A preparation process of lightweight soft label film

Abstract

The invention discloses a preparation process of a lightweight soft label film, and relates to the technical field of thin films. When preparing the lightweight soft label film, the invention first reacts polyvinyl chloride, aminated DOPO, and a benzophenone derivative to obtain modified polyvinyl chloride, reacts 2,4,6,8-tetramethyltetravinylcyclotetrasiloxane and 4-(dimethylamino)benzene-1-thiol to obtain a functionalized cyclosiloxane monomer; reacts the functionalized cyclosiloxane monomer with octamethylcyclotetrasiloxane to obtain a functionalized polysiloxane, reacts a polyester with the functionalized polysiloxane to obtain an organosilicon-modified polyester, and mixes the organosilicon-modified polyester with polyvinyl chloride to prepare a lightweight soft label film. The lightweight soft label film prepared by the invention has excellent heat resistance, UV aging resistance, and flame retardancy.

Description

Technical Field

[0001] The invention relates to the technical field of films, in particular to a preparation process of a lightweight soft label film. Background Art

[0002] As a common polymer material, polyvinyl chloride is widely used in the production of various label products due to its good physical and chemical properties. However, traditional polyvinyl chloride label films have some significant performance defects in practical applications;

[0003] First, conventional PVC label films are prone to color change and physical property degradation under long-term sunlight exposure, affecting the service life of the label; second, although traditional PVC materials have certain flame retardancy, they often fail to meet more stringent safety standards. In a fire or high temperature environment, these films may burn quickly; in a high temperature environment, these films are prone to deformation or size shrinkage, causing the label to distort or fall off, which is particularly prominent in processing such as thermal transfer printing;

[0004] In summary, although polyvinyl chloride is an economical and widely used material, its shortcomings in terms of UV aging resistance, flame retardancy and heat resistance limit its performance in advanced label applications. Therefore, developing a new type of lightweight soft label film that not only maintains the basic advantages of polyvinyl chloride but also improves these key properties is of great significance to meet the market demand for high-performance labels. Summary of the invention

[0005] The object of the present invention is to provide a preparation process of a lightweight soft label film to solve the problems existing in the prior art.

[0006] In order to solve the above technical problems, the present invention provides the following technical solutions:

[0007] A preparation process of a light and soft label film comprises the following steps: mixing modified polyvinyl chloride, organosilicon-modified polyester and calcium-zinc stabilizer to prepare the light and soft label film.

[0008] As an optimization, the modified polyvinyl chloride is prepared from polyvinyl chloride, aminated DOPO, and a benzophenone derivative.

[0009] As an optimization, the organosilicon-modified polyester is obtained by reacting a polyester obtained by reacting succinic acid and hexanediol with a functionalized polysiloxane.

[0010] As an optimization, the functionalized polysiloxane is obtained by reacting a functionalized polysiloxane monomer obtained by reacting 2,4,6,8-tetramethyltetravinylcyclotetrasiloxane and 4-(dimethylamino)benzene-1-thiol with octamethylcyclotetrasiloxane.

[0011] A preparation process of a lightweight soft label film comprises the following steps:

[0012] (1) mixing polyvinyl chloride, aminated DOPO, benzophenone derivative and N,N-dimethylacetamide in a mass ratio of 1:20-30:30-40:100-150, stirring at 80-90° C. for 3-4 hours, adding pure water 4-5 times the volume of N,N-dimethylacetamide, filtering and washing with pure water for 3-5 times, and drying at 50-60° C. for 6-8 hours to obtain modified polyvinyl chloride;

[0013] (2) 2,4,6,8-tetramethyltetravinylcyclotetrasiloxane, 4-(dimethylamino)benzene-1-thiol, azobisisobutyronitrile and anhydrous toluene are mixed in a mass ratio of 1:4.1-4.2:0.1-0.3:10-12, and three consecutive freeze-vacuum-thaw cycles are performed under sealed conditions for degassing, and then the temperature is raised to 100° C. in an argon atmosphere, and the reaction is performed for 2 hours. After cooling to room temperature, a 1 mol / L sodium bicarbonate aqueous solution with a volume of 4-5 times that of anhydrous toluene is added, and ethyl acetate is used for extraction, and the organic phase is washed 3-4 times with a 1 mol / L sodium bicarbonate aqueous solution, and then the organic phase is washed 3-4 times with pure water, and finally, the functionalized cyclosiloxane monomer is obtained by rotary evaporation at 80° C. for 5-10 minutes;

