A fold-resistant film material and a method of making the same

Abstract

The present application belongs to the field of textile flash evaporation technology, and particularly relates to a crease-resistant film material and a preparation method thereof. The present application aims at the technical problem of poor total crease recovery angle and crease resistance of the film material prepared by the method of flash evaporation spinning in the prior art, and provides a crease-resistant film material and a preparation method thereof. The raw material comprises polyethylene, the total crease recovery angle of the crease-resistant film material is 60-95°, which is tested by a horizontal method, and the crease resistance of the crease-resistant film material is greater than 4. The present application improves the raw material and the spinning process, so that the prepared film material has good total crease recovery angle and crease resistance, thereby overcoming the problems in the prior art. In addition, the present application fills zinc white in the urchin-shaped copper oxide microspheres, so as to play a uniform dispersion role, thereby having long-term slow-release antibacterial function.

Description

Technical Field

[0001] This invention belongs to the field of textile flash evaporation technology, and particularly relates to a fold-resistant film material and its preparation method. Background Technology

[0002] Flash spinning refers to the preparation of sheet materials using flash spinning technology, generally referring to the preparation of polyethylene or other thermoplastic polymers. Flash spinning is a spinning method where the polymer solution is at a temperature above the solvent's boiling point, and simultaneously extruded through a spinneret under high pressure to reach atmospheric pressure. During spinning, the sudden pressure drop causes the solvent to evaporate rapidly, resulting in extremely fine filaments that form flash fibers. These fibers are then laid up and hot-pressed to obtain polymer sheets. The most prominent phenomenon in flash spinning is phase separation. For example, during the dissolution process, the polymer and solvent are stirred under high temperature and pressure to form a homogeneous solution; in a low-pressure chamber, the pressure is slightly reduced, causing a certain degree of phase separation, forming a two-phase solution, one phase rich in polymer and the other rich in solvent; finally, when the solution enters room temperature and pressure air through the spinneret, the solvent converts into vapor and rapidly separates from the polymer. Currently, existing membrane materials prepared by flash spinning methods suffer from poor total crease recovery angle and folding endurance.

[0003] Chinese Patent Application No. CN202011373641.3 relates to a flash-evaporated nonwoven fabric and its preparation method. This invention addresses the problem in existing technologies where solid adsorbents are difficult to flow, requiring the switching of different equipment for adsorption and desorption. It provides a flash-evaporated nonwoven fabric and its preparation method, including steps for preparing a spinning solution, spinning, and tail gas treatment. The tail gas treatment involves conveying solvent vapor generated from solvent evaporation to the lower section of an adsorption tower via a fan. A liquid adsorbent for adsorbing the solvent vapor is sprayed from the upper section of the adsorption tower and mixes with the solvent vapor within the tower. After adsorption, the liquid is discharged from the bottom of the adsorption tower, and the gas is discharged from the top. This invention uses counter-current convection between the liquid adsorbent and the tail gas to achieve adsorption of solvent vapor in the tail gas. Compared to the existing technology using solid adsorbents, this simplifies the entire process and reduces production costs.

[0004] Chinese patent application CN202111434010.2 relates to a modified flash-evaporated polyethylene composite material, characterized in that the raw materials of the composite material are polyethylene and composite additives; the loss value of the flexural stiffness ΔG of the composite material is 0.05~0.4; ΔG=1G2 / G1; G1 is the flexural stiffness of the composite material without aging treatment, in mN·cm; G2 is the flexural stiffness of the composite material after aging treatment, in mN·cm; the flexural stiffness G2 of the composite material after aging treatment is 20~100 mN·cm. The product of this application still has a certain flexural stiffness after aging, which can extend the service life of the product. Summary of the Invention

[0005] The purpose of this invention is to address the above-mentioned problems by providing a fold-resistant film material and its preparation method.

[0006] To achieve the above objectives, the present invention adopts the following technical solutions:

[0007] A fold-resistant film material, the raw material of which includes polyethylene,

[0008] The total crease recovery angle of the fold-resistant film material is 60–95°, which is tested using the horizontal method.

[0009] The folding endurance of the folding film material is greater than 4.

[0010] The total crease recovery angle is 60-70°.

[0011] The total crease recovery angle is 70-80°.

[0012] The total crease recovery angle is 80-90°.

[0013] The total crease recovery angle is 90-95°.

[0014] The abrasion resistance index of the folding-resistant film material is 7000-13000 times / mg.

[0015] The wear resistance index is 7000-8000 times / mg.

[0016] The wear resistance index is 8000-9000 times / mg.

[0017] The wear resistance index is 9000-10000 times / mg.

[0018] The wear resistance index is 10,000 to 11,000 times / mg.

[0019] The wear resistance index is 11,000 to 12,000 times / mg.

[0020] The wear resistance index is 12,000 to 13,000 times / mg.

[0021] The wet tensile strength retention rate of the folding-resistant film material is 70-95%.

[0022] The wet tensile strength retention rate is 70-75%.

[0023] The wet tensile strength retention rate is 75-80%.

[0024] The wet tensile strength retention rate is 80-85%.

[0025] The wet tensile strength retention rate is 85-90%.

[0026] The wet tensile strength retention rate is 90-95%.

[0027] A method for preparing a fold-resistant film material, comprising the following specific steps:

[0028] (1) Preparation of modified polyethylene:

[0029] Sea urchin-shaped copper oxide microspheres were dispersed in a barium sulfide solution, and then a zinc sulfate solution was added. The precipitate was filtered and calcined to obtain inorganic particles of zinc barium white-filled sea urchin-shaped copper oxide microspheres. Then, the inorganic particles of zinc barium white-filled sea urchin-shaped copper oxide microspheres, titanate coupling agent, and polyethylene were mixed, and then melt-extruded and granulated to obtain modified polyethylene containing sea urchin-shaped copper oxide microspheres.

[0030] The molar ratio of barium sulfide in the barium sulfide solution to zinc sulfate in the zinc sulfate solution is 1:1.

[0031] The molar ratio of sea urchin-shaped copper oxide microspheres to barium sulfide in the barium sulfide solution is 1:3 to 1:7.

[0032] The mass fraction of inorganic particles in modified polyethylene is 3.5%–5.5%;

[0033] The mass fraction of titanate coupling agent in modified polyethylene is 0.25–1.5%;

[0034] The sea urchin-shaped copper oxide microspheres were tested by BET, and the specific surface area of ​​the microspheres was 28-30 m² / g. According to the pore size distribution obtained by the BJH method, the total pore volume was 0.05-0.1 cm³ / g, and the average pore radius was 3-10 nm.

[0035] The antibacterial mechanism of sea urchin-shaped copper oxide microspheres is as follows: When the sea urchin-shaped copper oxide microspheres are excited by light with energy greater than the band gap, the generated hole / electron pairs react with water and oxygen to produce free radicals. These oxidizing hydroxyl free radicals react chemically with organic molecules in the cells, decomposing the cells and thus achieving the antibacterial purpose.

[0036] (2) Preparation of spinning solution:

[0037] Modified polyethylene is dissolved in a spinning solvent to obtain a spinning solution;

[0038] The mass fraction of modified polyethylene in the spinning solution is 7-18%, preferably 10-13%;

[0039] The spinning solvent is a mixture of several of the following: aromatic hydrocarbons, aliphatic hydrocarbons, alicyclic hydrocarbons, unsaturated hydrocarbons, halogenated hydrocarbons, alcohols, esters, ethers, ketones, nitriles, amides, and fluorocarbons.

[0040] (3) Preparation of fold-resistant film material:

[0041] The spinning solution is flash-spun at 190–215°C to obtain flash-spun fibers, which are then laid into a web. The film material is first subjected to a hot pressing process, then calendered by a calender, and finally stretched by tension control before winding to obtain a fold-resistant film material.

