues in the acid copolymer is 100 wt%; and wherein from about 5% to about 100% of the carboxylic acid groups in the acid copolymer are neutralized with one or more bases comprising a metal cation; and wherein the laminate has a sound transmission rating of greater than 25 as measured by astm e 314; or wherein the laminate has an effective bending stiffness of from about 3.0mm to about 5.0mm as measured by astm c 158.

Chinese patent publication No. CN103533996B relates to a method of preparing a liquid filtration medium, comprising: flash spinning a 12 to 24% by weight solution of polyethylene in a spin agent consisting of a mixture of n-pentane and cyclopentane at a spinning temperature of 205 to 220 ℃ to form plexifilamentary fiber bundles, and collecting the plexifilamentary fiber bundles into an unbonded web; uniaxially stretching the unbonded web in the machine direction between heated stretching rolls positioned between 5cm and 30cm apart at a temperature between 124 ℃ and 154 ℃ and stretching 3% to 25% to form a stretched web; and bonding the stretched web between heated bonding rolls at a temperature between 124 ℃ and 154 ℃ to form a nonwoven sheet, wherein the nonwoven sheet has a water flow rate of at least 10ml/min/cm2/KPa and a tortuosity filter factor of at least 3.0, and wherein the nonwoven sheet is a nonwoven sheet that is unidirectionally stretched in a machine direction.

[ summary of the invention ]

The object of the present invention is to overcome the disadvantages of the prior art and to provide a printable polymer sheet and use.

The purpose of the invention is realized by the following technical scheme:

the printable polymer sheet is made of polyethylene with gram weight of 46-76 g/m ² ；

The strength of the positive printing surface is more than 3.4m/s;

the strength of the reverse printing surface is more than 2.8m/s;

the smoothness is 25-50 seconds;

the burst index is 6-12 kPa.m ² /g。

The positive printed surface strength of the polymer sheet is 3.4 to 4.4m/s or 4.4 to 5.4m/s or 5.4 to 6.4m/s.

The strength of the reverse printing surface of the polymer sheet is 2.8-3.8 m/s, or 3.8-4.8 m/s, or 4.8-5.8 m/s.

The polymer sheet has a smoothness of 25 to 35 seconds or 35 to 42 seconds or 42 to 50 seconds.

The polymer sheet has a burst index of 6 to 8kPa m ² (ii)/g or 8 to 10kPa · m ² (ii)/g or 10 to 12kPa · m ² /g。

The printable polymer sheet is prepared from modified polybutylene terephthalate powder.

The modified polybutylene terephthalate is modified polybutylene terephthalate doped with antimony white.

The mass fraction of the modified polybutylene terephthalate in the polymer sheet is 1.5-3%.

A method for producing a printable polymer sheet, comprising the technical steps of:

carrying out flash spinning on the spinning solution, then carrying out a lapping procedure on flash fibers, and carrying out hot press molding and calendaring processes on hot rolls to obtain a polymer sheet;

the spinning solution comprises modified polybutylene terephthalate and polyethylene, and a spinning solvent.

The preferable technical scheme is as follows:

the method comprises the following steps: (1) The preparation method comprises the following steps of dispersing antimony white powder and aluminum chloride powder in potassium hydroxide alkaline solution, then carrying out high-speed stirring and ultrasonic dispersion, separating precipitates, filtering, drying and calcining to obtain an aluminum oxide composite material adsorbed on the surface of the antimony white powder; (2) Stirring the aluminum oxide composite material adsorbed on the surface of antimony white powder at a high speed in an n-pentane solution, performing ultrasonic dispersion, and then adding 3-aminopropyltriethoxysilane for reaction; after the reaction is finished, centrifugal separation is carried out, and the solid is dried in vacuum to prepare the antimony white modified composite material with the adsorption functional group; (3) Then carrying out coarse grinding and fine grinding on the monobutyl maleate, the initiator dicumyl peroxide, the antimony white modified composite material and the PBT, and then carrying out melt extrusion granulation through an extruder to obtain the modified polybutylene terephthalate doped with antimony white.

The mass ratio of the antimony white powder to the aluminum chloride powder is 2.

The mass fraction of the antimony white powder in the potassium hydroxide alkaline solution is 5-10%, and the excess of the alkaline solution is kept.

