• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    The present invention relates to a fully 100% biodegradable composite film, its processing technology and its application. This fully 100% biodegradable composite film is structured in three layers, the outer film of which is composed of the following weight percent components: 80-95% polylactic acid, polyterephthalic acid-adipic acid-5-20 butylene glycol ester %; the intermediate film consists of the aqueous dispersion of the polyester-polyurethane elastomer; the inner film is composed of the following components in percentage of masses: polyterephthalic acid-adipic acid-butylene glycol ester at 70-90%, organic starch at 10-30%; the processing technology is as follows: S1, making the outer film; S2, printing ink; S3, manufacture of the internal film; S4, composition; S5, maturation. The fully 100% biodegradable composite film of the present invention can be used to form the three-sided sealed flattened bag, three-sided sealed holding bag, four-sided sealed bag, back-sealed bag, and back-sealed bag. maintaining band opening and closing, with the strengths, such that it can be degraded to 100%, and good barrier performance.
    公开号:FR3094918A1
    申请号:FR1912865
    申请日:2019-11-19
    公开日:2020-10-16
    发明作者:Shuangli LI；Peng Zhang
    申请人:Qingdao Zhoushi Plastic Packaging Co Ltd；
    IPC主号:
    专利说明:

    [0001] The present invention relates to the technical field of polymer materials, and specifically, it relates to a fully 100% biodegradable composite film, its processing technology and its application.
    [0002] State of the art
    [0003] Plastic flexible packaging has gradually become the mainstay of the packaging industry, the most important component of which is the composite barrier film, which is used to package various foods and medicines. Currently, the barrier materials commonly used in industry mainly include ethylene vinyl alcohol copolymer (EVOH) and polyvinylidene chloride (PDVC) etc, despite these materials have good barrier performance, but they do not are not biodegradable.
    [0004] Polylactic acid (PLA) is a fully biodegradable and environmentally friendly materials coated with good mechanical performance and biodegradability, with a wide source of raw materials, such as corn, wheat, cassava and other starches . It is easily replaced by the enzymatic decomposition of various microorganisms or animals and plants in nature, eventually forming water and carbon dioxide, and does not pollute the environment. It is considered the most promising biodegradable polymer material. Furthermore the toxicity of polylactic acid makes it possible to be used for packaging in direct contact with food, can be processed by general plastics processing processes, such as injection molding, extrusion, blowing, blow molding, spinning and other processing technology into a variety of packaging materials, it is widely used in various civil, industrial, agricultural and medical special fields.
    [0005] Among the current technologies, the Chinese invention patent document in application number of CN201410749335.3 relates to a fully biodegradable composite material, its processing technology and its application, including the components: 5-40 pcs of the filler biodegradable masterbatch inorganic filler, 40-80 pcs of biodegradable copolyester, 10-40 pcs of polylactic acid, 0.1-5 pcs of compatibilizing agent, of which, the inorganic filler mentioned is one or a combination of modified kaolin clay, silica modified or modified polynite.
    [0006] The present biodegradable composite material has better tear resistance and flexibility when making the package, but the barrier performance against water vapor and oxygen is poor when packing the food and the drug, and the biodegradation rate is not high. Therefore, realizing the invention of a coated composite film with 100% complete degradation and good barrier performance is a problem to be solved.
    [0007] Aiming at the insufficiency of existing technologies, the first aim of the present invention is to provide a fully 100% biodegradable composite film which has the advantages of complete degradation and good barrier performance.
    [0008] The second object of the present invention is to provide the processing technology of a fully 100% biodegradable composite film which has the advantages of simple manufacturing process and easy operation.
    [0009] The third object of the present invention is to provide the application of a fully 100% biodegradable composite film which has the advantages of 100% complete degradation of the formed package, and a rapid rate of degradation and good barrier performance.
    [0010] For these purposes, the object of the invention is a kind of fully 100% biodegradable composite film characterized by the three-layer structure, the outer film of which is composed of the following mass percentage components: 80-95% polylactic acid, polyterephthalic acid-adipic acid-butylene glycol ester 5-20%; - the intermediate film consists of the aqueous dispersion of the polyester-polyurethane elastomer; and - the internal film is composed of the following mass percentage components: polyterephthalic acid-adipic acid-butylene glycol ester at 70 to 90%, organic starch at 10 to 30%.
    [0011] The entirely 100% biodegradable composite film according to the invention may also have the following characteristics:
    [0012] - the outer film can be composed of the following mass percentage components: 85-90% polylactic acid, 10-15% polyterephthalic acid-adipic acid-butylene glycol ester; - the intermediate film may consist of the aqueous dispersion of the polyester-polyurethane elastomer; - the inner film can be composed of the following mass percentage components: polyterephthalic acid-adipic acid-butylene glycol ester 75-85%, organic starch 15-25%;
    [0013] - the outer film referred to may have a thickness of 0.015 to 0.1 mm, the inner film may have a thickness of 0.03 to 0.15 mm;
    [0014] - the mentioned biological starch can be produced by the following processes: (1) add bagasse in sodium hydroxide solution having a solid-liquid ratio of 1:20 to 25 and a concentration of 1%, then stir for 2 hours, and then filter, wash and dry; (2) dissolve aminotriacetic acid with 5% ammonia water, add dried bagasse and ammonium persulfate, react at 60-65°C for 1.5-2h, then wash and drying, the mass proportion of aminotriacetic acid, bagasse and ammonium persulfate is 1: (2 to 2.2): (0.8 to 1); (3) dissolving bagasse taken in step (2) in mixed solution in 20-30% concentration of 1-butyl-3-methylimidazolium chloride and 1-ethyl-3-acetate methylimidazolium, solid-liquid ratio of bagasse and mixed solution is 1:5 to 8, dissolution temperature is 80 to 90°C, stir for 1.5 to 2h, then filter, and pour filtrate in corn starch, potato starch and polypropylene carbonate in a mass ratio of 1:(0.6 to 0.9):(0.5 to 0.8):( 0.5 to 0.7), mix at a temperature of 35-45°C to form organic starch; and
    [0015] - the molecular weight of polylactic acid can be 100,000-200,000, and the molecular weight of polyterephthalic acid-adipic acid-butylene glycol ester can be 60,000-100,000.
    [0016] The invention extends to a process for manufacturing the composite film that is entirely 100% biodegradable, comprising the following steps: S1) The manufacture of the outer film: after mixing polylactic acid and polyterephthalic acid-adipic acid-butylene glycol ester homogeneously, pressing-in using a twin-screw extruder, which we a pressed is formed into film via film blowing machine, and then is formed into outer film after cooling, pulling and rolling; S2) the printing ink: printing the desired design on one side of the outer film, and drying it; S3) The manufacture of the inner film: after mixing polyterephthalic acid-adipic acid-butylene glycol ester and biological starch homogeneously, pressing it using a twin-screw extruder, which we have pressed is formed into film, and then is formed into inner film after cooling, pulling and rolling; S4) the composition: apply a layer of polyvinyl alcohol with the brush roller at a temperature of 35 to 50°C on the side of the printed design of the outer film. And then apply a layer of the aqueous dispersion of the polyester-polyurethane elastomer with the brush roller at the temperature of 35-50°C, finally press the outer film with the brush roller at the temperature of 35-50°C on the side coated with a layer of the aqueous dispersion of the polyester-polyurethane elastomer of the outer yarn, performing cooling, pulling and rolling on the formed composite film to form a semi-finished composite film; the coating amount of polyvinyl alcohol is 1.2 to 2 g/m 2 , and the coating amount of the aqueous dispersion of the polyester-polyurethane elastomer is 3 to 5 g/m 2 ; and S5) Maturation: put the semi-finished composite film into the maturing chamber, control the maturing temperature at 35-45°C, maturing time is 12-48h, and the finished composite film will be formed after maturing .