[0014] (3) octamethylcyclotetrasiloxane and functionalized cyclosiloxane monomer are mixed in a mass ratio of 1:1.5-1.7, and stirred for 20-30 min at 90° C. under nitrogen protection, with a stirring speed of 300-400 r / min, and the temperature is continuously raised to 100-110° C., and a 25 wt % aqueous solution of tetramethylammonium hydroxide with a mass of 0.02%-0.03% of octamethylcyclotetrasiloxane is added, and pure water with a mass of 0.3%-0.4% of octamethylcyclotetrasiloxane is added, and the reaction is continued for 2-3 h, and the temperature is continuously raised to 150° C. and the reaction is continued for 2-3 h to obtain functionalized polysiloxane;

[0015] (4) mixing polyester and functionalized polysiloxane in a mass ratio of 1:0.03-0.05, adding 0.5%-0.7% of dibutyltin dilaurate by mass of polyester under nitrogen protection, heating to 170-180° C. and reacting for 2-3 hours to obtain organosilicon-modified polyester;

[0016] (5) Add modified polyvinyl chloride, silicone modified polyester and calcium zinc stabilizer into a high-speed mixer, mix at a speed of 1000-1200 r / min for 20-30 min to obtain a mixture, use a two-roll mill to mix the mixture at 170° C. for 10 min, and after mixing, process it into a 0.03 mm thick film, form the film by static molding, and press it on a small tablet press. The specific conditions are hot pressing at 165-170° C. and 5 MPa for 3 min, hot pressing at 10 MPa for 5 min, then taking it out and cold pressing it at room temperature and 5 MPa to obtain a lightweight soft label film.

[0017] As an optimization, the preparation method of the aminated DOPO in step (1) is: 10-(2,5-dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide, p-fluoronitrobenzene, cesium fluoride and N,N-dimethylacetamide are mixed uniformly in a mass ratio of 1:3-3.5:3-3.5:25-30, and stirred for reaction for 9-10 hours at a temperature of 150-160° C. under nitrogen protection, and a stirring speed of 300-400 r / min, and filtered and poured the filtrate into an ethanol aqueous solution, wherein the volume ratio of anhydrous ethanol to pure water in the ethanol aqueous solution is 1:2, filtered and washed with the ethanol aqueous solution for 3-4 times, and dried at 110-120° C. for 6-8 hours to obtain aminated DOPO.

[0018] As an optimization, the preparation method of the benzophenone derivative in step (1) is: 3-chloropropionyl chloride, 2,2',4,4'-tetrahydroxybenzophenone, triethylamine and dichloromethane are mixed uniformly in a mass ratio of 2:1:1:200, stirred at 0-4°C for 20-30min, stirring speed 300-400r / min, heated to 20-25°C and continued to stir for 5-6h, added with pure water of equal volume to dichloromethane, separated and collected the lower organic phase, continued to add methanol of equal volume to dichloromethane at 50°C, cooled to room temperature and filtered, and dried at 50-60°C for 6-8h to obtain a benzophenone derivative.

[0019] As an optimization, the preparation method of the polyester in step (4) is: mixing succinic acid and hexylene glycol in a molar ratio of 1:1.1-1.2, adding tetrabutyl titanate with a mass% of 0.3%-0.5% of succinic acid at 120°C in a nitrogen atmosphere, heating to 170°C for reaction for 3-4h, and continuing to heat to 190°C for reaction for 2h to obtain polyester.

[0020] As an optimization, the weighed amounts of the modified polyvinyl chloride, silicone-modified polyester and calcium-zinc stabilizer in step (5) are, by mass, 100 parts of modified polyvinyl chloride, 30-40 parts of silicone-modified polyester and 2-3 parts of calcium-zinc stabilizer, wherein the model of the calcium-zinc stabilizer is P1129-1.