The mass concentration of the aluminum oxide composite material adsorbed on the surface of the antimony white powder in n-pentane is 15-50 g/L.

The 3-aminopropyl triethoxysilane accounts for 2-5% of the mass of the aluminum oxide composite material adsorbed on the surface of the antimony white powder; preferably 4%.

The mass fraction of the maleic acid monobutyl ester in the modified polybutylene terephthalate doped with antimony white is 0.5-2%.

The mass fraction of the initiator dicumyl peroxide in the modified polybutylene terephthalate doped with antimony white is 0.1-1%.

The mass fraction of the antimony white modified composite material in the modified polybutylene terephthalate doped with antimony white is 2-5%.

The modified polybutylene terephthalate powder doped with antimony white is obtained by carrying out coarse grinding and fine grinding on monobutyl maleate, antimony white modified composite material and PBT, and then carrying out extrusion granulation through an extruder, wherein the grafting ratio is 1.5-2%.

The high-speed stirring process comprises the following steps: the stirring speed is 1500-2500 rpm, and the stirring time is 0.5-2 hours.

An ultrasonic dispersion process: the dispersing time is 2 to 3 hours.

The calcining process comprises the following steps: the temperature rise rate of the calcination is 10 ℃/min, and the temperature is raised to 450 ℃.

The rough grinding process comprises the following steps: the grinding speed is 500-750 rpm, and the grinding time is 0.5-1 hour.

And (3) a fine grinding process: the grinding speed is 1500-2500 rpm, and the grinding time is 1-2 hours.

According to the method, precipitated aluminum hydroxide is firstly formed on the surface of antimony white powder, and then aluminum oxide is generated through a calcining process, namely, the antimony white powder is coated with a layer of protective layer aluminum oxide, so that the long-acting slow-release whitening effect is achieved (for example, performance test data of comparative example 1 is poor) compared with the case that the antimony white powder is directly added into a flash evaporation sheet, and meanwhile, due to the fact that inorganic matters (aluminum oxide composite materials adsorbed on the surface of the antimony white powder) enter fiber gaps of the flash evaporation sheet, smoothness of the inorganic matters is improved, and printability is improved (for example, performance test data of comparative example 2 is poor); meanwhile, the surface of the antimony white powder is adsorbed with the alumina composite material, hydroxyl grafting is firstly carried out (by utilizing the polyhydroxy characteristic of n-pentane solution), and then amino grafting is added (by utilizing the amino of 3-aminopropyltriethoxysilane); the surface of the inorganic substance (the alumina composite material is adsorbed on the surface of the antimony white powder) is subjected to surface clustering, so that the grafting reaction in the subsequent melt extrusion process is facilitated (for example, the performance test data of comparative example 3 is poor). The method comprises the steps of adding a coarse grinding process and a fine grinding process before a melt extrusion process step, and utilizing a dry powder ball mill; the raw materials can be ground to ensure that the raw materials are fully contacted and dispersed, the extrusion dispersion difficulty is avoided, various components are doped with each other, the surface activity is improved, the material dispersion is more uniform, and the dispersibility of a final product obtained by melt extrusion is facilitated (for example, the performance test data of a comparative example 4 is poor). According to the preparation method, the alkyl chain polar monomer grafted in the PBT particle can reduce the interfacial tension with a polyethylene matrix in the future flash spinning process, improve the compatibility of the modified polybutylene terephthalate doped with antimony oxide and the polyethylene monomer, and facilitate the flash spinning process, which is one of the factors for selecting the material. However, when the content of the modified polybutylene terephthalate doped with antimony white reaches a certain level in the sheet, the effect of the modified polybutylene terephthalate on promoting dispersion and interfacial adhesion of polyethylene is no longer obvious, namely, the modified polybutylene terephthalate doped with antimony white does not play a role in improving the performance with the increase of the addition amount (such as the performance test data of comparative examples 8-11 are poor). The application utilizes the addition of inorganic matters to improve the printability of the sheet, and simultaneously utilizes the high toughness of the PBT to improve the technical problem that the polyethylene sheet has insufficient toughness to cause poor printability.