    [0017] The process for manufacturing the entirely 100% biodegradable composite film according to the invention may also have the following characteristics:
    [0018] - the temperatures of each zone of the film blowing machine mentioned in step S1 can be the following: zone 1: 145 to 155°C, zone 2: 155 to 165°C, zone 3: 160 to 170°C , zone 4: 165 to 175°C, zone 5: 170 to 180°C, zone 6: 170 to 180°C; and the temperatures of each zone of the film blowing machine referred to in step S3 may be as follows: zone 1: 115 to 125°C, zone 2: 125 to 130°C, zone 3: 125 to 130°C , zone 4: 130 to 140°C, zone 5: 140 to 150°C, zone 6: 150 to 160°C;
    [0019] - the bonding pressure of the inner and outer film mentioned in step S4 can be 0.1-0.8MPa, and the pressing time is the pressing time can be 0.5-1min/mm; and
    [0020] - the traction speed mentioned in step S1, S2 and S4 can be from 100 to 200 m/min, the unwinding tension of the internal and external film mentioned in step S4 can be from 6 to 8 kg/m , the unwinding tension of the half-finished composite film can be 7 to 12 kg/m.
    [0021] The invention extends to an application of the 100% fully biodegradable composite film to form the three-side-sealed flattened bag, the three-side-sealed holding bag, the four-side-sealed bag, the back-sealed bag and the holding bag in opening and closing tape.
    [0022] In order to achieve the said first object, the present invention provides the following technical program: a fully 100% biodegradable composite film structured in three layers, the outer film of which is composed of the following mass percentage components: polylactic acid at 80-95 %, polyterephthalic acid-adipic acid-butylene glycol ester 5-20%;
    [0023] The intermediate film consists of the aqueous dispersion of the polyester-polyurethane elastomer;
    [0024] The inner film is composed of the following mass percentage components: polyterephthalic acid-adipic acid-butylene glycol ester 70-90%, organic starch 10-30%;
    [0025] By adopting the said technical program, polylactic acid has strong mechanical strength, good processing properties and outstanding biocompatibility, but its toughness is poor, the brittleness is large, and polyterephthalic acid-adipic acid-butylene glycol ester also has good toughness as the fully biodegradable material. Polyterephthalic acid-adipic acid-butylene glycol ester and polylactic acid are combined as the outer film, the correct content control of polyterephthalic acid-adipic acid-butylene glycol ester and polylactic acid makes it possible to accelerate the rate of hydrolysis of the ester bonds of PBAT and PLA, thereby increasing the rate of degradation of the composite film, by using the aqueous dispersion of the polyester-polyurethane elastomer as the intermediate film, bond and compound the outer film and the inner film, the aqueous dispersion of the polyester-polyurethane elastomer has excellent shear strength and impact resistance, has excellent flexibility characteristics, can improve the mechanical properties of the composite film , and the aqueous dispersion of the polyester-polyurethane elastomer has good degradation property, the inner film is composed of polyterephthalic acid-adipi acid than -butylene glycol ester and biological starch, polyterephthalic acid-adipic acid-butylene glycol ester has high heat resistance, hardness and fatigue resistance, and biological starch can be completely degraded in various environments, then decomposed into carbon dioxide and water, without any environmental pollution, and polyterephthalic acid-adipic acid-butylene glycol ester and biological starch are mixed together to obtain biodegradable polyterephthalic acid-adipic acid-butylene glycol ester of modified starch filler which overcomes the disadvantages of moisture absorption, brittleness and difficulty in plasticization of starch and reasonable control of starch content polyterephthalic acid-adipic acid-butylene glycol ester and biological starch can accelerate the rate of biodegradation, while combining polyterephthalic acid-adipic acid-butylene glycol ester and t polylactic acid to form the outer film, as well as combining polyterephthalic acid-adipic acid-butylene glycol ester and bio-starch to form the inner film, and the outer film and the inner film are combined to improve the barrier properties of polylactic acid.
    [0026] In addition, the discussed outer film is composed of the following mass percent components: polylactic acid 85-90%, polyterephthalic acid-adipic acid-butylene glycol ester 10-15%;
    [0027] The intermediate film consists of the aqueous dispersion of the polyester-polyurethane elastomer;
    [0028] The inner film is composed of the following mass percentage components: polyterephthalic acid-adipic acid-butylene glycol ester 75-85%, organic starch 15-25%.
    [0029] By adopting the said technical program, the ratio of the raw material components in the outer film and the inner film is more accurate, so that the produced composite film has faster biodegradation speed and better barrier property.
    [0030] Further, the evoked outer film has a thickness of 0.015-0.1mm, the inner film having a thickness of 0.03-0.15mm.
    [0031] By adopting the said technical program, the thickness of the outer film and the inner film is appropriate, so that the strength, toughness, tear resistance and barrier property of the composite film are better.
    [0032] In addition, the mentioned biological starch is produced by the following processes:
    [0033] (1) Add bagasse in sodium hydroxide solution having a solid-liquid ratio of 1:20-25 and a concentration of 1%, then stir for 2 hours, and then filter, wash and dry;
    [0034] (2) Dissolve aminotriacetic acid with 5% ammonia water, add dried bagasse and ammonium persulfate, react at 60-65°C for 1.5-2h, then wash and dry , the mass proportion of aminotriacetic acid, bagasse and ammonium persulfate is 1: (2-2.2): (0.8-1);
    [0035] (3) Dissolve bagasse taken in step (2) in mixed solution in 20-30% concentration of 1-butyl-3-methylimidazolium chloride and 1-ethyl-3-acetate methylimidazolium, solid-liquid ratio of bagasse and mixed solution is 1:5 to 8, dissolution temperature is 80-90°C, stir for 1.5-2h, then filter, and pour filtrate into corn starch, potato starch and polypropylene carbonate in a mass proportion of 1:(0.6-0.9):(0.5-0.8):(0.5-0.7), mix them to a temperature of 35-45°C to form organic starch.
    [0036] By adopting the said technical program, bagasse contains a large amount of bagasse fiber and is treated with sodium hydroxide solution to remove macromolecular impurities on the surface of bagasse fiber and remove hemicellulose, lignin and silica gel and other impurities coated on the surface of bagasse fibers to obtain the surface of bagasse fibers initiated extruded sheets, gloss, and bagasse fibers with good interfacial adhesion, nitrilotriacetic acid grafted bagasse after the alkali treatment, an increase in oxygen-containing functional groups, so as to improve the surface roughness, and achieve good bonding between bagasse and corn starch, corn starch potato and polypropylene carbonate, when subjected to external stress, external stress transmitted effectively, so that the tensile property and elongation rate of composite films rise, polypropylene carbonate, corn starch, potato starch and bagasse can be used at the same time, and then combined with polylactic acid in the outer film to improve the property water vapor and oxygen barrier of the composite film.
    [0037] In addition, the molecular weight of polylactic acid is 100,000-200,000, and the molecular weight of polyterephthalic acid-adipic acid-butylene glycol ester is 60,000-100,000.