[0021] As an optimization, the polyvinyl chloride model described in step (1) is SG5.

[0022] Compared with the prior art, the beneficial effects achieved by the present invention are:

[0023] When preparing a light-weight soft label film, the present invention firstly reacts polyvinyl chloride, aminated DOPO and a benzophenone derivative to obtain modified polyvinyl chloride, reacts 2,4,6,8-tetramethyltetravinylcyclotetrasiloxane and 4-(dimethylamino)benzene-1-thiol to obtain a functionalized cyclosiloxane monomer; reacts the functionalized cyclosiloxane monomer and octamethylcyclotetrasiloxane to obtain a functionalized polysiloxane, reacts polyester and the functionalized polysiloxane to obtain an organosilicon-modified polyester, and mixes the organosilicon-modified polyester with polyvinyl chloride to prepare the light-weight soft label film.

[0024] Firstly, polyvinyl chloride, aminated DOPO and benzophenone derivatives are used to prepare modified polyvinyl chloride. Aminated DOPO is prepared by reacting 10-(2,5-dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide and p-fluoronitrobenzene through the reaction of hydroxyl and fluorine. Benzophenone derivatives are prepared by reacting 3-chloropropionyl chloride and 2,2',4,4'-tetrahydroxybenzophenone through the reaction of hydroxyl and acyl chloride. DOPO, as a kind of organic compound containing phosphorus, decomposes at high temperature to form a carbonized protective layer, which can provide excellent flame retardancy for polyvinyl chloride film. The interaction between hydroxyl and carbonyl on benzophenone derivative can absorb ultraviolet rays, thus giving the polyvinyl chloride film excellent anti-ultraviolet aging performance.

[0025] Secondly, 2,4,6,8-tetramethyltetravinylcyclotetrasiloxane and 4-(dimethylamino)benzene-1-thiol are reacted to obtain a functionalized cyclosiloxane monomer, and a tertiary amine-containing cyclosiloxane is prepared through a mercapto-ene click chemistry reaction. The functionalized cyclosiloxane monomer is reacted with octamethylcyclotetrasiloxane to obtain a functionalized polysiloxane, and a polyester obtained by reacting succinic acid and hexanediol is reacted with the functionalized polysiloxane to obtain a modified polyester. The functionalized polysiloxane is prepared by ring-opening octamethylcyclotetrasiloxane and the functionalized cyclosiloxane monomer, and then using water as a capping agent to obtain a double-terminal hydroxyl-containing linear polysiloxane containing a tertiary amine. The double-terminal hydroxyl-containing linear polysiloxane can react with the polyester. The presence of the polysiloxane can provide good heat resistance for the polyvinyl chloride film.

[0026] Finally, modified polyvinyl chloride, silicone-modified polyester and calcium-zinc stabilizer were mixed and a lightweight soft label film was prepared by a casting method. The silicone-modified polyester and modified polyvinyl chloride have good compatibility, which can not only break the interaction between the molecular chains of modified polyvinyl chloride and increase the plasticity and flexibility of modified polyvinyl chloride, but also the chlorine on the benzophenone derivative grafted on the modified polyvinyl chloride can attack the polyester on the silicone modification to form a quaternary ammonium salt structure with antibacterial effect, thus giving the film certain antibacterial properties. DETAILED DESCRIPTION

[0027] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative work are within the scope of protection of the present invention.

[0028] The calcium zinc stabilizer used in the following examples and comparative examples is model P1129-1, purchased from Changzhou Youjia New Material Technology Co., Ltd., and the polyvinyl chloride model is SG5, purchased from Guangzhou Xinkaiyuan Chemical Co., Ltd.