Step two: dissolving the modified polybutylene terephthalate doped with antimony white prepared in the step one and polyethylene particles in a spinning solvent, and controlling the pressure of the spinning solution to be 40-80 bar to obtain the spinning solution;

the mass fraction of the modified polybutylene terephthalate doped with antimony white and the polyethylene particles in the spinning solution is 10-13%; when the mass fraction of the raw material in the spinning solution is too high or too low, the final properties of the product are significantly affected (e.g., the performance test data of comparative examples 5-7 are poor).

The mass fraction of the modified polybutylene terephthalate in the modified polybutylene terephthalate doped with antimony white and polyethylene particle mixture is 1.5-3%.

The spinning solvent is selected from one or more than two of aromatic hydrocarbons, aliphatic hydrocarbons, alicyclic hydrocarbons, unsaturated hydrocarbons, halogenated hydrocarbons, esters, ethers and fluorocarbon compounds.

The spinning solvent is preferably 1, 2-dichloroethylene, 2, 3-dihydrodecafluoropentane and 1, 2-tetrafluoro-2-chloroethane, and the volume ratio of the three is 6.

Step three: carrying out flash spinning on the spinning solution prepared in the step two, and then carrying out a lapping procedure on flash fibers, and carrying out hot press molding and calendaring processes on hot rolls to obtain polymer sheets; wherein the spinning temperature is 200-220 ℃, and the spinning pressure is 40-80 bar.

Use of a printable polymer sheet for printing packaging material.

The polymer sheet prepared by flash evaporation has excellent waterproof and air permeability, can isolate chemical liquid and dry and wet particles, and does not influence the physical properties of the polymer sheet after being soaked in water. Therefore, the paper can be used as high-grade paper such as various book paper, ground blueprint, coin paper and the like, for manufacturing outdoor maps, military charts, outdoor posters, flags and the like, is not afraid of wind and rain, and is an ideal material for use in severe environments.

Compared with the prior art, the invention has the following positive effects:

the application utilizes the addition of inorganic matters to improve the printability of the sheet, and simultaneously utilizes the high toughness of the PBT to improve the technical problem that the polyethylene has insufficient toughness to cause poor printability.

[ detailed description ] embodiments

The following provides specific embodiments of a printable polymer sheet and applications of the present invention.

The specific test methods for the samples prepared in this application:

1. printing surface strength:

the printing surface strength is the speed at which the material surface is printed at a continuously increasing speed until the material surface starts to fluff, expressed in m/s.

The strength of the printing surface is tested in national standard GB/T22365-2008,

as defined herein: the front side of the sample was tested for positive print surface strength, and the other side of the sample was tested for reverse print surface strength.

The higher the printing surface strength, the more advantageous the printing. However, the printed surface strength is too high, which results in a softer product, and the strength of the product is too low.

2. Smoothness:

smoothness: the time required for a certain amount of air to escape from the atmosphere between the sample surface and the annular plate surface under a specific contact condition and a certain pressure difference is in seconds.

The smoothness is measured according to national standard GB/T456-2002, paper and paperboard smoothness measurement (the peck method), 10 test samples are taken, the front smoothness and the back smoothness of each test sample are respectively measured, and then the average is carried out to obtain the sample smoothness.

When the smoothness is high, the tightness is made large, resulting in a decrease in ink-absorbing performance, and therefore the smoothness is not likely to be excessively high. When the smoothness is lower, it is softer and the strength of the product is too low. In combination with other performance parameters, the application selects the interval range with the smoothness of 25-50 s so as to enable the product to have better printing effect.

3. Burst index:

burst index is the burst divided by the quantification; the bursting strength is the maximum pressure when the elastic rubber film breaks the circular area of the paper pattern under the pressure exerted by a hydraulic system.

The test standard for burst index is described in national Standard GB/T1539-2007/ISO 2759, IDT, 2001. Sampling according to standard requirements, firstly carrying out warm-wet price treatment on the sample, wherein the process conditions of the warm-wet processing treatment are as follows: RH at 22-24 deg.C and 48-52% for 4 hr. And testing the samples after the warm-wet treatment under the following test conditions: the test environment temperature is 22-24 ℃, the test environment humidity is 48-52% RH.