    [0038] In order to achieve the said second object, the present invention proposes the following technical program: a fully 100% biodegradable composite film processing technology includes the following steps:
    [0039] S1. The manufacture of the outer film: after mixing polylactic acid and polyterephthalic acid-adipic acid-butylene glycol ester homogeneously, pressing-in using a twin-screw extruder, which we pressed is formed into film through the film blowing machine, and then is formed into outer film after cooling, pulling and rolling;
    [0040] S2. Printing ink: print the desired design on one side of the outer film, and dry it;
    [0041] S3. The manufacture of the inner film: after mixing polyterephthalic acid-adipic acid-butylene glycol ester and biological starch homogeneously, pressing it using a twin-screw extruder, which we pressed is formed into a film, and then is formed into an inner film after cooling, pulling and rolling;
    [0042] S4. The composition: apply a layer of polyvinyl alcohol with the brush roller at a temperature of 35 to 50°C on the side of the printed design of the outer film. And then apply a layer of the aqueous dispersion of the polyester-polyurethane elastomer with the brush roller at the temperature of 35-50°C, finally press the outer film with the brush roller at the temperature of 35-50°C on the side coated with a layer of the aqueous dispersion of the polyester-polyurethane elastomer of the outer yarn, performing cooling, pulling and rolling on the formed composite film to form a semi-finished composite film; the coating amount of polyvinyl alcohol is (1.2-2) g/m 2 , and the coating amount of the aqueous dispersion of the polyester-polyurethane elastomer is (3-5) g/m 2 ;
    [0043] S5. Maturation: put the semi-finished composite film into the maturing chamber, control the maturing temperature at 35-45°C, the maturing time is 12-48h, and the finished composite film will be formed after maturing.
    [0044] By adopting the said technical program, the process is simple and the operation is easy, the application of polyvinyl alcohol between the outer film and the inner film can increase the barrier property of the composite film, at the same time, the composite film formed is resistant to tearing and stretching. Moreover, it can be completely biodegraded without environmental pollution.
    [0045] Further, the temperatures of each zone of the film blowing machine discussed in step S1 are as follows: zone 1: 145-155°C, zone 2: 155-165°C, zone 3: 160-170° C, zone 4: 165-175°C, zone 5: 170-180°C, zone 6: 170-180°C; and the temperatures of each zone of the film blowing machine referred to in step S3 are as follows: zone 1: 115-125°C, zone 2: 125-130°C, zone 3: 125-130°C, zone 4: 130-140°C, zone 5: 140-150°C, zone 6: 150-160°C.
    [0046] Furthermore, the bonding pressure of the inner and outer film discussed in step S4 is 0.1-0.8MPa, and the pressure time is the pressure time is (0.5-1)min/mm.
    [0047] Further, the pulling speed mentioned in the step of S1, S2 and S4 is 100-200m/min, the inner and outer film unwinding tension mentioned in the step S4 is (6-8) kg/ m, the unwinding tension of the half-finished composite film is (7-12) kg/m.
    [0048] To achieve the said third object, the present invention provides the following technical program: the application of a completely 100% biodegradable composite film, this mentioned fully 100% biodegradable composite film can be used to form the three-sealed flattened bag sides, the three side sealed bag, the four side sealed bag, the back sealed bag and the opening and closing band bag.
    [0049] In summary, the present invention has the following beneficial effects:
    [0050] First, since the present invention uses polylactic acid and polyterephthalic acid-adipic acid-butylene glycol ester to form the outer film of the composite film, and polyterephthalic acid-adipic acid-butylene ester glycol and biological starch to form the inner film of the composite film, and the aqueous dispersion of the polyester-polyurethane elastomer as the intermediate film, since the biodegradable polylactic acid has good film-forming property and that the film has high transparency, stiffness and hardness, the addition of the biodegradable polyterephthalic acid-adipic acid-butylene glycol ester can improve the properties of tensile, impact resistance, toughness, tear resistance and raising the rate of biodegradation rate; And improve the barrier and biodegradation properties of the film by combining polyterephthalic acid-adipic acid-butylene glycol ester and biological starch.
    [0051] Secondly, the present invention chooses good quality bagasse, corn starch, potato starch and polypropylene carbonate to form biological starch, the surface property of treated bagasse is improved and the adhesion with polypropylene carbonate is high, mixing biological starch with the addition of bagasse and polypropylene carbonate with polyterephthalic acid-adipic acid-butylene glycol ester, the Polypropylene carbonate is the fully biodegradable material having good airtightness, and cooperation with the polylactic acid of the outer film can raise the barrier properties and the biodegradability rate of the composite film, while the bagasse fiber can improve the tensile properties and tear resistance of the composite film.
    [0052] Third, in the present invention, applying polyvinyl alcohol which is a biodegradable polymer material and has an excellent barrier property to the outer film. It is applied between the outer film and the inner film to elevate the barrier properties of the composite film.
    [0053] detailed description
    [0054] The present invention will be described in more detail below with reference to embodiments.
    [0055] Example of making 1-3 of organic starch
    [0056] In the manufacturing example of 1-3, the bagasse chosen is that sold by Boguan agricultural development Co., Ltd in Nanning of Guangxi in diameter of 2-15mm, the corn starch chosen is that sold by Hemao chemical industry Co. ., ltd. in Suzhou in model number of HM017, the potato starch chosen is that sold by Dakui chemical industry Co., Ltd in Jinan in commodity number of DKHG-MSDF-12, the polypropylene carbonate chosen is that of BioCO 2 (TM) 100 sold by Mengxi Hi-tech Materials Co., Ltd in Inner Mongolia.
    [0057] Manufacturing Example 1: (1) Add bagasse to sodium hydroxide solution having a solid-liquid ratio of 1:20 and a concentration of 1%, then stir for 2 hours, and then filter, wash and to dry;
    [0058] (2) Dissolve aminotriacetic acid with 5% ammonia water, add dried bagasse and ammonium persulfate, react at a temperature of 60°C for 1.5h, then wash and dry, the proportion of mass of aminotriacetic acid, bagasse and ammonium persulfate is 1: 2: 0.8;
    [0059] (3) Dissolving bagasse taken in step (2) in mixed solution in 20% concentration of 1-butyl-3-methylimidazolium chloride and 1-ethyl-3-methylimidazolium acetate, the solid-liquid ratio of bagasse and the mixed solution is 1:5, the mass ratio of 1-butyl-3-methylimidazolium chloride and 1-ethyl-3-methylimidazolium acetate is 1: 1, the dissolution temperature is 80°C, stir for 1.5h, then filter, and pour filtrate into corn starch, potato starch and polypropylene carbonate in mass proportion of 1:0.6:0.5:0.5, mix at a temperature of 35°C to form organic starch. The glass transition temperature of polypropylene carbonate is 40°C, the molecular weight is 200,000.
    [0060] Manufacturing Example 2: (1) Add bagasse to sodium hydroxide solution having a solid-liquid ratio of 1:23 and a concentration of 1%, then stir for 2.3 hours, and then filter, wash and to dry;
    [0061] (2) Dissolve aminotriacetic acid with 5% ammonia water, add dried bagasse and ammonium persulfate, react at a temperature of 63°C for 1.8h, then wash and dry, the proportion of mass of aminotriacetic acid, bagasse and ammonium persulfate is 1: 2.1: 0.9;
    [0062] (3) Dissolving bagasse taken in step (2) in mixed solution in 25% concentration of 1-butyl-3-methylimidazolium chloride and 1-ethyl-3-methylimidazolium acetate, the solid-liquid ratio of bagasse and the mixed solution is 1:6.5, the mass ratio of 1-butyl-3-methylimidazolium chloride and 1-ethyl-3-methylimidazolium acetate is 1: 1.5, dissolution temperature is 85°C, stir for 1.8h, then filter, and pour filtrate into corn starch, potato starch and polypropylene carbonate in mass proportion of 1:0.7:0.6:0.6, mix at a temperature of 40°C to form organic starch. The glass transition temperature of polypropylene carbonate is 45°C, the molecular weight is 230,000.