[0042] The hot pressing process uses hot rollers for hot pressing, and the hot pressing temperature is 110-125℃.

[0043] The calendering process uses a calendering machine with a roller surface temperature of T1 and a melt melting point of 135℃. Definition: T = T1 - 135℃; T is -2 to 20℃, preferably 0 to 10℃, and most preferably 0 to 5℃.

[0044] Test methods and corresponding test standards for physical property parameters:

[0045] 1. Total crease recovery angle

[0046] GB / T 3819-1997 Textiles - Determination of Crease Resilience of Fabrics - Recovery Angle Method

[0047] Principle: Samples of a certain shape and size are stacked and pressurized under specified conditions for a certain period of time. After the load is removed, the samples are allowed to recover for a certain period of time, and then the crease recovery angle is measured. The measured angle represents the crease recovery ability of the fabric.

[0048] Recovery angle: Under specified conditions, after the load is removed from a folded specimen and a certain period of time has elapsed, the angle formed between the two folded surfaces.

[0049] Crease horizontal recovery: When the crease of the sample recovers, the crease line is parallel to the horizontal plane, and the recovery angle is measured.

[0050] The total crease recovery angle is the sum of the average warp crease recovery angle and the average weft crease recovery angle, and is tested according to the horizontal method in 9.1 of GB / T 3819-1997.

[0051] 2. Flexural endurance

[0052] GB / T 457-2008 Determination of folding endurance of paper and paperboard

[0053] Principle: Under standard conditions, the specimen is subjected to longitudinal tension, folding backward and forward until the specimen breaks.

[0054] Flexural endurance: The logarithm of the number of double folds (base 10) at which the specimen breaks under standard tension conditions.

[0055] Folding endurance: The anti-positive number of the average folding endurance. In this test, the sample was found to have a folding endurance greater than 10,000 times.

[0056] 3. Abrasion resistance index

[0057] GB / T 21196.3-2007 Textiles - Martindale Method - Determination of Abrasion Resistance of Fabrics - Part 3: Determination of Mass Loss

[0058] Principle: A circular sample placed in the sample holder of a Martindale abrasion tester is subjected to a specified frictional load and undergoes planar motion with a Liszt-shaped trajectory to rub against a standard abrasive. The sample holder can rotate freely around its axis perpendicular to the horizontal plane. During the test, the mass of the sample is weighed at intervals, and the abrasion resistance of the fabric is determined based on the mass loss of the sample.

[0059] The wear resistance index is the ratio of the total number of friction cycles to the mass loss.

[0060] 4. Wet tensile strength retention rate

[0061] GB / T 24328.4-2009 Toilet paper and its products - Part 4: Determination of wet tensile strength

[0062] Principle: A sample of specified size is immersed in water for a specified time under specified conditions, and then stretched at a constant speed until it breaks on a tensile strength tester, and the tensile strength is recorded.

[0063] Wet tensile strength: The maximum tensile strength that a wet specimen per unit width can withstand before fracture when it is immersed in distilled water, expressed in N / m.

[0064] Wet tensile strength retention rate: The ratio of the tensile strength of the same sample after wetting to the tensile strength before wetting under standard atmospheric pressure, expressed as a percentage.

[0065] The test conditions for this application are: constant tensile speed of 50 mm / min; immersion time of 8 hours and temperature of 40℃.

[0066] 5. Antibacterial rate

[0067] GB / T 20944.2-2007 Evaluation of antimicrobial properties of textiles - Part 2: Absorption method

[0068] Antibacterial properties: The sample has the ability to inhibit bacterial growth.

[0069] Principle: The sample and control sample are inoculated with test bacterial solution respectively; then immediate elution and elution after incubation are performed respectively. The number of bacteria in the eluent is measured and the inhibition value or inhibition rate is calculated to evaluate the antibacterial effect.

[0070] The bacterial strains used in this application are: Staphylococcus aureus (abbreviation S), Klebsiella pneumoniae (abbreviation K), and Escherichia coli (abbreviation E). In Table 1, S represents the inhibition rate against Staphylococcus aureus, K represents the inhibition rate against Klebsiella pneumoniae, and E represents the inhibition rate against Escherichia coli.

[0071] Compared with existing technologies, the advantages of this invention are:

[0072] 1. This invention improves the raw materials and spinning process, so that the resulting membrane material has better total crease recovery angle and folding resistance, thereby overcoming the problems existing in the prior art.

[0073] 2. This invention utilizes the urchin-shaped copper oxide microspheres to fill with zinc barium white, achieving uniform dispersion. At the same time, it can cover the black color of the urchin-shaped copper oxide microspheres themselves, and provide a slow-release antibacterial function (with a longer-lasting antibacterial effect than ordinary copper oxide particles). This avoids negative impacts on the printing and color of the final product film material and provides a long-lasting slow-release antibacterial function. Detailed Implementation

[0074] The present invention will now be described in further detail with reference to specific embodiments.

[0075] Example 1

[0076] This embodiment provides a method for preparing a fold-resistant film material, specifically including the following steps:

[0077] (1) Preparation of modified polyethylene:

[0078] Sea urchin-shaped copper oxide microspheres were dispersed in a barium sulfide solution, and then a zinc sulfate solution was added. The precipitate was filtered and calcined to obtain inorganic particles of zinc barium white-filled sea urchin-shaped copper oxide microspheres. Then, the inorganic particles of zinc barium white-filled sea urchin-shaped copper oxide microspheres, titanate coupling agent, and polyethylene were mixed, and then melt-extruded and granulated to obtain modified polyethylene containing sea urchin-shaped copper oxide microspheres.

[0079] The molar ratio of barium sulfide in the barium sulfide solution to zinc sulfate in the zinc sulfate solution is 1:1.

[0080] The molar ratio of sea urchin-shaped copper oxide microspheres to barium sulfide in the barium sulfide solution is 1:3;

[0081] The mass fraction of inorganic particles in the modified polyethylene is 3.5%;

[0082] The mass fraction of titanate coupling agent in modified polyethylene is 0.25%;

[0083] (2) Preparation of spinning solution:

[0084] Modified polyethylene is dissolved in a spinning solvent to obtain a spinning solution;

[0085] The mass fraction of modified polyethylene in the spinning solution is 10%;

[0086] The spinning solvent is a mixture of dichloromethane, 1,1-dichloro-2,2,2-trifluoroethane (HC-123), 1,1,1,3,3-pentafluorobutane, and 1H,6H-perfluorohexane; the mass ratio of the four is 6:3:1:1.

[0087] (3) Preparation of fold-resistant film material:

[0088] The spinning solution is flash-spun at 195℃ to obtain flash fibers, which are then laid into a web. The web is first hot-pressed, then calendered using a calender, and finally stretched under tension control before winding to obtain a fold-resistant film material. Specifically, the film material enters the calender at a speed of 100 m / min, and after passing through the calender, it is stretched and wound under tension control before the winding machine at a speed of 110 m / min. The elongation rate during this process is 10%.

[0089] The hot pressing process uses hot rollers for hot pressing at a temperature of 110℃.

[0090] The calendering process uses a calendering machine. The roller surface temperature of the calendering machine is T1, and the melting point of the melt is 135℃. Definition: T = T1 - 135℃; T is 0℃.

[0091] The product test data for Example 1 are shown in Table 1.

[0092] Example 2

[0093] This embodiment provides a method for preparing a fold-resistant film material, specifically including the following steps:

[0094] (1) Preparation of modified polyethylene:

[0095] Sea urchin-shaped copper oxide microspheres were dispersed in a barium sulfide solution, and then a zinc sulfate solution was added. The precipitate was filtered and calcined to obtain inorganic particles of zinc barium white-filled sea urchin-shaped copper oxide microspheres. Then, the inorganic particles of zinc barium white-filled sea urchin-shaped copper oxide microspheres, titanate coupling agent, and polyethylene were mixed, and then melt-extruded and granulated to obtain modified polyethylene containing sea urchin-shaped copper oxide microspheres.