For the burst index, the larger the better. Therefore, in the performance parameters of the burst index, the surface printing strength, the smoothness and the D65 brightness, a dynamic balance needs to be found, that is, the burst index has a certain value on the premise of having a better printing effect.

4. D65 luminance:

the D65 brightness was measured according to the national standard GB/T7974-2013, according to the paper and board test method, wherein the front and back of the sample were measured separately and then averaged to obtain the D65 brightness.

Sheet materials, especially for outdoor packaging, must have a high brightness due to printing requirements, and relatively speaking, the higher the brightness, the better the resistance to yellowing caused by aging of the sheet material itself.

Example 1

the method comprises the following steps: (1) The preparation method comprises the following steps of dispersing antimony white powder and aluminum chloride powder in a potassium hydroxide alkaline solution, then carrying out high-speed stirring and ultrasonic dispersion, separating precipitates, filtering, drying, and calcining to obtain an aluminum oxide composite material adsorbed on the surface of the antimony white powder; (2) Stirring the aluminum oxide composite material adsorbed on the surface of antimony white powder at a high speed in an n-pentane solution, performing ultrasonic dispersion, and then adding 3-aminopropyltriethoxysilane for reaction; after the reaction is finished, centrifugal separation is carried out, and the solid is dried in vacuum to prepare the antimony white modified composite material with the adsorption functional group; (3) Then carrying out coarse grinding and fine grinding on the monobutyl maleate, the initiator dicumyl peroxide, the antimony white modified composite material and the PBT, and then carrying out melt extrusion granulation through an extruder to obtain the modified polybutylene terephthalate doped with antimony white.

The mass fraction of the antimony white powder in the potassium hydroxide alkaline solution is 5%, and the excess of the alkaline solution is kept.

The mass concentration of the aluminum oxide composite material adsorbed on the surface of the antimony white powder in n-pentane is 21g/L.

The 3-aminopropyl triethoxysilane is the mass 2 of the composite material of the aluminum oxide adsorbed on the surface of the antimony white powder. 2.5 percent.

The mass fraction of the maleic acid monobutyl ester in the modified polybutylene terephthalate doped with antimony white is 0.5%.

The mass fraction of the initiator dicumyl peroxide in the modified polybutylene terephthalate doped with antimony white is 0.2%.

The mass fraction of the antimony white modified composite material in the modified polybutylene terephthalate doped with antimony white is 2%.

The modified polybutylene terephthalate powder doped with antimony white is obtained by firstly carrying out coarse grinding and fine grinding on monobutyl maleate, antimony white modified composite material and PBT, and then carrying out extrusion granulation through an extruder, wherein the grafting ratio is 1.5%.

The high-speed stirring process comprises the following steps: the stirring speed was 1500 rpm and the stirring time was 1 hour.

An ultrasonic dispersion process: the dispersion time was 2 hours.

The rough grinding process comprises the following steps: the grinding speed was 550rpm, and the grinding time was 0.5 hour.

And (3) fine grinding process: the milling speed was 1600rpm and the milling time was 1 hour.

Step two: dissolving the modified polybutylene terephthalate doped with antimony oxide prepared in the step one and polyethylene particles in a spinning solvent, and controlling the pressure of the spinning solution to be 40-50 bar to obtain the spinning solution;

the mass fraction of the modified polybutylene terephthalate doped with antimony white and the polyethylene particles in the spinning solution is 10.5%;

the mass fraction of the modified polybutylene terephthalate in the modified polybutylene terephthalate doped with antimony white and the polyethylene particle mixture is 1.5%.

The spinning solvent is 1, 2-dichloroethylene, 2, 3-dihydrodecafluoropentane and 1, 2-tetrafluoro-2-chloroethane, and the volume ratio of the three is 6.

Step three: carrying out flash spinning on the spinning solution prepared in the step two, and then carrying out a lapping procedure on flash fibers, and carrying out hot press molding and calendaring processes on hot rolls to obtain polymer sheets; wherein the spinning temperature is 200-220 ℃, and the spinning pressure is 40-50 bar. Performance test methods the results of the test data are presented in table 1, supra.