    [0063] Manufacturing Example 3: (1) Add bagasse to sodium hydroxide solution having a solid-liquid ratio of 1:25 and a concentration of 1%, then stir for 2.5 hours, and then filter, wash and to dry;
    [0064] (2) Dissolve aminotriacetic acid with 5% ammonia water, add dried bagasse and ammonium persulfate, react at a temperature of 65°C for 2h, then wash and dry, the mass proportion of aminotriacetic acid, bagasse and ammonium persulfate is 1: 2.2: 1;
    [0065] (3) Dissolving bagasse taken in step (2) in mixed solution in 30% concentration of 1-butyl-3-methylimidazolium chloride and 1-ethyl-3-methylimidazolium acetate, the solid-liquid ratio of bagasse and the mixed solution is 1:8, the mass ratio of 1-butyl-3-methylimidazolium chloride and 1-ethyl-3-methylimidazolium acetate is 1: 1.4, the dissolution temperature is 90°C, stir for 2h, then filter, and pour filtrate into corn starch, potato starch and polypropylene carbonate in mass proportion of 1:0.9:0.8:0.7, mix at a temperature of 45°C to form organic starch. The glass transition temperature of polypropylene carbonate is 50°C, the molecular weight is 250,000.
    [0066] Application example
    [0067] The polylactic acid chosen is that sold by Jinfa technology Co., Ltd in model Flex-262, the polyterephthalic acid-adipic acid-butylene glycol ester chosen is that sold by Jinfa technology Co., Ltd in model Flex- 64D, the aqueous dispersion of the polyester-polyurethane elastomer chosen is that sold by BASF in Germany in model Epotal®ECO3702, the polyvinyl alcohol chosen is that sold by Boshun chemical industry Co., Ltd. In Shenzhen in brand number of 2488, and corn starch is the one sold by Hemao chemical industry Co., Ltd. in Suzhou in model of HM017, and the potato starch is that sold by Dakui Chemical Industry Co., Ltd in Jinan in commodity number of DKHG-MSDF-12.
    [0068] Application example 1: 100% fully biodegradable composite film, including outer film, middle film and inner film, the raw material proportion of outer film and inner film is shown in table 1, the biological starch in the inner film is produced according to manufacturing example 1, the outer film thickness is 0.015mm, the inner film thickness is 0.03mm, the molecular weight of polyterephthalic acid-adipic acid- butylene glycol ester is 60,000 and the molecular weight of polylactic acid is 100,000.
    [0069] The 100% fully biodegradable composite film processing technology includes the following steps:
    [0070] S1. The manufacture of the outer film: after mixing 81% polylactic acid and polyterephthalic acid-adipic acid-19% butylene glycol ester homogeneously, pressing-by using a twin-screw extruder, this that which has been pressed is formed into a film through the film blowing machine, and then is formed into an outer film after cooling, pulling and rolling, the temperatures of each area of the film blowing machine are as follows : zone 1: 145°C, zone 2: 155°C, zone 3: 160°C, zone 4: 165°C, zone 5: 170°C, zone 6: 170°C, and the tensile speed of the film external is 100m/min.
    [0071] S2. Printing ink: print the desired design on one side of the outer film, and dry it;
    [0072] S3. The manufacture of the inner film: after mixing polyterephthalic acid-adipic acid-butylene glycol ester 71% and organic starch 29% homogeneously, pressing-in using a twin-screw extruder, this which was pressed is formed into film, and then is formed into inner film after cooling, pulling and rolling, the temperatures of each zone of the film blowing machine are as follows: zone 1: 115°C , zone 2: 125°C, zone 3: 125°C, zone 4: 130°C, zone 5: 140°C, zone 6: 150°C, and the tensile speed of the internal film is 100 m/min.
    [0073] S4. The composition: apply a layer of polyvinyl alcohol with the brush roller at a temperature of 35°C on the side of the printed design of the outer film. And then apply a layer of the aqueous dispersion of the polyester-polyurethane elastomer with the brush roller at a temperature of 35°C, finally press the outer film with the brush roller
    [0074] mass percentage Material composition of the outer film Composition of inner film materials Thickness/mm/internal/external Application example 1 81% polylactic acid Polyterephthalic acid-adipic acid-butylene glycol ester 19% Polyterephthalic acid-adipic acid-butylene glycol ester 71% 29% organic starch 0.015 / 0.03 Application example 2 8.5% polylactic acid Polyterephthalic acid-adipic acid-butylene glycol ester 15% Polyterephthalic acid-adipic acid-butylene glycol ester 75% 25% organic starch 0.75 / 0.09 Application example 3 90% polylactic acid Polyterephthalic acid-adipic acid-butylene glycol ester 10% Polyterephthalic acid-adipic acid-butylene glycol ester 80% 20% organic starch 0.1 /0.15 Application example 4 93% polylactic acid Polyterephthalic acid-adipic acid-butylene glycol ester 7% Polyterephthalic acid-adipic acid-butylene glycol ester 85% 15% organic starch 0.075 /0.09 Application example 5 95% polylactic acid Polyterephthalic acid-adipic acid-butylene glycol ester 5% Polyterephthalic acid-adipic acid-butylene glycol ester 90% 10% organic starch 0.1 / 0.15
    [0075] at a temperature of 35°C on the side coated with a layer of the aqueous dispersion of the polyester-polyurethane elastomer of the outer yarn, performing cooling, pulling and rolling on the formed composite film to form a composite film Half finished; the coating amount of polyvinyl alcohol is 1.2g/m 2 , and the coating amount of the aqueous dispersion of the polyester-polyurethane elastomer is 3 g/m 2 ，the unwinding tension of the outer film and the internal film is 6 kg/m, the bonding pressure is 0.1 MPa, the pressing time is 0.5 min/mm, and the winding tension of the semi-finished composite film is 7 kg/m.
    [0076] S5. Maturation: put the semi-finished composite film into the maturing chamber, control the maturing temperature to 35°C, maturing time is 12h, and the finished composite film will be formed after maturing.
    [0077] Table 1, the material composition of the inner and outer film of Example 1-5.
    [0078] Application example 2: 100% fully biodegradable composite film, including outer film, middle film and inner film, the raw material proportion of outer film and inner film is shown in table 1, the bio-starch in the inner film is produced according to manufacturing example 1, the outer film thickness is 0.35mm, the inner film thickness is 0.06mm, the molecular weight of polyterephthalic acid-adipic acid- butylene glycol ester is 80,000 and the molecular weight of polylactic acid is 150,000.
    [0079] The 100% fully biodegradable composite film processing technology includes the following steps:
    [0080] S1. The manufacture of the outer film: after mixing 85% polylactic acid and polyterephthalic acid-adipic acid-15% butylene glycol ester homogeneously, pressing-by using a twin-screw extruder, this that which has been pressed is formed into a film through the film blowing machine, and then is formed into an outer film after cooling, pulling and rolling, the temperatures of each area of the film blowing machine are as follows : zone 1: 150°C, zone 2: 160°C, zone 3: 165°C, zone 4: 170°C, zone 5: 175°C, zone 6: 175°C, and the tensile speed of the film external is 150m/min.