[0029] Example 1

[0030] A preparation process of a lightweight soft label film comprises the following preparation steps:

[0031] (1) 10-(2,5-dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide, p-fluoronitrobenzene, cesium fluoride and N,N-dimethylacetamide were mixed uniformly in a mass ratio of 1:3:3:25, stirred for 10 hours at a temperature of 160° C. under nitrogen protection, and the stirring speed was 400 r / min. The filtrate was filtered and poured into an ethanol aqueous solution, wherein the volume ratio of anhydrous ethanol to pure water in the ethanol aqueous solution was 1:2, filtered and the precipitate was washed 4 times with the ethanol aqueous solution, and heated at 120° C. Dry at 40°C for 8 hours to obtain aminated DOPO; 3-chloropropionyl chloride, 2,2',4,4'-tetrahydroxybenzophenone, triethylamine and dichloromethane were mixed at a mass ratio of 2:1:1:200, stirred at 4°C for 30 minutes, stirring speed 400r / min, heated to 25°C and continued to stir for 6 hours, added pure water with an equal volume of dichloromethane, separated and collected the lower organic phase, continued to add methanol with an equal volume of dichloromethane at 50°C, cooled to room temperature and filtered, and dried at 60°C for 8 hours to obtain benzophenone derivatives. Polyvinyl chloride, aminated DOPO, benzophenone derivatives and N,N-dimethylacetamide were mixed at a mass ratio of 1:20:30:100, stirred at 90°C for 4 hours, added pure water 4 times the volume of N,N-dimethylacetamide, filtered and washed 5 times with pure water, and dried at 60°C for 8 hours to obtain modified polyvinyl chloride;

[0032] (2) 2,4,6,8-tetramethyltetravinylcyclotetrasiloxane, 4-(dimethylamino)benzene-1-thiol, azobisisobutyronitrile and anhydrous toluene were mixed in a mass ratio of 1:4.1:0.1:10, and degassed by three consecutive freeze-vacuum-thaw cycles under sealed conditions. Then, the mixture was heated to 100° C. in an argon atmosphere and reacted for 2 h. After cooling to room temperature, a 1 mol / L sodium bicarbonate aqueous solution with a volume of 5 times that of anhydrous toluene was added, and the mixture was extracted with ethyl acetate. The organic phase was washed 4 times with a 1 mol / L sodium bicarbonate aqueous solution, and then washed 4 times with pure water. Finally, the functionalized cyclosiloxane monomer was obtained by rotary evaporation at 80° C. for 10 min.

[0033] (3) octamethylcyclotetrasiloxane and functionalized cyclosiloxane monomers were mixed in a mass ratio of 1:1.5, stirred and mixed for 30 min at 90° C. under nitrogen protection, with a stirring speed of 400 r / min, and then heated to 110° C., and a 25 wt % aqueous solution of tetramethylammonium hydroxide (0.02% by mass of octamethylcyclotetrasiloxane) was added, and pure water (0.3% by mass of octamethylcyclotetrasiloxane) was added, and the reaction was continued for 3 h, and then the temperature was continued to be raised to 150° C. and reacted for 3 h to obtain functionalized polysiloxane;

[0034] (4) Succinic acid and hexylene glycol were mixed in a molar ratio of 1:1.1, tetrabutyl titanate (0.3% by weight of succinic acid) was added at 120°C in a nitrogen atmosphere, the temperature was raised to 170°C for reaction for 4 hours, and the temperature was further raised to 190°C for reaction for 2 hours to obtain polyester; polyester and functionalized polysiloxane were mixed in a mass ratio of 1:0.03, dibutyltin dilaurate (0.5% by weight of polyester) was added under nitrogen protection, the temperature was raised to 180°C for reaction for 3 hours to obtain silicone-modified polyester;

[0035] (5) Weigh 100 parts of modified polyvinyl chloride, 30 parts of organosilicon-modified polyester, and 2 parts of calcium-zinc stabilizer by mass, add the modified polyvinyl chloride, organosilicon-modified polyester, and calcium-zinc stabilizer into a high-speed mixer, mix at a speed of 1200 r / min for 30 minutes to obtain a mixture, use a two-roll mill to mix the mixture at 170° C. for 10 minutes, and after mixing, process the mixture into a 0.03 mm thick film, form the film by static molding, and press the film on a small tablet press. The specific conditions are hot pressing at 170° C. and 5 MPa for 3 minutes, hot pressing at 10 MPa for 5 minutes, then taking out and cold pressing at room temperature and 5 MPa to obtain a lightweight soft label film.