Example 2

the method comprises the following steps: (1) The preparation method comprises the following steps of dispersing antimony white powder and aluminum chloride powder in a potassium hydroxide alkaline solution, then carrying out high-speed stirring and ultrasonic dispersion, separating precipitates, filtering, drying, and calcining to obtain an aluminum oxide composite material adsorbed on the surface of the antimony white powder; (2) Stirring the aluminum oxide composite material adsorbed on the surface of antimony white powder at a high speed in a n-pentane solution, performing ultrasonic dispersion, and then adding 3-aminopropyltriethoxysilane for reaction; after the reaction is finished, centrifugal separation is carried out, and the solid is dried in vacuum to prepare the antimony white modified composite material with the adsorption functional group; (3) Then carrying out coarse grinding and fine grinding on the monobutyl maleate, the initiator dicumyl peroxide, the antimony white modified composite material and the PBT, and then carrying out melt extrusion granulation through an extruder to obtain the modified polybutylene terephthalate doped with antimony white.

The mass ratio of the antimony white powder to the aluminum chloride powder is 3.

The mass fraction of the antimony white powder in the potassium hydroxide alkaline solution is 7%, and the excess of the alkaline solution is kept.

The mass concentration of the aluminum oxide composite material adsorbed on the surface of the antimony white powder in n-pentane is 27g/L.

The 3-aminopropyl triethoxysilane accounts for 4% of the mass of the alumina composite material adsorbed on the surface of the antimony white powder.

The mass fraction of the monobutyl maleate in the modified polybutylene terephthalate doped with antimony white is 1 percent.

The mass fraction of the initiator dicumyl peroxide in the modified polybutylene terephthalate doped with antimony white is 0.6%.

The mass fraction of the antimony white modified composite material in the modified polybutylene terephthalate doped with antimony white is 4%.

The modified polybutylene terephthalate powder doped with antimony white is obtained by firstly carrying out coarse grinding and fine grinding on monobutyl maleate, antimony white modified composite material and PBT, and then carrying out extrusion granulation through an extruder, wherein the grafting ratio is 1.7%.

The high-speed stirring process comprises the following steps: the stirring speed was 2100 rpm and the stirring time was 1 hour.

An ultrasonic dispersion process: the dispersion time was 2.5 hours.

The rough grinding process comprises the following steps: the milling speed was 650rpm and the milling time was 1 hour.

And (3) a fine grinding process: the milling speed was 2200rpm and the milling time was 2 hours.

Step two: dissolving the modified polybutylene terephthalate doped with antimony oxide prepared in the step one and polyethylene particles in a spinning solvent, and controlling the pressure of the spinning solution to be 50-60 bar to obtain the spinning solution;

the mass fraction of the modified polybutylene terephthalate doped with antimony white and the polyethylene particles in the spinning solution is 11.5%;

the mass fraction of the modified polybutylene terephthalate in the modified polybutylene terephthalate doped with antimony white and polyethylene particle mixture is 2%.

Step three: carrying out flash spinning on the spinning solution prepared in the second step, and then carrying out a lapping procedure on flash-spun fibers, and then carrying out hot press molding and calendaring processes of a hot roller to obtain polymer sheets; wherein the spinning temperature is 200-220 ℃, and the spinning pressure is 50-60 bar. Performance test methods the results of the test data are presented in table 1, supra.

Example 3

the method comprises the following steps: (1) The preparation method comprises the following steps of dispersing antimony white powder and aluminum chloride powder in potassium hydroxide alkaline solution, then carrying out high-speed stirring and ultrasonic dispersion, separating precipitates, filtering, drying and calcining to obtain an aluminum oxide composite material adsorbed on the surface of the antimony white powder; (2) Stirring the aluminum oxide composite material adsorbed on the surface of antimony white powder at a high speed in an n-pentane solution, performing ultrasonic dispersion, and then adding 3-aminopropyltriethoxysilane for reaction; after the reaction is finished, centrifugal separation is carried out, and the solid is dried in vacuum to prepare the antimony white modified composite material with the adsorption functional group; (3) And then carrying out coarse grinding and fine grinding on the monobutyl maleate, the initiator dicumyl peroxide, the antimony white modified composite material and the PBT, and then carrying out melt extrusion granulation through an extruder to obtain the modified polybutylene terephthalate doped with antimony white.

The mass ratio of the antimony white powder to the aluminum chloride powder is 4.