    [0081] S2. Printing ink: print the desired design on one side of the outer film, and dry it;
    [0082] S3. The manufacture of the inner film: after mixing 75% polyterephthalic acid-adipic acid-butylene glycol ester and 25% organic starch homogeneously, pressing-in using a twin-screw extruder, this which was pressed is formed into film, and then is formed into inner film after cooling, pulling and rolling, the temperatures of each zone of the film blowing machine are as follows: zone 1: 120°C , zone 2: 130°C, zone 3: 130°C, zone 4: 135°C, zone 5: 145°C, zone 6: 155°C, and the tensile speed of the internal film is 100 m/min.
    [0083] S4. The composition: apply a layer of polyvinyl alcohol with the brush roller at a temperature of 45°C on the side of the printed design of the outer film. And then apply a layer of the aqueous dispersion of the polyester-polyurethane elastomer with the brush roller at a temperature of 45°C, finally press the outer film with the brush roller at a temperature of 45°C on the side coated with a layer of the aqueous dispersion of the polyester-polyurethane elastomer of the outer yarn, performing the cooling, pulling and rolling on the formed composite film to form a semi-finished composite film; the coating amount of polyvinyl alcohol is 1.6g/m 2 , and the coating amount of the aqueous dispersion of the polyester-polyurethane elastomer is 4g/m 2 ，the unwinding tension of the outer film and the internal film is 7 kg/m, the bonding pressure is 0.4 MPa, the pressing time is 0.8 min/mm, and the winding tension of the semi-finished composite film is 10 kg/m.
    [0084] S5. Maturation: put the semi-finished composite film into the maturing chamber, control the maturing temperature to 40°C, maturing time is 30h, and the finished composite film will be formed after maturing.
    [0085] Application example 3: 100% fully biodegradable composite film, including outer film, middle film and inner film, the raw material proportion of outer film and inner film is shown in table 1, the biological starch in the inner film is produced according to manufacturing example 3, outer film thickness is 0.58mm, inner film thickness is 0.09mm, the molecular weight of polyterephthalic acid-adipic acid- butylene glycol ester is 100,000 and the molecular weight of polylactic acid is 200,000.
    [0086] The 100% fully biodegradable composite film processing technology includes the following steps:
    [0087] S1. The manufacture of the outer film: after mixing 90% polylactic acid and polyterephthalic acid-adipic acid-10% butylene glycol ester homogeneously, pressing-by using a twin-screw extruder, this which was pressed is formed into a film through the film blowing machine, and then is formed into an outer film after cooling, pulling and rolling, the temperatures of each area of the film blowing machine mentioned in step S1 are as follows: zone 1: 155°C, zone 2: 165°C, zone 3: 170°C, zone 4: 175°C, zone 5: 180°C, zone 6: 180°C, and the pulling speed of the outer film is 200m/min.
    [0088] S2. Printing ink: print the desired design on one side of the outer film, and dry it;
    [0089] S3. The manufacture of the inner film: after mixing 80% polyterephthalic acid-adipic acid-butylene glycol ester and 20% organic starch homogeneously, pressing-in using a twin-screw extruder, this that was pressed is formed into a film, and then is formed into an inner film after cooling, pulling and rolling, the temperatures of each area of the film blowing machine referred to in step S1 are as follows: zone 1: 125°C, zone 2: 135°C, zone 3: 135°C, zone 4: 140°C, zone 5: 150°C, zone 6: 160°C, and the internal film tensile speed is 200m/min.
    [0090] S4. The composition: apply a layer of polyvinyl alcohol with the brush roller at a temperature of 50°C on the side of the printed design of the outer film. And then apply a layer of the aqueous dispersion of the polyester-polyurethane elastomer with the brush roller at a temperature of 50°C, finally press the outer film with the brush roller at a temperature of 50°C on the side coated with a layer of the aqueous dispersion of the polyester-polyurethane elastomer of the outer yarn, performing the cooling, pulling and rolling on the formed composite film to form a semi-finished composite film; the coating amount of polyvinyl alcohol is 2g/m 2 , and the coating amount of the aqueous dispersion of the polyester-polyurethane elastomer is 5g/m 2 ，the unwinding tension of the outer film and the film internal is 8 kg/m, the bonding pressure is 0.8 MPa, the pressing time is 1 min/mm, and the winding tension of the semi-finished composite film is 12 kg/m.
    [0091] S5. Maturation: put the semi-finished composite film into the maturing chamber, control the maturing temperature to 45°C, the maturing time is 48h, and the finished composite film will be formed after maturing.
    [0092] Application example 4: A fully 100% biodegradable composite film, which differs from application example 1 is that the composition of the raw material and the thickness of the inner and outer film are shown in Table 1. The The bio-starch is corn starch, and the processing technology of the fully 100% biodegradable composite film is the same as that of Application Example 1.
    [0093] Application Example 5: A fully 100% biodegradable composite film, which differs from Application Example 1 is that the composition of the raw material and the thickness of the inner and outer film are shown in Table 1. The biological starch is potato starch, and the processing technology of the fully 100% biodegradable composite film is the same as that of Application Example 1.
    [0094] Example of comparison
    [0095] Comparison example 1-4: A fully 100% biodegradable composite film, which differs from application example 1 is that the raw material composition of the outer film is shown in Table 2.
    [0096] Comparison example 5-8: A fully 100% biodegradable composite film, which differs from application example 1 is that the raw material composition of the inner film is shown in Table 2.
    [0097] Comparison Example 9: A film formed from the biodegradable composite material PLA/PBAT produced in Application Example 1 of Chinese patent document in application number CN201210289135.5 was used as the contrast, (1) dry PLA (4032D ) and PBAT for 12 h in the blow dryer at 80°C, and calcium carbonate for 6 hours, (2) then mix 90 parts PLA, 10 parts PBAT, 0.04 part 2.2'-bis(2-oxazoline ), 2.4 parts hexamethylene diisocyanate, 0.6 part calcium stearate, 0.1 part antioxidant 1010, 10 parts calcium carbonate in a high frequency blender at room temperature for 5 minutes; (3) add mixture obtained in twin screw machine to get extrusion granulation, temperature of each area of twin screw machine is: area 1: 150°C, area 2: 160°C, area 3 : 160°C, zone 4: 170°C, zone 5: 170°C, zone 6: 175°C, machine head: 180°C; the screw rotation speed is 200 rpm/min, and the aspect ratio L/Dest is 40/1; (4) drying the granulation obtained in step (3) in the blow dryer at 80°C for 12 hours; (5) Add dried granulation in step (4) into the single screw machine to make blow molding. The temperature of each zone of the single screw machine is: zone 1: 120°C, zone 2: 140°C, zone 3: 160°C, zone 4: 170°C, zone 5: 170°C, zone 6 : 170°C, machine head: 165°C; the screw rotation speed is 150 rpm/min, and the aspect ratio L/D is 25/1; the ratio of the die diameter of the single screw extruder and that of the bubble tube is 3:1.
    [0098] Comparison Example 10: A film formed of the PBAT biodegradable composite material of modified plasticity starch produced in Application Example 1 of Chinese patent document in application number CN201210553133.2 was used as the contrast, take the sawn sheet of PBAT (Mw160000, MI0. 5g/10min (150°C, 2160g)) at 84wt%, tapioca starch at 10wt%, plasticizer in total content 6wt%, including glycerin at 2.4 %, 1.2% formamide, 2.4% urea; starch gelatinization temperature is 85°C, twin screw extruder rate is 10r/min, vacuum degree when drying starch plasticity and PBAT is 1.3KPa, the drying temperature is 90°C for 9 hours, the melting temperature is 115°C, and the extrusion rate is 15r/min.