[0096] The molar ratio of barium sulfide in the barium sulfide solution to zinc sulfate in the zinc sulfate solution is 1:1.

[0097] The molar ratio of sea urchin-shaped copper oxide microspheres to barium sulfide in the barium sulfide solution is 1:4;

[0098] The mass fraction of inorganic particles in the modified polyethylene is 4%;

[0099] The mass fraction of titanate coupling agent in modified polyethylene is 0.5%;

[0100] (2) Preparation of spinning solution:

[0101] Modified polyethylene is dissolved in a spinning solvent to obtain a spinning solution;

[0102] The mass fraction of modified polyethylene in the spinning solution is 11%;

[0103] The spinning solvent is a mixture of dichloromethane, 1,1-dichloro-2,2,2-trifluoroethane (HC-123), 1,1,1,3,3-pentafluorobutane, and 1H,6H-perfluorohexane; the mass ratio of the four is 6:3:1:1.

[0104] (3) Preparation of fold-resistant film material:

[0105] The spinning solution is flash-spun at 200℃ to obtain flash fibers, which are then laid into a web. The web is first hot-pressed, then calendered using a calender, and finally stretched under tension control before being wound up to obtain a fold-resistant film material. The film material enters the calender at a speed of 100 m / min, and after passing through the calender, it is stretched and wound up under tension control before the winding machine at a speed of 115 m / min. The elongation rate during this process is 15%.

[0106] The hot pressing process uses hot rollers for hot pressing at a temperature of 115℃.

[0107] The calendering process uses a calendering machine. The roller surface temperature of the calendering machine is T1, and the melting point of the melt is 135℃. Definition: T = T1 - 135℃; T is 2℃.

[0108] The product test data for Example 2 are shown in Table 1.

[0109] Example 3

[0110] This embodiment provides a method for preparing a fold-resistant film material, specifically including the following steps:

[0111] (1) Preparation of modified polyethylene:

[0112] Sea urchin-shaped copper oxide microspheres were dispersed in a barium sulfide solution, and then a zinc sulfate solution was added. The precipitate was filtered and calcined to obtain inorganic particles of zinc barium white-filled sea urchin-shaped copper oxide microspheres. Then, the inorganic particles of zinc barium white-filled sea urchin-shaped copper oxide microspheres, titanate coupling agent, and polyethylene were mixed, and then melt-extruded and granulated to obtain modified polyethylene containing sea urchin-shaped copper oxide microspheres.

[0113] The molar ratio of barium sulfide in the barium sulfide solution to zinc sulfate in the zinc sulfate solution is 1:1.

[0114] The molar ratio of sea urchin-shaped copper oxide microspheres to barium sulfide in the barium sulfide solution is 1:5;

[0115] The mass fraction of inorganic particles in the modified polyethylene is 4.5%;

[0116] The mass fraction of titanate coupling agent in modified polyethylene is 0.75%;

[0117] (2) Preparation of spinning solution:

[0118] Modified polyethylene is dissolved in a spinning solvent to obtain a spinning solution;

[0119] The mass fraction of modified polyethylene in the spinning solution is 12%;

[0120] The spinning solvent is a mixture of dichloromethane, 1,1-dichloro-2,2,2-trifluoroethane (HC-123), 1,1,1,3,3-pentafluorobutane, and 1H,6H-perfluorohexane; the mass ratio of the four is 6:3:1:1.

[0121] (3) Preparation of fold-resistant film materials:

[0122] The spinning solution is flash-spun at 205℃ to obtain flash fibers, which are then laid into a web. First, a hot-pressing process is performed, followed by calendering the membrane material through a calender. Then, it is stretched under tension control before being wound up to obtain a fold-resistant film material. Specifically, the membrane material enters the calender at a speed of 100 m / min, and after passing through the calender, it is stretched and wound up under tension control before the winding machine at a speed of 120 m / min; the elongation rate during this process is 20%.

[0123] The hot pressing process uses hot rollers for hot pressing at a temperature of 120℃.

[0124] The calendering process uses a calendering machine. The roller surface temperature of the calendering machine is T1, and the melting point of the melt is 135℃. Definition: T = T1 - 135℃; T is 4℃.

[0125] The product test data for Example 3 are shown in Table 1.

[0126] In addition, the product of Example 3 underwent hot air aging treatment. The specific procedure was as follows: the sample was placed horizontally in an oven at 80°C for 168 hours; it was then removed and left to stand at 23°C for 24 hours, and the change in antibacterial rate after hot air aging was tested. The antibacterial rate S against Staphylococcus aureus was 96.6%, the antibacterial rate K against Klebsiella pneumoniae was 96.3%, and the antibacterial rate E against Escherichia coli was 96.2%.

[0127] Example 4

[0128] This embodiment provides a method for preparing a fold-resistant film material, specifically including the following steps:

[0129] (1) Preparation of modified polyethylene:

[0130] Sea urchin-shaped copper oxide microspheres were dispersed in a barium sulfide solution, and then a zinc sulfate solution was added. The precipitate was filtered and calcined to obtain inorganic particles of zinc barium white-filled sea urchin-shaped copper oxide microspheres. Then, the inorganic particles of zinc barium white-filled sea urchin-shaped copper oxide microspheres, titanate coupling agent, and polyethylene were mixed, and then melt-extruded and granulated to obtain modified polyethylene containing sea urchin-shaped copper oxide microspheres.

[0131] The molar ratio of barium sulfide in the barium sulfide solution to zinc sulfate in the zinc sulfate solution is 1:1.

[0132] The molar ratio of sea urchin-shaped copper oxide microspheres to barium sulfide in the barium sulfide solution is 1:6.

[0133] The mass fraction of inorganic particles in the modified polyethylene is 5%;

[0134] The mass fraction of the titanate coupling agent in the modified polyethylene is 1%;

[0135] (2) Preparation of spinning solution:

[0136] Modified polyethylene is dissolved in a spinning solvent to obtain a spinning solution;

[0137] The mass fraction of modified polyethylene in the spinning solution is 12.5%;

[0138] The spinning solvent is a mixture of dichloromethane, 1,1-dichloro-2,2,2-trifluoroethane (HC-123), 1,1,1,3,3-pentafluorobutane, and 1H,6H-perfluorohexane; the mass ratio of the four is 6:3:1:1.

[0139] (3) Preparation of fold-resistant film materials:

[0140] The spinning solution is flash-spun at 210℃ to obtain flash fibers, which are then laid into a web. First, a hot-pressing process is performed, followed by calendering the membrane material through a calender. Then, it is stretched under tension control before being wound up to obtain a fold-resistant film material. Specifically, the membrane material enters the calender at a speed of 100 m / min, and after passing through the calender, it is stretched and wound up under tension control before the winding machine at a speed of 125 m / min; the elongation rate during this process is 25%.

[0141] The hot pressing process uses hot rollers for hot pressing at a temperature of 120℃.

[0142] The calendering process uses a calendering machine. The roller surface temperature of the calendering machine is T1, and the melting point of the melt is 135℃. Definition: T = T1 - 135℃; T is 6℃.

[0143] The product test data for Example 4 are shown in Table 1.

[0144] Example 5

[0145] This embodiment provides a method for preparing a fold-resistant film material, specifically including the following steps:

[0146] (1) Preparation of modified polyethylene:

[0147] Sea urchin-shaped copper oxide microspheres were dispersed in a barium sulfide solution, and then a zinc sulfate solution was added. The precipitate was filtered and calcined to obtain inorganic particles of zinc barium white-filled sea urchin-shaped copper oxide microspheres. Then, the inorganic particles of zinc barium white-filled sea urchin-shaped copper oxide microspheres, titanate coupling agent, and polyethylene were mixed, and then melt-extruded and granulated to obtain modified polyethylene containing sea urchin-shaped copper oxide microspheres.