The mass fraction of the antimony white powder in the potassium hydroxide alkaline solution is 10%, and the excess of the alkaline solution is kept.

The mass concentration of the aluminum oxide composite material adsorbed on the surface of the antimony white powder in n-pentane is 45g/L.

The 3-aminopropyl triethoxysilane accounts for 5 percent of the mass of the aluminum oxide composite material adsorbed on the surface of the antimony white powder.

The mass fraction of the monobutyl maleate in the modified polybutylene terephthalate doped with antimony white is 2%.

The mass fraction of the initiator dicumyl peroxide in the modified polybutylene terephthalate doped with antimony white is 0.8%.

The mass fraction of the antimony white modified composite material in the modified polybutylene terephthalate doped with antimony white is 5%.

The modified polybutylene terephthalate powder doped with antimony white is obtained by carrying out coarse grinding and fine grinding on monobutyl maleate, antimony white modified composite material and PBT, and then carrying out extrusion granulation through an extruder, wherein the grafting ratio is 2% in the process.

The high-speed stirring process comprises the following steps: the stirring speed was 2500rpm and the stirring time was 2 hours.

An ultrasonic dispersion process: the dispersion time was 3 hours.

The rough grinding process comprises the following steps: the milling speed was 750rpm and the milling time was 1 hour.

And (3) fine grinding process: the milling speed was 2500rpm and the milling time was 2 hours.

Step two: dissolving the modified polybutylene terephthalate doped with antimony oxide prepared in the step one and polyethylene particles in a spinning solvent, and controlling the pressure of the spinning solution to be 60-70 bar to obtain the spinning solution;

the mass fraction of the modified polybutylene terephthalate doped with antimony white and the polyethylene particles in the spinning solution is 12.5%;

the mass fraction of the modified polybutylene terephthalate in the modified polybutylene terephthalate doped with antimony white and the polyethylene particle mixture is 3%.

Step three: carrying out flash spinning on the spinning solution prepared in the step two, and then carrying out a lapping procedure on flash fibers, and carrying out hot press molding and calendaring processes on hot rolls to obtain polymer sheets; wherein the spinning temperature is 200-220 ℃, and the spinning pressure is 60-70 bar. Performance test methods the results of the test data are presented in table 1, supra.

Comparative example 1

the method comprises the following steps: (1) Mixing antimony white powder, aluminum oxide, monobutyl maleate, an initiator dicumyl peroxide, an antimony white modified composite material and PBT, and then carrying out melt extrusion granulation by an extruder to obtain the modified polybutylene terephthalate doped with antimony white.

The mass fraction of the antimony white powder in the modified polybutylene terephthalate doped with antimony white is 3%;

the mass fraction of the alumina in the modified polybutylene terephthalate doped with antimony white is 1 percent;

the mass fraction of the maleic acid monobutyl ester in the modified polybutylene terephthalate doped with antimony white is 1 percent.

Step three: carrying out flash spinning on the spinning solution prepared in the step two, and then carrying out a lapping procedure on flash fibers, and carrying out hot press molding and calendaring processes on hot rolls to obtain polymer sheets; wherein the spinning temperature is 200-220 ℃, and the spinning pressure is 50-60 bar. Performance test methods the results of the test data are presented in table 1, supra.

Comparative example 2

the method comprises the following steps: (1) Stirring antimony white powder at a high speed in an n-pentane solution, carrying out ultrasonic dispersion, and then adding 3-aminopropyltriethoxysilane for reaction; after the reaction is finished, centrifugal separation is carried out, and the solid is dried in vacuum to prepare the antimony white modified composite material with the adsorption functional group; (2) Then carrying out coarse grinding and fine grinding on the monobutyl maleate, the initiator dicumyl peroxide, the antimony white modified composite material and the PBT, and then carrying out melt extrusion granulation through an extruder to obtain the modified polybutylene terephthalate doped with antimony white.

The mass concentration of the antimony white powder in n-pentane is 27g/L.

The 3-aminopropyl triethoxysilane accounts for 4% of the mass of the antimony white powder.

And (3) fine grinding process: the milling speed was 2200rpm and the milling time was 2 hours.