    [0099] Comparison example 11: A composite film completely 100% biodegradable, which differs from application example 1 is that the film concerned in comparison example 9 is formed into an outer film, and the degradable material concerned Comparative Example 10 was formed into an inner film, and was formed into a composite film in the same manner as in Example 1.
    [0100] Table 2, the material composition of the outer film of comparison example 1-4 and the inner film of comparison example 5-8.
    [0101] mass percentage Polylactic acid Polyterephthalic acid-adipic acid-butylene glycol ester Organic starch Comparison example 1 70% 30% / Comparison example 2 75% 25% / Comparison example 3 98% 2% / Comparison example 4 100% 0 / Comparison example 5 / 60% 40% Comparison example 6 / 65% 35% Comparison example 7 / 95% 5% Example of comparison 8 / 100% 0
    [0102] Application Example: Form the composite film according to the methods of Application Example 1-5 and Comparison Example 1-9, and form into packing bag of 650 × (370 +100 x 2 ) × 0.045mm, by cutting, bending and edge, take 100 bags each application and comparison example, and detect the performance of each bag according to following criteria, take the average of detection results of each of 100 bags formed according to the application or comparison example, and record the detection results in Table 3.
    [0103] 1.Tensile strength: Tested in accordance with GB13022-1991 “Method of Testing Tensile Properties of Plastic Film”;
    [0104] 2. Elongation rate at break: checked according to GBB/T1040.3-2006 "Determination of tensile properties - Part 3: Test conditions of film and sheet";
    [0105] 3. Water vapor transmission rate: in accordance with GB/T21529-2008 “Determination of water vapor transmission rate of plastic film and sheet”;
    [0106] 4. Oxygen transmission rate: Complies with GB/ T19789-2005 “Coulomb Test Method of Plastic Film and Sheet Packaging Material for Oxygen Permeability”;
    [0107] 5. Biodegradation rate: HJ/T209-2005 "Technical Requirements for Environmental Labeling Products - Packaging Products" to do the test.
    [0108] Table 3, test results of composite film packaging bags formed in each of application examples and comparison examples.
    [0109] Sensing element Tensile strength / MPa Elongation rate at break / % Water vapor transmission rate/ % Oxygen transmission rate / % Biodegradation rate / % horizontal vertical horizontal vertical 80d 90d 100d 110d 120d Application example 1 27.3 31.2 187.2 112.3 11.2 32.4 67.6 82.7 93.4 100 100 Application example 2 28.1 31.7 192.1 128.2 10.4 26.4 69.3 84.4 95.2 100 100 Application example 3 28.8 32.1 196.2 136.6 9.8 20.3 72.2 86.3 96.8 100 100 Application example 4 29.3 32.3 211.3 178.3 7.5 14.4 74.8 88.9 98.8 100 100 Application example 5 29.5 33.4 214.3 189.3 7.3 13.6 76.5 90.2 99.2 100 100 Comparison example 1 21.1 28.3 145.2 112.8 32.4 61.2 52.1 72.3 86.5 92.2 92.2 Comparison example 2 22.7 29.4 148.5 110.6 30.6 55.7 53.8 73.3 88.4 93.2 93.2 Comparison example 3 24.2 29.6 147.2 121.2 21.8 50.3 56.0 76.8 88.9 94.3 94.3 Comparison example 4 23.3 28.5 145.7 115.6 28.1 43.2 52.7 71.6 83.3 93.1 93.1 Comparison example 5 18.4 22.4 112.8 101.6 32.4 54.6 67.3 82.3 92.4 100 100 Comparison example 6 19.3 24.2 117.5 111.4 28.5 45.7 64.4 81.8 91.4 99.6 99.6 Comparison example 7 26.1 28.4 148.6 118.4 31.6 52.6 58.8 76.3 88.5 93.1 93.1 Example of comparison 8 25.6 27.8 142.5 115.4 28.7 43.7 51.3 70.5 81.5 90.3 90.3 Example of comparison 9 28.9 32.1 189.7 181.5 23.8 24.3 51.6 81.4 92.6 95.6 98.5 Comparison ratio 10 29.4 31.7 191.7 183.4 25.4 25.3 57.3 83.7 93.6 98.6 99.6 Example of comparison 11 28.6 30.7 189.5 182.4 22.1 23.7 56.7 83.9 93.7 98.9 99.7
    [0110] From the data in Table 3, all is strong the vertical and horizontal tensile strength of the packaging bag formed by composite film of Application Example 1-5, and the rate of elongation at break is high, and the water vapor transmission rate is 7.3-11.2%, the oxygen transmission rate is 13.6-32.4%, the biodegradation rate reaches 67.6-76.5% by the 80th day, and reached nearly 100% by the 100th day, by the 110th day all the degradation is complete, it means that the tensile strength, breaking elongation rate and barrier property of the composite film formed by the present invention is high, and it can be 100% degraded, and the degradation speed is fast.
    [0111] In Comparative Example 1, the content of polylactic acid of the outer film is 70%, and that of polyterephthalic acid-adipic acid-butylene glycol ester is 30%, according to the result of test, compared with the application example 1, the mechanical properties of the packaging bag formed by the composite film of the comparison example 1 are lowered, and the permeability to water vapor and oxygen is increased, the biodegradation rate is slowed down, and the degradation rate has precisely reached 92.2% on the 110th day, and the degradation rate does not change when on the 120th day, it means that when the polylactic acid content is lowered and that in polyterephthalic acid-adipic acid-butylene glycol ester is increased, all the properties of the composite film are reduced.
    [0112] In Comparison Example 2, the content of polylactic acid of the outer film is 75%, and that of polyterephthalic acid-adipic acid-butylene glycol ester is 25%, the tensile strength, the elongation at break rate, barrier properties and biodegradation rate were significantly worse than those of application example 1. Compared to comparison example 1, all properties were improved, that means that when the content of polylactic acid is increased and that of polyterephthalic acid-adipic acid-butylene glycol ester is decreased, all the properties of the composite film are stronger, such as tensile strength, barrier properties and biodegradation rate, etc.
    [0113] In Comparative Example 3, the content of polylactic acid in the outer film is 98%, and that of polyterephthalic acid-adipic acid-butylene glycol ester is 2%, compared with Example d. 1-5 application, the content of polylactic acid is increased, and that of polyterephthalic acid-adipic acid-butylene glycol ester is lowered, according to the test data, the packaging bag formed by the film composite of Comparative Example 3, whose tensile properties, rate of elongation at break, barrier properties and rate of biodegradation were markedly worse. The degradation rate has precisely reached 94.3% on the 110th day, which means that when the polylactic acid content is increased and that of polyterephthalic acid-adipic acid-butylene glycol ester is lowered, the barrier properties and the biodegradation rate of the composite film are less strong.
    [0114] In Comparison Example 4, since polyterephthalic acid-adipic acid-butylene glycol ester was not added to the outer film, according to the data in Table 3, the packaging bag formed by composite film of application example 4, the tensile strength, barrier properties and biodegradation rate all are worse, that means polylactic acid which cooperates with polyterephthalic acid-adipic acid-ester of butylene glycol can improve the barrier properties and the biodegradation rate of the composite film.
    [0115] From the comparison of the contents of polylactic acid and polyterephthalic acid-adipic acid-butylene glycol ester of Comparative Example 1-4, if the addition amount of polylactic acid is controlled from 80-95 %, that of polyterephthalic acid-adipic acid-butylene glycol ester is controlled by 5-20%, which can improve the barrier properties and biodegradation rate of the packaging bag.