[0148] The molar ratio of barium sulfide in the barium sulfide solution to zinc sulfate in the zinc sulfate solution is 1:1.

[0149] The molar ratio of sea urchin-shaped copper oxide microspheres to barium sulfide in the barium sulfide solution is 1:7;

[0150] The mass fraction of inorganic particles in the modified polyethylene is 5.5%;

[0151] The mass fraction of titanate coupling agent in modified polyethylene is 1.25%;

[0152] (2) Preparation of spinning solution:

[0153] Modified polyethylene is dissolved in a spinning solvent to obtain a spinning solution;

[0154] The mass fraction of modified polyethylene in the spinning solution is 13%;

[0155] The spinning solvent is a mixture of dichloromethane, 1,1-dichloro-2,2,2-trifluoroethane (HC-123), 1,1,1,3,3-pentafluorobutane, and 1H,6H-perfluorohexane; the mass ratio of the four is 6:3:1:1.

[0156] (3) Preparation of fold-resistant film materials:

[0157] The spinning solution is flash-spun at 215℃ to obtain flash fibers, which are then laid into a web. The web is first hot-pressed, then calendered using a calender, and finally stretched under tension control before being wound up to obtain a fold-resistant film material. Specifically, the film material enters the calender at a speed of 100 m / min, and after passing through the calender, it is stretched and wound up under tension control at a speed of 130 m / min; the elongation during this process is 30%.

[0158] The hot pressing process uses hot rollers for hot pressing at a temperature of 125℃.

[0159] The calendering process uses a calendering machine. The roller surface temperature of the calendering machine is T1, and the melting point of the melt is 135℃. Definition: T = T1 - 135℃; T is 8℃.

[0160] The product test data for Example 5 are shown in Table 1.

[0161] Comparative Example 1

[0162] This comparative example provides a method for preparing a fold-resistant film material, specifically including the following steps:

[0163] (1) Preparation of modified polyethylene:

[0164] Sea urchin-shaped copper oxide microspheres, zinc barium white, titanate coupling agent and polyethylene are first mixed, and then melt extruded and granulated to obtain modified polyethylene containing sea urchin-shaped copper oxide microspheres.

[0165] The mass fraction of urchin-shaped copper oxide microspheres in modified polyethylene is 1%.

[0166] The mass fraction of zinc barium white in modified polyethylene is 3.5%;

[0167] The mass fraction of titanate coupling agent in modified polyethylene is 0.75%;

[0168] (2) Preparation of spinning solution:

[0169] Modified polyethylene is dissolved in a spinning solvent to obtain a spinning solution;

[0170] The mass fraction of modified polyethylene in the spinning solution is 12%;

[0171] The spinning solvent is a mixture of dichloromethane, 1,1-dichloro-2,2,2-trifluoroethane (HC-123), 1,1,1,3,3-pentafluorobutane, and 1H,6H-perfluorohexane; the mass ratio of the four is 6:3:1:1.

[0172] (3) Preparation of fold-resistant film materials:

[0173] The spinning solution is flash-spun at 205℃ to obtain flash fibers, which are then laid into a web. First, a hot-pressing process is performed, followed by calendering the membrane material through a calender. Then, it is stretched under tension control before being wound up to obtain a fold-resistant film material. Specifically, the membrane material enters the calender at a speed of 100 m / min, and after passing through the calender, it is stretched and wound up under tension control before the winding machine at a speed of 120 m / min; the elongation rate during this process is 20%.

[0174] The hot pressing process uses hot rollers for hot pressing at a temperature of 120℃.

[0175] The calendering process uses a calendering machine. The roller surface temperature of the calendering machine is T1, and the melting point of the melt is 135℃. Definition: T = T1 - 135℃; T is 4℃.

[0176] The product test data for Comparative Example 1 are shown in Table 1.

[0177] Comparative Example 2

[0178] This comparative example provides a method for preparing a fold-resistant film material, specifically including the following steps:

[0179] (1) Preparation of modified polyethylene:

[0180] Copper oxide powder was dispersed in barium sulfide solution, and then zinc sulfate solution was added. The precipitate was filtered and calcined to obtain inorganic particles of zinc barium white-filled sea urchin-shaped copper oxide microspheres. Then, the inorganic particles of zinc barium white-filled sea urchin-shaped copper oxide microspheres, titanate coupling agent and polyethylene were mixed, and then melt extruded and granulated to obtain modified polyethylene containing copper oxide.

[0181] The molar ratio of barium sulfide in the barium sulfide solution to zinc sulfate in the zinc sulfate solution is 1:1.

[0182] The molar ratio of copper oxide powder to barium sulfide in the barium sulfide solution is 1:5;

[0183] The mass fraction of inorganic particles in the modified polyethylene is 4.5%;

[0184] The mass fraction of titanate coupling agent in modified polyethylene is 0.75%;

[0185] (2) Preparation of spinning solution:

[0186] Modified polyethylene is dissolved in a spinning solvent to obtain a spinning solution;

[0187] The mass fraction of modified polyethylene in the spinning solution is 12%;

[0188] The spinning solvent is a mixture of dichloromethane, 1,1-dichloro-2,2,2-trifluoroethane (HC-123), 1,1,1,3,3-pentafluorobutane, and 1H,6H-perfluorohexane; the mass ratio of the four is 6:3:1:1.

[0189] (3) Preparation of fold-resistant film materials:

[0190] The spinning solution is flash-spun at 205℃ to obtain flash fibers, which are then laid into a web. First, a hot-pressing process is performed, followed by calendering the membrane material through a calender. Then, it is stretched under tension control before being wound up to obtain a fold-resistant film material. Specifically, the membrane material enters the calender at a speed of 100 m / min, and after passing through the calender, it is stretched and wound up under tension control before the winding machine at a speed of 120 m / min; the elongation rate during this process is 20%.

[0191] The hot pressing process uses hot rollers for hot pressing at a temperature of 120℃.

[0192] The calendering process uses a calendering machine. The roller surface temperature of the calendering machine is T1, and the melting point of the melt is 135℃. Definition: T = T1 - 135℃; T is 4℃.

[0193] The product test data for Comparative Example 2 are shown in Table 1.

[0194] In addition, the product of Comparative Example 2 underwent hot air aging treatment. The specific procedure was as follows: the sample was placed horizontally in an oven at 80°C for 168 hours; it was then removed and allowed to stand at 23°C for 24 hours, and the change in antibacterial rate after hot air aging was tested. The antibacterial rate S against Staphylococcus aureus was 85.1%, the antibacterial rate K against Klebsiella pneumoniae was 86.8%, and the antibacterial rate E against Escherichia coli was 84.9%. Compared with Example 3, the antibacterial performance decreased significantly.

[0195] Comparative Example 3

[0196] This comparative example provides a method for preparing a fold-resistant film material, specifically including the following steps:

[0197] (1) Preparation of modified polyethylene:

[0198] Sea urchin-shaped copper oxide microspheres were dispersed in a barium sulfide solution, and then a zinc sulfate solution was added. The precipitate was filtered and calcined to obtain inorganic particles of zinc barium white-filled sea urchin-shaped copper oxide microspheres. Then, the inorganic particles of zinc barium white-filled sea urchin-shaped copper oxide microspheres, titanate coupling agent, and polyethylene were mixed, and then melt-extruded and granulated to obtain modified polyethylene containing sea urchin-shaped copper oxide microspheres.

[0199] The molar ratio of barium sulfide in the barium sulfide solution to zinc sulfate in the zinc sulfate solution is 1:1.