Comparative example 3

the method comprises the following steps: (1) The preparation method comprises the following steps of dispersing antimony white powder and aluminum chloride powder in a potassium hydroxide alkaline solution, then carrying out high-speed stirring and ultrasonic dispersion, separating precipitates, filtering, drying, and calcining to obtain an aluminum oxide composite material adsorbed on the surface of the antimony white powder; (2) Then carrying out coarse grinding and fine grinding on the monobutyl maleate, the initiator dicumyl peroxide, the aluminum oxide composite material adsorbed on the surface of the antimony white powder and the PBT, and then carrying out melt extrusion granulation through an extruder to obtain the modified polybutylene terephthalate doped with antimony white.

The mass fraction of the composite material adsorbing aluminum oxide on the surface of the white powder in the modified polybutylene terephthalate doped with antimony white is 4%.

An ultrasonic dispersion process: the dispersion time was 2.5 hours.

Step two: dissolving the modified polybutylene terephthalate doped with antimony white prepared in the step one and polyethylene particles in a spinning solvent, and controlling the pressure of the spinning solution to be 50-60 bar to obtain the spinning solution;

Comparative example 4

the method comprises the following steps: (1) The preparation method comprises the following steps of dispersing antimony white powder and aluminum chloride powder in a potassium hydroxide alkaline solution, then carrying out high-speed stirring and ultrasonic dispersion, separating precipitates, filtering, drying, and calcining to obtain an aluminum oxide composite material adsorbed on the surface of the antimony white powder; (2) Stirring the aluminum oxide composite material adsorbed on the surface of antimony white powder at a high speed in an n-pentane solution, performing ultrasonic dispersion, and then adding 3-aminopropyltriethoxysilane for reaction; after the reaction is finished, centrifugal separation is carried out, and the solid is dried in vacuum to prepare the antimony white modified composite material with the adsorption functional group; (3) And then mixing an initiator dicumyl peroxide, the antimony white modified composite material and the PBT, and performing melt extrusion granulation by an extruder to obtain the modified polybutylene terephthalate doped with antimony white.

The 3-aminopropyl triethoxysilane accounts for 4% of the mass of the aluminum oxide composite material adsorbed on the surface of the antimony white powder.

An ultrasonic dispersion process: the dispersion time was 2.5 hours.

Comparative example 5

The modified polybutylene terephthalate powder doped with antimony white is obtained by carrying out coarse grinding and fine grinding on monobutyl maleate, antimony white modified composite material and PBT, and then carrying out extrusion granulation through an extruder, wherein the grafting ratio is 1.7%.

An ultrasonic dispersion process: the dispersion time was 2.5 hours.

The calcining process comprises the following steps: the temperature rise rate of calcination is 10 ℃/min, and the temperature is raised to 450 ℃.

the mass fraction of the modified polybutylene terephthalate doped with antimony white and the polyethylene particles in the spinning solution is 9.5 percent

Comparative example 6

the method comprises the following steps: (1) The preparation method comprises the following steps of dispersing antimony white powder and aluminum chloride powder in a potassium hydroxide alkaline solution, then carrying out high-speed stirring and ultrasonic dispersion, separating precipitates, filtering, drying, and calcining to obtain an aluminum oxide composite material adsorbed on the surface of the antimony white powder; (2) Stirring the aluminum oxide composite material adsorbed on the surface of antimony white powder at a high speed in an n-pentane solution, performing ultrasonic dispersion, and then adding 3-aminopropyltriethoxysilane for reaction; after the reaction is finished, centrifugal separation is carried out, and the solid is dried in vacuum to prepare the antimony white modified composite material with the adsorption functional group; (3) And then carrying out coarse grinding and fine grinding on the monobutyl maleate, the initiator dicumyl peroxide, the antimony white modified composite material and the PBT, and then carrying out melt extrusion granulation through an extruder to obtain the modified polybutylene terephthalate doped with antimony white.

An ultrasonic dispersion process: the dispersion time was 2.5 hours.

And (3) a calcination process: the temperature rise rate of the calcination is 10 ℃/min, and the temperature is raised to 450 ℃.