    [0116] In Comparative Example 5, the addition amount of the polyterephthalic acid-adipic acid-butylene glycol ester of the inner film is 60%, and that of the biological starch is 40%, the content of the bio-starch is increased, according to the data in the table, the biodegradation rate of the packaging bag is a little different from that of the application example 1-5, but the tensile strength, the rate of elongation at break and barrier properties are less good.
    [0117] In the comparison example 6, the content of polyterephthalic acid-adipic acid-butylene glycol ester of the inner film is 65%, and that of the biological starch is 35%, the packaging bag formed from the composite film in comparison example 6, all the properties are worse than that of application example 1, and are better than that of comparison example 5, it means that when the content of polyterephthalic acid -adipic acid-butylene glycol ester is increased and that of biological starch is lowered, the barrier properties and the rate of biodegradation can be improved.
    [0118] In Comparative Example 7, the content of polyterephthalic acid-adipic acid-butylene glycol ester of the inner film is 95%, and that of biological starch is 5%, according to the results of test, when the polyterephthalic acid-adipic acid-butylene glycol ester content is increased, the barrier properties, biodegradation rate and tensile strength of the packing bag are worse.
    [0119] In Comparison Example 8, since the bio-starch was not added to the inner film, based on the test data, the barrier properties and the biodegradation rate of the packaging bag not d Biological starch are less good, it means that the biological starch which cooperates with polyterephthalic acid-adipic acid-butylene glycol ester can improve the barrier properties and the biodegradation rate of the composite film.
    [0120] From the comparison of the contents of organic starch and polyterephthalic acid-adipic acid-butylene glycol ester of Comparative Example 5-8, if the content of polyterephthalic acid-adipic acid-butylene glycol ester of inner film is controlled by 70-90%, that of biological starch is controlled by 10-30%, which can improve the barrier properties and the biodegradation rate of the packaging bag.
    [0121] The film of Comparison Example 9 and 10 is formed by the present technology, the composite film of Comparison Example 11, the outer film of which is formed from the film of Comparison Example 9, and the inner film is formed of the film of comparison example 10, according to the data in the table, the tensile strength and elongation rate at break of comparison example 9, 10, 11 are good, the rate of biodegradation can reach nearly 100% by day 120, but barrier properties are poor.
    [0122] 2, Detection of compost degradation rate: Form the composite film according to the manner of Application Example 1-5, and detect according to EN13432 "Requirements for the testing and final evaluation of building materials". 'packaging by recycling through compost and biological decomposition', the virgin group is the degradable film sold in the market, the detection results are shown in Table 4.
    [0123] Table 4, detection results of the compost degradation rate of the composite film of Example 1-5.
    [0124] Sensing element Chemical properties Aerobic degradation rate/% Compost decay rate /% Biological toxicity / 90d 120d 150d 180d 6 weeks 9 weeks 12 week Germination rate /% Average daily plant gain /g Application example 1 Heavy metal does not cross the limit 84.6 94.3 98.9 100 91.2 96.8 100 97.5 1.5 Application example 2 Heavy metal does not cross the limit 89.4 97.7 100 100 90.2 95.6 99.3 96.8 1.6Application example 3 Heavy metal does not cross the limit 94.6 100 100 100 91.3 97.3 100 98.6 1.8Application example 4 Heavy metal does not cross the limit 87.8 98.4 99.8 100 90.4 96.3 99.5 98.2 1.7 Application example 5 Heavy metal does not cross the limit 87.2 93.6 97.3 100 91.3 98.4 100 97.6 1.6 Blank group Heavy metal does not cross the limit 67.5 72.1 79.5 87.1 64.2 71.3 78.4 76.2 1.2
    [0125] According to the data shown in Table 4, there is no heavy metal in the fully degradable composite film formed according to Application Example 1-5, and the compost degradation rate can reach 100% at 120-180th day, and 99.3-100% can be decomposed into the piece which can pass the sieve in diameter of 22mm, no biological toxicity, the germination rate is high after planting the tree, and the growth speed is fast.
    权利要求:
    Claims (10)
    [0001]
    A kind of 100% fully biodegradable composite film characterized by the three-layer structure, the outer film of which is composed of the following mass percentage components: 80-95% polylactic acid, polyterephthalic acid-adipic acid-butylene glycol ester at 5-20%; - the intermediate film consists of the aqueous dispersion of the polyester-polyurethane elastomer; and - the internal film is composed of the following mass percentage components: polyterephthalic acid-adipic acid-butylene glycol ester at 70 to 90%, organic starch at 10 to 30%.
    [0002]
    The characteristic of the fully 100% biodegradable composite film referred to in claim 1 is that the outer film is composed of the following mass percentage components: 85-90% polylactic acid, polyterephthalic acid-adipic acid-butylene glycol ester 10 at 15%; - the intermediate film consists of the aqueous dispersion of the polyester-polyurethane elastomer; - the internal film is composed of the following mass percentage components: polyterephthalic acid-adipic acid-butylene glycol ester at 75 to 85%, organic starch at 15 to 25%.
    [0003]
    The feature of the fully 100% biodegradable composite film referred to in claim 1 is that the referred outer film has a thickness of 0.015 to 0.1 mm, the inner film having a thickness of 0.03 to 0.15 mm.
    [0004]
    The feature of the fully 100% biodegradable composite film referred to in claim 1 is that the referred to biological starch is produced by the following processes: (1) add bagasse in sodium hydroxide solution having a solid-liquid ratio of 1:20 to 25 and a concentration of 1%, then stir for 2 hours, and then filter, wash and dry; (2) dissolve aminotriacetic acid with 5% ammonia water, add dried bagasse and ammonium persulfate, react at 60-65°C for 1.5-2h, then wash and drying, the mass proportion of aminotriacetic acid, bagasse and ammonium persulfate is 1: (2 to 2.2): (0.8 to 1); (3) dissolving bagasse taken in step (2) in mixed solution in 20-30% concentration of 1-butyl-3-methylimidazolium chloride and 1-ethyl-3-acetate methylimidazolium, solid-liquid ratio of bagasse and mixed solution is 1:5 to 8, dissolution temperature is 80 to 90°C, stir for 1.5 to 2h, then filter, and pour filtrate in corn starch, potato starch and polypropylene carbonate in a mass ratio of 1:(0.6 to 0.9):(0.5 to 0.8):( 0.5 to 0.7), mix at a temperature of 35-45°C to form organic starch.
    [0005]
    The characteristic of the fully 100% biodegradable composite film referred to in claim 1 is that the molecular weight of polylactic acid is 100,000 to 200,000, and the molecular weight of polyterephthalic acid-adipic acid-butylene glycol ester is 60,000 to 100,000.