[0200] The molar ratio of sea urchin-shaped copper oxide microspheres to barium sulfide in the barium sulfide solution is 1:5;

[0201] The mass fraction of inorganic particles in the modified polyethylene is 4.5%;

[0202] The mass fraction of titanate coupling agent in modified polyethylene is 0.75%;

[0203] (2) Preparation of spinning solution:

[0204] Modified polyethylene is dissolved in a spinning solvent to obtain a spinning solution;

[0205] The mass fraction of modified polyethylene in the spinning solution is 12%;

[0206] The spinning solvent is a mixture of dichloromethane, 1,1-dichloro-2,2,2-trifluoroethane (HC-123), 1,1,1,3,3-pentafluorobutane, and 1H,6H-perfluorohexane; the mass ratio of the four is 6:3:1:1.

[0207] (3) Preparation of fold-resistant film materials:

[0208] The spinning solution is flash-spun at 205℃ to obtain flash fibers, which are then laid into a web. First, a hot-pressing process is performed, followed by calendering the membrane material through a calender. Then, it is stretched under tension control before being wound up to obtain a fold-resistant film material. Specifically, the membrane material enters the calender at a speed of 100 m / min, and after passing through the calender, it is stretched and wound up under tension control before the winding machine at a speed of 120 m / min; the elongation rate during this process is 20%.

[0209] The hot pressing process uses hot rollers for hot pressing at a temperature of 120℃.

[0210] The calendering process uses a calendering machine. The roller surface temperature of the calendering machine is T1, and the melting point of the melt is 135℃. Definition: T = T1 - 135℃; T is -4.5℃.

[0211] The product test data for Comparative Example 3 are shown in Table 1.

[0212] Comparative Example 4

[0213] This comparative example provides a method for preparing a fold-resistant film material, specifically including the following steps:

[0214] (1) Preparation of modified polyethylene:

[0215] Sea urchin-shaped copper oxide microspheres were dispersed in a barium sulfide solution, and then a zinc sulfate solution was added. The precipitate was filtered and calcined to obtain inorganic particles of zinc barium white-filled sea urchin-shaped copper oxide microspheres. Then, the inorganic particles of zinc barium white-filled sea urchin-shaped copper oxide microspheres, titanate coupling agent, and polyethylene were mixed, and then melt-extruded and granulated to obtain modified polyethylene containing sea urchin-shaped copper oxide microspheres.

[0216] The molar ratio of barium sulfide in the barium sulfide solution to zinc sulfate in the zinc sulfate solution is 1:1.

[0217] The molar ratio of sea urchin-shaped copper oxide microspheres to barium sulfide in the barium sulfide solution is 1:5;

[0218] The mass fraction of inorganic particles in the modified polyethylene is 4.5%;

[0219] The mass fraction of titanate coupling agent in modified polyethylene is 0.75%;

[0220] (2) Preparation of spinning solution:

[0221] Modified polyethylene is dissolved in a spinning solvent to obtain a spinning solution;

[0222] The mass fraction of modified polyethylene in the spinning solution is 12%;

[0223] The spinning solvent is a mixture of dichloromethane, 1,1-dichloro-2,2,2-trifluoroethane (HC-123), 1,1,1,3,3-pentafluorobutane, and 1H,6H-perfluorohexane; the mass ratio of the four is 6:3:1:1.

[0224] (3) Preparation of fold-resistant film materials:

[0225] The spinning solution is flash-spun at 205℃ to obtain flash fibers, which are then laid into a web. First, a hot-pressing process is performed, followed by calendering the membrane material through a calender. Then, it is stretched under tension control before being wound up to obtain a fold-resistant film material. Specifically, the membrane material enters the calender at a speed of 100 m / min, and after passing through the calender, it is stretched and wound up under tension control before the winding machine at a speed of 120 m / min; the elongation rate during this process is 20%.

[0226] The hot pressing process uses hot rollers for hot pressing at a temperature of 120℃.

[0227] The calendering process uses a calendering machine. The roller surface temperature of the calendering machine is T1, and the melting point of the melt is 135℃. Definition: T = T1 - 135℃; T is -3.5℃.

[0228] The product test data for Comparative Example 4 are shown in Table 1.

[0229] Comparative Example 5

[0230] This comparative example provides a method for preparing a fold-resistant film material, specifically including the following steps:

[0231] (1) Preparation of modified polyethylene:

[0232] Sea urchin-shaped copper oxide microspheres were dispersed in a barium sulfide solution, and then a zinc sulfate solution was added. The precipitate was filtered and calcined to obtain inorganic particles of zinc barium white-filled sea urchin-shaped copper oxide microspheres. Then, the inorganic particles of zinc barium white-filled sea urchin-shaped copper oxide microspheres, titanate coupling agent, and polyethylene were mixed, and then melt-extruded and granulated to obtain modified polyethylene containing sea urchin-shaped copper oxide microspheres.

[0233] The molar ratio of barium sulfide in the barium sulfide solution to zinc sulfate in the zinc sulfate solution is 1:1.

[0234] The molar ratio of sea urchin-shaped copper oxide microspheres to barium sulfide in the barium sulfide solution is 1:5;

[0235] The mass fraction of inorganic particles in the modified polyethylene is 4.5%;

[0236] The mass fraction of titanate coupling agent in modified polyethylene is 0.75%;

[0237] (2) Preparation of spinning solution:

[0238] Modified polyethylene is dissolved in a spinning solvent to obtain a spinning solution;

[0239] The mass fraction of modified polyethylene in the spinning solution is 12%;

[0240] The spinning solvent is a mixture of dichloromethane, 1,1-dichloro-2,2,2-trifluoroethane (HC-123), 1,1,1,3,3-pentafluorobutane, and 1H,6H-perfluorohexane; the mass ratio of the four is 6:3:1:1.

[0241] (3) Preparation of fold-resistant film materials:

[0242] The spinning solution is flash-spun at 205℃ to obtain flash fibers, which are then laid into a web. First, a hot-pressing process is performed, followed by calendering the membrane material through a calender. Then, it is stretched under tension control before being wound up to obtain a fold-resistant film material. Specifically, the membrane material enters the calender at a speed of 100 m / min, and after passing through the calender, it is stretched and wound up under tension control before the winding machine at a speed of 120 m / min; the elongation rate during this process is 20%.

[0243] The hot pressing process uses hot rollers for hot pressing at a temperature of 120℃.

[0244] The calendering process uses a calendering machine. The roller surface temperature of the calendering machine is T1, and the melting point of the melt is 135℃. Definition: T = T1 - 135℃; T is 22.5℃.

[0245] The product test data for Comparative Example 5 are shown in Table 1.

[0246] Comparative Example 6

[0247] This comparative example provides a method for preparing a fold-resistant film material, specifically including the following steps:

[0248] (1) Preparation of modified polyethylene:

[0249] Sea urchin-shaped copper oxide microspheres were dispersed in a barium sulfide solution, and then a zinc sulfate solution was added. The precipitate was filtered and calcined to obtain inorganic particles of zinc barium white-filled sea urchin-shaped copper oxide microspheres. Then, the inorganic particles of zinc barium white-filled sea urchin-shaped copper oxide microspheres, titanate coupling agent, and polyethylene were mixed, and then melt-extruded and granulated to obtain modified polyethylene containing sea urchin-shaped copper oxide microspheres.

[0250] The molar ratio of barium sulfide in the barium sulfide solution to zinc sulfate in the zinc sulfate solution is 1:1.

[0251] The molar ratio of sea urchin-shaped copper oxide microspheres to barium sulfide in the barium sulfide solution is 1:5;

[0252] The mass fraction of inorganic particles in the modified polyethylene is 4.5%;

[0253] The mass fraction of titanate coupling agent in modified polyethylene is 0.75%;

[0254] (2) Preparation of spinning solution:

[0255] Modified polyethylene is dissolved in a spinning solvent to obtain a spinning solution;

[0256] The mass fraction of modified polyethylene in the spinning solution is 12%;

[0257] The spinning solvent is a mixture of dichloromethane, 1,1-dichloro-2,2,2-trifluoroethane (HC-123), 1,1,1,3,3-pentafluorobutane, and 1H,6H-perfluorohexane; the mass ratio of the four is 6:3:1:1.