And (3) a coarse grinding process: the milling speed was 650rpm and the milling time was 1 hour.

the mass fraction of the modified polybutylene terephthalate doped with antimony white and the polyethylene particles in the spinning solution is 13.5 percent;

Comparative example 7

And (3) a high-speed stirring process: the stirring speed was 2100 rpm and the stirring time was 1 hour.

An ultrasonic dispersion process: the dispersion time was 2.5 hours.

the mass fraction of the modified polybutylene terephthalate doped with antimony white and the polyethylene particles in the spinning solution is 14.5%;

Comparative example 8

An ultrasonic dispersion process: the dispersion time was 2.5 hours.

the mass fraction of the modified polybutylene terephthalate in the modified polybutylene terephthalate doped with antimony white and the polyethylene particle mixture is 0.5%.

Comparative example 9

An ultrasonic dispersion process: the dispersion time was 2.5 hours.

the mass fraction of the modified polybutylene terephthalate in the modified polybutylene terephthalate doped with antimony white and polyethylene particle mixture is 1%.

Comparative example 10

An ultrasonic dispersion process: the dispersion time was 2.5 hours.

the mass fraction of the modified polybutylene terephthalate in the modified polybutylene terephthalate doped with antimony white and the polyethylene particle mixture is 3.5%.

Comparative example 11

the method comprises the following steps: (1) The preparation method comprises the following steps of dispersing antimony white powder and aluminum chloride powder in a potassium hydroxide alkaline solution, then carrying out high-speed stirring and ultrasonic dispersion, separating precipitates, filtering, drying, and calcining to obtain an aluminum oxide composite material adsorbed on the surface of the antimony white powder; (2) Stirring the aluminum oxide composite material adsorbed on the surface of antimony white powder at a high speed in a n-pentane solution, performing ultrasonic dispersion, and then adding 3-aminopropyltriethoxysilane for reaction; after the reaction is finished, centrifugal separation is carried out, and the solid is dried in vacuum to prepare the antimony white modified composite material with the adsorption functional group; (3) And then carrying out coarse grinding and fine grinding on the monobutyl maleate, the initiator dicumyl peroxide, the antimony white modified composite material and the PBT, and then carrying out melt extrusion granulation through an extruder to obtain the modified polybutylene terephthalate doped with antimony white.

An ultrasonic dispersion process: the dispersion time was 2.5 hours.

the mass fraction of the modified polybutylene terephthalate in the modified polybutylene terephthalate doped with antimony white and polyethylene particle mixture is 4%.

TABLE 1

The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, several modifications and decorations can be made without departing from the concept of the present invention, and these modifications and decorations should also be regarded as being within the protection scope of the present invention.

Claims

1. A printable polymer sheet, characterized in that it is made of polyethylene and has a basis weight of 46-76 g/m ² ；

The strength of the positive printing surface is more than 3.4m/s;

the strength of the reverse printing surface is more than 2.8m/s;

the smoothness is 25-50 seconds;

the burst index is 6-12 kPa.m ² /g。

2. The printable polymer sheet of claim 1, wherein the polymer sheet has a positive printing surface strength of 3.4 to 4.4m/s or 4.4 to 5.4m/s or 5.4 to 6.4m/s.

3. The printable polymer sheet of claim 1, wherein the reverse printing surface strength of the polymer sheet is 2.8 to 3.8m/s or 3.8 to 4.8m/s or 4.8 to 5.8m/s.

4. A printable polymer sheet according to claim 1, wherein the polymer sheet has a smoothness of 25 to 35 seconds or 35 to 42 seconds or 42 to 50 seconds.

5. The printable polymer sheet of claim 1, wherein the polymer sheet has a burst index of 6 to 8 kPa-m ² (ii)/g or 8 to 10kPa · m ² (ii)/g or 10 to 12kPa · m ² /g。

6. The printable polymer sheet of claim 1, wherein the polymer sheet material further comprises modified polybutylene terephthalate.

7. The printable polymer sheet of claim 6, wherein the modified polybutylene terephthalate is modified polybutylene terephthalate doped with antimony white.

8. The printable polymer sheet of claim 6, wherein the modified polybutylene terephthalate is present in the polymer sheet in an amount of 1.5 to 3% by weight.

9. A method for producing a printable polymer sheet, comprising the technical steps of:

10. Use of a printable polymer sheet for printing packaging material.