    [0006]
    The feature of the 100% fully biodegradable composite film processing technology referred to by any article of any one of claims 1 to 5 is that the following steps are included: S1) The manufacture of the outer film: after mixing polylactic acid and polyterephthalic acid-adipic acid-butylene glycol ester homogeneously, pressing-in using a twin-screw extruder, which we a pressed is formed into film via film blowing machine, and then is formed into outer film after cooling, pulling and rolling; S2) the printing ink: printing the desired design on one side of the outer film, and drying it; S3) The manufacture of the inner film: after mixing polyterephthalic acid-adipic acid-butylene glycol ester and biological starch homogeneously, pressing it using a twin-screw extruder, which we have pressed is formed into film, and then is formed into inner film after cooling, pulling and rolling; S4) the composition: apply a layer of polyvinyl alcohol with the brush roller at a temperature of 35 to 50°C on the side of the printed design of the outer film, and then apply a layer of the aqueous dispersion of the elastomer of polyester-polyurethane with the brush roller at a temperature of 35-50°C, finally press the outer film with the brush roller at a temperature of 35-50°C on the side coated with a layer of the aqueous dispersion of the polyester-polyurethane elastomer of the outer yarn, performing cooling, pulling and rolling on the formed composite film to form a semi-finished composite film; the coating amount of polyvinyl alcohol is 1.2 to 2 g/m 2 , and the coating amount of the aqueous dispersion of the polyester-polyurethane elastomer is 3 to 5 g/m 2 ; and S5) Maturation: put the semi-finished composite film into the maturing chamber, control the maturing temperature at 35-45°C, maturing time is 12-48h, and the finished composite film will be formed after maturing .
    [0007]
    The characteristic of the fully 100% biodegradable composite film referred to in claim 6 is that the temperatures of each zone of the film blowing machine referred to in step S1 are as follows: zone 1: 145 to 155°C, zone 2 :155 to 165°C, zone 3: 160 to 170°C, zone 4: 165 to 175°C, zone 5: 170 to 180°C, zone 6: 170 to 180°C; and the temperatures of each zone of the film blowing machine referred to in step S3 are as follows: zone 1: 115 to 125°C, zone 2: 125 to 130°C, zone 3: 125 to 130°C, zone 4: 130 to 140°C, zone 5: 140 to 150°C, zone 6: 150 to 160°C.
    [0008]
    The characteristic of the fully 100% biodegradable composite film referred to in claim 6 is that the bonding pressure of the inner and outer film referred to in step S4 is 0.1 to 0.8MPa, and the pressure time is the time of pressure is 0.5 to 1 min/mm.
    [0009]
    The characteristic of the fully 100% biodegradable composite film referred to in claim 6 is that the pulling speed referred to in the step of S1, S2 and S4 is 100 to 200 m/min, the internal and external film unwinding tension mentioned in step S4 is 6 to 8 kg/m, the unwinding tension of the half-finished composite film is 7 to 12 kg/m.
    [0010]
    The feature of the application of the 100% fully biodegradable composite film referred to by any article in any one of claims 1 to 5 is that this 100% fully biodegradable composite film can be used to form the sealed flat bag three-side sealed bag, three-side sealed bag, four-side sealed bag, back-sealed bag and open-and-close strip bag.
    类似技术:
    公开号 | 公开日 | 专利标题
    Lopez et al.2014|Thermo-compression of biodegradable thermoplastic corn starch films containing chitin and chitosan
    FR3094918A1|2020-10-16|Fully 100% biodegradable composite film, its processing technology and application
    Elkhaoulani et al.2013|Mechanical and thermal properties of polymer composite based on natural fibers: Moroccan hemp fibers/polypropylene
    AU2012356192B2|2016-06-30|Multi-layered film containing a biopolymer
    RU2561103C2|2015-08-20|Mixtures of polylactic acid and water-soluble polymer
    US5654353A|1997-08-05|Biodegradable composition, a process for preparing the same and the use thereof
    FR2957928A1|2011-09-30|PLANT BASED COMPOSITIONS AND PROCESS FOR PREPARING SUCH COMPOSITIONS
    FR2932488A1|2009-12-18|CIPO - Patent - 2581626 Canadian Intellectual Property Office Symbol of the Government of Canada CA 2461392 STARCH - BASED THERMOPLASTIC OR ELASTOMERIC COMPOSITIONS AND PROCESS FOR THE PREPARATION OF SUCH COMPOSITIONS.
    FR2927088A1|2009-08-07|PLASTICIZED STARCH THERMOPLASTIC COMPOSITIONS AND PROCESS FOR THE PREPARATION OF SUCH COMPOSITIONS.
    FR2927084A1|2009-08-07|PROCESS FOR THE PREPARATION OF THERMOPLASTIC COMPOSITIONS BASED ON PLASTICIZED STARCH AND COMPOSITIONS THUS OBTAINED
    US10457023B2|2019-10-29|Bi-axially stretched article and silage film
    FR2927083A1|2009-08-07|Preparing thermoplastic composition based on amylaceous soluble material, comprises selecting a soluble amylaceous material and a binding agents and incorporating the binding agent in amylaceous soluble material by thermomechanical mixing
    CN109504042A|2019-03-22|PHA modified TPS/PBAT biodegradable resin and preparation method thereof
    EP3221390B1|2018-09-05|Composition of polyester and thermoplastic starch, having improved mechanical properties
    EP2516535A1|2012-10-31|Compositions containing plant matter and synthetic fibres and method for preparing such compositions
    FR3098443A1|2021-01-15|A fully high mechanical strength biodegradable composite film, its processing technology and application
    Ng et al.2022|Preliminary evaluation of the properties and biodegradability of glycerol-and sorbitol-plasticized potato-based bioplastics
    González et al.2011|Starch-based polymers for food packaging
    FR2791603A1|2000-10-06|Water-resistant biodegradable composite material useful for making containers comprises a core of thermoplastic starch and a shell of a biodegradable polymer having a low melting point and a high viscosity
    EP3548546B1|2021-06-02|Biaxially stretched starch-based foil
    JP2005336423A|2005-12-08|Method for manufacturing water-resistant, transparent, thermoplastic organic composition, and thermoplastic organic composition obtained thereby
    EP0440557A2|1991-08-07|Saponified ethylene-vinyl-acetate composition containing hydrotalcite and use thereof
    CN113773559A|2021-12-10|Biodegradable composite modified film bag particle material and preparation method thereof
    FR2990209A1|2013-11-08|FOAMS BASED ON THERMOPLASTIC STARCH AND POLYOLEFIN
    FR3106592A1|2021-07-30|Process for the Preparation of an Enzyme Masterbatch
    同族专利:
    公开号 | 公开日
    CN110091564B|2021-07-30|
    CN110091564A|2019-08-06|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    CN105492207A|2013-06-27|2016-04-13|富特罗股份有限公司|Multilayer film comprising biopolymers|
    CN104151622B|2014-08-08|2016-09-07|华中科技大学|A kind of biodegradable cellulose intermingling material and preparation method thereof|
    CN206884315U|2017-04-10|2018-01-16|广州市粤盛工贸有限公司|A kind of degradable films|
    JP3216909U|2017-12-08|2018-07-05|ユー．エス．パシフィック ノンウーブンス インダストリー リミテッドＵ．Ｓ．Ｐａｃｉｆｉｃ Ｎｏｎｗｏｖｅｎｓ Ｉｎｄｕｓｔｒｙ Ｌｉｍｉｔｅｄ|Biodegradable laminated material|CN111454584A|2020-04-26|2020-07-28|刘科勇|Non-toxic environment-friendly degradable packaging material and preparation method thereof|
    CN113427839A|2021-08-26|2021-09-24|金石科技发展有限公司|Composite film bag and preparation method thereof|
    法律状态:
    2020-11-20| PLFP| Fee payment|Year of fee payment: 2 |
    2021-11-22| PLFP| Fee payment|Year of fee payment: 3 |
    优先权:
    申请号 | 申请日 | 专利标题
    CN201910300685.4A|CN110091564B|2019-04-15|2019-04-15|Full-biological 100% full-degradable composite membrane and processing technology and application thereof|
    CN201910300685.4|2019-04-15|
    [返回顶部]