[0258] (3) Preparation of fold-resistant film materials:

[0259] The spinning solution is flash-spun at 205℃ to obtain flash fibers, which are then laid into a web. First, a hot-pressing process is performed, followed by calendering the membrane material through a calender. Then, it is stretched under tension control before being wound up to obtain a fold-resistant film material. Specifically, the membrane material enters the calender at a speed of 100 m / min, and after passing through the calender, it is stretched and wound up under tension control before the winding machine at a speed of 120 m / min; the elongation rate during this process is 20%.

[0260] The hot pressing process uses hot rollers for hot pressing at a temperature of 120℃.

[0261] The calendering process uses a calendering machine. The roller surface temperature of the calendering machine is T1, and the melting point of the melt is 135℃. Definition: T = T1 - 135℃; T is 25℃.

[0262] The product in Comparative Example 6 was severely plasticized and was therefore a non-compliant product, so it was not tested further.

[0263] Comparative Example 7

[0264] This comparative example provides a method for preparing a fold-resistant film material, specifically including the following steps:

[0265] (1) Preparation of modified polyethylene:

[0266] Sea urchin-shaped copper oxide microspheres were dispersed in a barium sulfide solution, and then a zinc sulfate solution was added. The precipitate was filtered and calcined to obtain inorganic particles of zinc barium white-filled sea urchin-shaped copper oxide microspheres. Then, the inorganic particles of zinc barium white-filled sea urchin-shaped copper oxide microspheres, titanate coupling agent, and polyethylene were mixed, and then melt-extruded and granulated to obtain modified polyethylene containing sea urchin-shaped copper oxide microspheres.

[0267] The molar ratio of barium sulfide in the barium sulfide solution to zinc sulfate in the zinc sulfate solution is 1:1.

[0268] The molar ratio of sea urchin-shaped copper oxide microspheres to barium sulfide in the barium sulfide solution is 1:5;

[0269] The mass fraction of inorganic particles in the modified polyethylene is 4.5%;

[0270] The mass fraction of titanate coupling agent in modified polyethylene is 0.75%;

[0271] (2) Preparation of spinning solution:

[0272] Modified polyethylene is dissolved in a spinning solvent to obtain a spinning solution;

[0273] The mass fraction of modified polyethylene in the spinning solution is 12%;

[0274] The spinning solvent is a mixture of dichloromethane, 1,1-dichloro-2,2,2-trifluoroethane (HC-123), 1,1,1,3,3-pentafluorobutane, and 1H,6H-perfluorohexane; the mass ratio of the four is 6:3:1:1.

[0275] (3) Preparation of fold-resistant film materials:

[0276] The spinning solution is flash-spun at 205℃ to obtain flash fibers, which are then laid into a web. First, a hot-pressing process is performed, followed by calendering the membrane material through a calender. Then, it is stretched under tension control before being wound up to obtain a fold-resistant film material. Specifically, the membrane material enters the calender at a speed of 100 m / min, and after passing through the calender, it is stretched and wound up under tension control before the winding machine at a speed of 106 m / min; the elongation during this process is 6%.

[0277] The hot pressing process uses hot rollers for hot pressing at a temperature of 120℃.

[0278] The calendering process uses a calendering machine. The roller surface temperature of the calendering machine is T1, and the melting point of the melt is 135℃. Definition: T = T1 - 135℃; T is 4℃.

[0279] The product test data for Comparative Example 7 are shown in Table 1.

[0280] Comparative Example 8

[0281] This comparative example provides a method for preparing a fold-resistant film material, specifically including the following steps:

[0282] (1) Preparation of modified polyethylene:

[0283] Sea urchin-shaped copper oxide microspheres were dispersed in a barium sulfide solution, and then a zinc sulfate solution was added. The precipitate was filtered and calcined to obtain inorganic particles of zinc barium white-filled sea urchin-shaped copper oxide microspheres. Then, the inorganic particles of zinc barium white-filled sea urchin-shaped copper oxide microspheres, titanate coupling agent, and polyethylene were mixed, and then melt-extruded and granulated to obtain modified polyethylene containing sea urchin-shaped copper oxide microspheres.

[0284] The molar ratio of barium sulfide in the barium sulfide solution to zinc sulfate in the zinc sulfate solution is 1:1.

[0285] The molar ratio of sea urchin-shaped copper oxide microspheres to barium sulfide in the barium sulfide solution is 1:5;

[0286] The mass fraction of inorganic particles in the modified polyethylene is 4.5%;

[0287] The mass fraction of titanate coupling agent in modified polyethylene is 0.75%;

[0288] (2) Preparation of spinning solution:

[0289] Modified polyethylene is dissolved in a spinning solvent to obtain a spinning solution;

[0290] The mass fraction of modified polyethylene in the spinning solution is 12%;

[0291] The spinning solvent is a mixture of dichloromethane, 1,1-dichloro-2,2,2-trifluoroethane (HC-123), 1,1,1,3,3-pentafluorobutane, and 1H,6H-perfluorohexane; the mass ratio of the four is 6:3:1:1.

[0292] (3) Preparation of fold-resistant film materials:

[0293] The spinning solution is flash-spun at 205℃ to obtain flash fibers, which are then laid into a web. First, a hot-pressing process is performed, followed by calendering the film material through a calender. Then, it is stretched under tension control before being wound up to obtain a fold-resistant film material. Specifically, the film material enters the calender at a speed of 100 m / min, and after passing through the calender, it is stretched and wound up under tension control before the winding machine at a speed of 108 m / min; the elongation during this process is 8%.

[0294] The hot pressing process uses hot rollers for hot pressing at a temperature of 120℃.

[0295] The calendering process uses a calendering machine. The roller surface temperature of the calendering machine is T1, and the melting point of the melt is 135℃. Definition: T = T1 - 135℃; T is 4℃.

[0296] The product test data for Comparative Example 8 are shown in Table 1.

[0297] Comparative Example 9

[0298] This comparative example provides a method for preparing a fold-resistant film material, specifically including the following steps:

[0299] (1) Preparation of modified polyethylene:

[0300] Sea urchin-shaped copper oxide microspheres were dispersed in a barium sulfide solution, and then a zinc sulfate solution was added. The precipitate was filtered and calcined to obtain inorganic particles of zinc barium white-filled sea urchin-shaped copper oxide microspheres. Then, the inorganic particles of zinc barium white-filled sea urchin-shaped copper oxide microspheres, titanate coupling agent, and polyethylene were mixed, and then melt-extruded and granulated to obtain modified polyethylene containing sea urchin-shaped copper oxide microspheres.

[0301] The molar ratio of barium sulfide in the barium sulfide solution to zinc sulfate in the zinc sulfate solution is 1:1.

[0302] The molar ratio of sea urchin-shaped copper oxide microspheres to barium sulfide in the barium sulfide solution is 1:5;

[0303] The mass fraction of inorganic particles in the modified polyethylene is 4.5%;

[0304] The mass fraction of titanate coupling agent in modified polyethylene is 0.75%;

[0305] (2) Preparation of spinning solution:

[0306] Modified polyethylene is dissolved in a spinning solvent to obtain a spinning solution;

[0307] The mass fraction of modified polyethylene in the spinning solution is 12%;

[0308] The spinning solvent is a mixture of dichloromethane, 1,1-dichloro-2,2,2-trifluoroethane (HC-123), 1,1,1,3,3-pentafluorobutane, and 1H,6H-perfluorohexane; the mass ratio of the four is 6:3:1:1.

[0309] (3) Preparation of fold-resistant film materials:

[0310] The spinning solution is flash-spun at 205℃ to obtain flash fibers, which are then laid into a web. First, a hot-pressing process is performed, followed by calendering the film material through a calender. Then, it is stretched under tension control before being wound up to obtain a fold-resistant film material. Specifically, the film material enters the calender at a speed of 100 m / min, and after passing through the calender, it is stretched and wound up under tension control before the winding machine at a speed of 132 m / min; the elongation during this process is 32%.

[0311] The hot pressing process uses hot rollers for hot pressing at a temperature of 120℃.

[0312] The calendering process uses a calendering machine. The roller surface temperature of the calendering machine is T1, and the melting point of the melt is 135℃. Definition: T = T1 - 135℃; T is 4℃.

[0313] The product test data for Comparative Example 9 are shown in Table 1.

[0314] Comparative Example 10

[0315] This comparative example provides a method for preparing a fold-resistant film material, specifically including the following steps:

[0316] (1) Preparation of modified polyethylene:

[0317] Sea urchin-shaped copper oxide microspheres were dispersed in a barium sulfide solution, and then a zinc sulfate solution was added. The precipitate was filtered and calcined to obtain inorganic particles of zinc barium white-filled sea urchin-shaped copper oxide microspheres. Then, the inorganic particles of zinc barium white-filled sea urchin-shaped copper oxide microspheres, titanate coupling agent, and polyethylene were mixed, and then melt-extruded and granulated to obtain modified polyethylene containing sea urchin-shaped copper oxide microspheres.

[0318] The molar ratio of barium sulfide in the barium sulfide solution to zinc sulfate in the zinc sulfate solution is 1:1.

[0319] The molar ratio of sea urchin-shaped copper oxide microspheres to barium sulfide in the barium sulfide solution is 1:5;

[0320] The mass fraction of inorganic particles in the modified polyethylene is 4.5%;

[0321] The mass fraction of titanate coupling agent in modified polyethylene is 0.75%;

[0322] (2) Preparation of spinning solution:

[0323] Modified polyethylene is dissolved in a spinning solvent to obtain a spinning solution;

[0324] The mass fraction of modified polyethylene in the spinning solution is 12%;

[0325] The spinning solvent is a mixture of dichloromethane, 1,1-dichloro-2,2,2-trifluoroethane (HC-123), 1,1,1,3,3-pentafluorobutane, and 1H,6H-perfluorohexane; the mass ratio of the four is 6:3:1:1.

[0326] (3) Preparation of fold-resistant film materials:

[0327] The spinning solution is flash-spun at 205℃ to obtain flash fibers, which are then laid into a web. First, a hot-pressing process is performed, followed by calendering the film material through a calender. Then, it is stretched under tension control before being wound up to obtain a fold-resistant film material. Specifically, the film material enters the calender at a speed of 100 m / min, and after passing through the calender, it is stretched and wound up under tension control before the winding machine at a speed of 135 m / min; the elongation rate during this process is 35%.

[0328] The hot pressing process uses hot rollers for hot pressing at a temperature of 120℃.

[0329] The calendering process uses a calendering machine. The roller surface temperature of the calendering machine is T1, and the melting point of the melt is 135℃. Definition: T = T1 - 135℃; T is 4℃.

[0330] The product test data for Comparative Example 10 are shown in Table 1.

[0331] Comparative Example 11

[0332] This comparative example provides a method for preparing a fold-resistant film material, specifically including the following steps:

[0333] (1) Preparation of modified polyethylene:

[0334] Sea urchin-shaped copper oxide microspheres were dispersed in a barium sulfide solution, and then a zinc sulfate solution was added. The precipitate was filtered and calcined to obtain inorganic particles of zinc barium white-filled sea urchin-shaped copper oxide microspheres. Then, the inorganic particles of zinc barium white-filled sea urchin-shaped copper oxide microspheres, titanate coupling agent, and polyethylene were mixed, and then melt-extruded and granulated to obtain modified polyethylene containing sea urchin-shaped copper oxide microspheres.

[0335] The molar ratio of barium sulfide in the barium sulfide solution to zinc sulfate in the zinc sulfate solution is 1:1.

[0336] The molar ratio of sea urchin-shaped copper oxide microspheres to barium sulfide in the barium sulfide solution is 1:5;

[0337] The mass fraction of inorganic particles in the modified polyethylene is 6%;

[0338] The mass fraction of titanate coupling agent in modified polyethylene is 0.75%;

[0339] (2) Preparation of spinning solution:

[0340] Modified polyethylene is dissolved in a spinning solvent to obtain a spinning solution;

[0341] The mass fraction of modified polyethylene in the spinning solution is 12%;

[0342] The spinning solvent is a mixture of dichloromethane, 1,1-dichloro-2,2,2-trifluoroethane (HC-123), 1,1,1,3,3-pentafluorobutane, and 1H,6H-perfluorohexane; the mass ratio of the four is 6:3:1:1.

[0343] (3) Preparation of fold-resistant film materials:

[0344] The spinning solution is flash-spun at 205℃ to obtain flash fibers, which are then laid into a web. First, a hot-pressing process is performed, followed by calendering the membrane material through a calender. Then, it is stretched under tension control before being wound up to obtain a fold-resistant film material. Specifically, the membrane material enters the calender at a speed of 100 m / min, and after passing through the calender, it is stretched and wound up under tension control before the winding machine at a speed of 120 m / min; the elongation rate during this process is 20%.

[0345] The hot pressing process uses hot rollers for hot pressing at a temperature of 120℃.

[0346] The calendering process uses a calendering machine. The roller surface temperature of the calendering machine is T1, and the melting point of the melt is 135℃. Definition: T = T1 - 135℃; T is 4℃.

[0347] The product test data for Comparative Example 11 are shown in Table 1.

[0348] Comparative Example 12

[0349] This comparative example provides a method for preparing a fold-resistant film material, specifically including the following steps:

[0350] (1) Preparation of modified polyethylene:

[0351] Sea urchin-shaped copper oxide microspheres were dispersed in a barium sulfide solution, and then a zinc sulfate solution was added. The precipitate was filtered and calcined to obtain inorganic particles of zinc barium white-filled sea urchin-shaped copper oxide microspheres. Then, the inorganic particles of zinc barium white-filled sea urchin-shaped copper oxide microspheres, titanate coupling agent, and polyethylene were mixed, and then melt-extruded and granulated to obtain modified polyethylene containing sea urchin-shaped copper oxide microspheres.

[0352] The molar ratio of barium sulfide in the barium sulfide solution to zinc sulfate in the zinc sulfate solution is 1:1.

[0353] The molar ratio of sea urchin-shaped copper oxide microspheres to barium sulfide in the barium sulfide solution is 1:5;

[0354] The mass fraction of inorganic particles in the modified polyethylene is 7%;

[0355] The mass fraction of titanate coupling agent in modified polyethylene is 0.75%;

[0356] (2) Preparation of spinning solution:

[0357] Modified polyethylene is dissolved in a spinning solvent to obtain a spinning solution;

[0358] The mass fraction of modified polyethylene in the spinning solution is 12%;

[0359] The spinning solvent is a mixture of dichloromethane, 1,1-dichloro-2,2,2-trifluoroethane (HC-123), 1,1,1,3,3-pentafluorobutane, and 1H,6H-perfluorohexane; the mass ratio of the four is 6:3:1:1.

[0360] (3) Preparation of fold-resistant film material:

[0361] The spinning solution is flash-spun at 205℃ to obtain flash fibers, which are then laid into a web. First, a hot-pressing process is performed, followed by calendering the membrane material through a calender. Then, it is stretched under tension control before being wound up to obtain a fold-resistant film material. Specifically, the membrane material enters the calender at a speed of 100 m / min, and after passing through the calender, it is stretched and wound up under tension control before the winding machine at a speed of 120 m / min; the elongation rate during this process is 20%.

[0362] The hot pressing process uses hot rollers for hot pressing at a temperature of 120℃.

[0363] The calendering process uses a calendering machine. The roller surface temperature of the calendering machine is T1, and the melting point of the melt is 135℃. Definition: T = T1 - 135℃; T is 4℃.

[0364] The product test data for Comparative Example 12 are shown in Table 1.

[0365] Comparative Example 13

[0366] This comparative example provides a method for preparing a fold-resistant film material, specifically including the following steps:

[0367] (1) Preparation of modified polyethylene:

[0368] Sea urchin-shaped copper oxide microspheres were dispersed in a barium sulfide solution, and then a zinc sulfate solution was added. The precipitate was filtered and calcined to obtain inorganic particles of zinc barium white-filled sea urchin-shaped copper oxide microspheres. Then, the inorganic particles of zinc barium white-filled sea urchin-shaped copper oxide microspheres, titanate coupling agent, and polyethylene were mixed, and then melt-extruded and granulated to obtain modified polyethylene containing sea urchin-shaped copper oxide microspheres.

[0369] The molar ratio of barium sulfide in the barium sulfide solution to zinc sulfate in the zinc sulfate solution is 1:1.

[0370] The molar ratio of sea urchin-shaped copper oxide microspheres to barium sulfide in the barium sulfide solution is 1:5;

[0371] The mass fraction of inorganic particles in the modified polyethylene is 8%;

[0372] The mass fraction of titanate coupling agent in modified polyethylene is 0.75%;

[0373] (2) Preparation of spinning solution:

[0374] Modified polyethylene is dissolved in a spinning solvent to obtain a spinning solution;

[0375] The mass fraction of modified polyethylene in the spinning solution is 12%;

[0376] The spinning solvent is a mixture of dichloromethane, 1,1-dichloro-2,2,2-trifluoroethane (HC-123), 1,1,1,3,3-pentafluorobutane, and 1H,6H-perfluorohexane; the mass ratio of the four is 6:3:1:1.

[0377] (3) Preparation of fold-resistant film material:

[0378] The spinning solution is flash-spun at 205℃ to obtain flash fibers, which are then laid into a web. First, a hot-pressing process is performed, followed by calendering the membrane material through a calender. Then, it is stretched under tension control before being wound up to obtain a fold-resistant film material. Specifically, the membrane material enters the calender at a speed of 100 m / min, and after passing through the calender, it is stretched and wound up under tension control before the winding machine at a speed of 120 m / min; the elongation rate during this process is 20%.

[0379] The hot pressing process uses hot rollers for hot pressing at a temperature of 120℃.

[0380] The calendering process uses a calendering machine. The roller surface temperature of the calendering machine is T1, and the melting point of the melt is 135℃. Definition: T = T1 - 135℃; T is 4℃.

[0381] The product test data for Comparative Example 13 are shown in Table 1.

[0382] Table 1

[0383]

[0384]

[0385] Results analysis: By comparing the test data of Example 3 and Comparative Example 1, it can be seen that the method of filling zinc barium white onto sea urchin-shaped copper oxide microspheres in this invention can make the final membrane material have better wet tensile strength retention rate and antibacterial effect.

[0386] By comparing the test data and hot air aging treatment data of Example 3 and Comparative Example 2, it can be seen that the use of the sea urchin-shaped copper oxide microspheres in this invention can make the final membrane material have better long-lasting bactericidal performance.

[0387] By comparing the test data of Example 3 and Comparative Examples 3-6, it can be seen that by using the T value in this invention, the final membrane material can achieve better performance in terms of abrasion resistance index, total crease recovery angle, and wet tensile strength retention rate. While a T value that is too small will result in a larger total crease recovery angle, the abrasion resistance index and wet tensile strength retention rate will decrease significantly. While a T value that is too large will result in a larger abrasion resistance index and wet tensile strength retention rate, the total crease recovery angle will decrease significantly, and there is even a risk that the product will be severely plasticized and become a substandard product.

[0388] By comparing the test data of Example 3 and Comparative Examples 7-10, it can be seen that by using the winding speed and elongation of the present invention, the final film material can have a larger total crease recovery angle.

[0389] By comparing the test data of Example 3 and Comparative Examples 7-10, it can be seen that by using the amount of inorganic particles added in this invention, the final membrane material can have a larger total crease recovery angle.

[0390] The specific embodiments described herein are merely illustrative of the spirit of the invention. Those skilled in the art to which this invention pertains may make various modifications or additions to the described specific embodiments or use similar methods to substitute them, without departing from the spirit of the invention or exceeding the scope defined by the appended claims.

Claims

1. A fold-resistant film material, characterized in that: Its raw materials include polyethylene, and the total crease recovery angle of the folding film material is 60-95°, which is tested by the horizontal method; the folding endurance of the folding film material is greater than 4. The abrasion resistance index of the folding-resistant film material is 7000–13000 cycles / mg; The wet tensile strength retention rate of the folding-resistant film material is 70-95%; The fold-resistant film material is prepared by the following method: (1) Preparation of modified polyethylene: Sea urchin-shaped copper oxide microspheres were dispersed in a barium sulfide solution, and then a zinc sulfate solution was added. The precipitate was filtered and calcined to obtain inorganic particles of zinc barium white-filled sea urchin-shaped copper oxide microspheres. Then, the inorganic particles of zinc barium white-filled sea urchin-shaped copper oxide microspheres, titanate coupling agent, and polyethylene were mixed, and then melt-extruded and granulated to obtain modified polyethylene containing sea urchin-shaped copper oxide microspheres. The molar ratio of barium sulfide in the barium sulfide solution to zinc sulfate in the zinc sulfate solution is 1:

1. The molar ratio of sea urchin-shaped copper oxide microspheres to barium sulfide in the barium sulfide solution is 1:3 to 1:

7. The mass fraction of inorganic particles in modified polyethylene is 3.5%–5.5%; The mass fraction of titanate coupling agent in modified polyethylene is 0.25%–1.5%; (2) Preparation of spinning solution: Modified polyethylene is dissolved in a spinning solvent to obtain a spinning solution; The mass fraction of modified polyethylene in the spinning solution is 7-18%; The spinning solvent is a mixture of various aromatic hydrocarbons, aliphatic hydrocarbons, alicyclic hydrocarbons, unsaturated hydrocarbons, halogenated hydrocarbons, alcohols, esters, ethers, ketones, nitriles, amides, and fluorocarbons; (3) Preparation of fold-resistant film material: The spinning solution is flash-spun at 190–215°C to obtain flash-spun fibers, which are then laid into a web. The film material is first subjected to a hot pressing process, then calendered by a calender, and finally stretched by tension control before winding to obtain a fold-resistant film material.

2. The fold-resistant film material as described in claim 1, characterized in that: The total crease recovery angle is 70-80°.

3. The fold-resistant film material as described in claim 1, characterized in that: The total crease recovery angle is 80-90°.

4. The fold-resistant film material as described in claim 1, characterized in that: The wear resistance index is 8000-9000 times / mg.

5. The fold-resistant film material as described in claim 1, characterized in that: The wear resistance index is 9000-10000 times / mg.

6. The fold-resistant film material as described in claim 1, characterized in that: The wear resistance index is 10,000 to 11,000 times / mg.

7. The fold-resistant film material as described in claim 1, characterized in that: The wear resistance index is 11,000 to 12,000 times / mg.

8. The fold-resistant film material as described in claim 1, characterized in that: The wet tensile strength retention rate of the folding-resistant film material is 80-85%.

9. The fold-resistant film material as described in claim 1, characterized in that: The wet tensile strength retention rate of the folding-resistant film material is 85-90%.

Images