[0036] Example 2

[0037] A preparation process of a lightweight soft label film comprises the following preparation steps:

[0038] (1) 10-(2,5-dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide, p-fluoronitrobenzene, cesium fluoride and N,N-dimethylacetamide were mixed in a mass ratio of 1:3.2:3.3:27, and stirred for 9.5 hours at a temperature of 155°C under nitrogen protection, and the stirring speed was 350 r / min. The filtrate was filtered and poured into an ethanol aqueous solution, wherein the volume ratio of anhydrous ethanol to pure water in the ethanol aqueous solution was 1:2, and the precipitate was washed 3 times with the ethanol aqueous solution, and dried at 115°C for 7 hours to obtain aminated DOPO; 3-chloropropionyl chloride, 2,2',4,4'-tetrahydroxybenzophenone, triethylamine and dichloromethane were mixed in a mass ratio of 2:1 :1:200, stir evenly at 3°C ​​for 25 min, stirring speed 350r / min, heat to 22°C and continue stirring for 5.5h, add pure water of equal volume to dichloromethane, separate and collect the lower organic phase, continue to add methanol of equal volume to dichloromethane at 50°C, cool to room temperature and filter, dry at 55°C for 7h to obtain benzophenone derivative; mix polyvinyl chloride, aminated DOPO, benzophenone derivative and N,N-dimethylacetamide in a mass ratio of 1:25:35:120, stir at 85°C for 3.5h, add pure water of 4.5 times the volume of N,N-dimethylacetamide, filter and wash 4 times with pure water, dry at 55°C for 7h to obtain modified polyvinyl chloride;

[0039] (2) 2,4,6,8-tetramethyltetravinylcyclotetrasiloxane, 4-(dimethylamino)benzene-1-thiol, azobisisobutyronitrile and anhydrous toluene were mixed in a mass ratio of 1:4.15:0.2:11, and degassed by three consecutive freeze-vacuum-thaw cycles under sealed conditions. Then, the mixture was heated to 100° C. in an argon atmosphere and reacted for 2 h. After cooling to room temperature, a 1 mol / L sodium bicarbonate aqueous solution with a volume of 4.5 times that of anhydrous toluene was added, and extracted with ethyl acetate. The organic phase was washed three times with a 1 mol / L sodium bicarbonate aqueous solution, and then washed three times with pure water. Finally, the functionalized cyclosiloxane monomer was obtained by rotary evaporation at 80° C. for 7 min.

[0040] (3) octamethylcyclotetrasiloxane and functionalized cyclosiloxane monomer were mixed in a mass ratio of 1:1.6, stirred and mixed for 25 min at 90° C. under nitrogen protection, with a stirring speed of 350 r / min, and then heated to 105° C., and a 25 wt % aqueous solution of tetramethylammonium hydroxide (0.025% by mass of octamethylcyclotetrasiloxane) was added, and pure water (0.35% by mass of octamethylcyclotetrasiloxane) was added, and the reaction was continued for 2.5 h, and then the temperature was continued to be raised to 150° C. and reacted for 2.5 h to obtain functionalized polysiloxane;

[0041] (4) Succinic acid and hexylene glycol were mixed in a molar ratio of 1:1.15, tetrabutyl titanate (0.4% by weight of succinic acid) was added at 120°C in a nitrogen atmosphere, the temperature was raised to 170°C for reaction for 3.5 hours, and the temperature was further raised to 190°C for reaction for 2 hours to obtain polyester; polyester and functionalized polysiloxane were mixed in a mass ratio of 1:0.04, dibutyltin dilaurate (0.6% by weight of polyester) was added under nitrogen protection, the temperature was raised to 175°C for reaction for 2.5 hours to obtain silicone-modified polyester;

[0042] (5) Weigh 100 parts of modified polyvinyl chloride, 35 parts of silicone modified polyester, and 2 parts of calcium zinc stabilizer by mass, add the modified polyvinyl chloride, silicone modified polyester, and calcium zinc stabilizer into a high-speed mixer, mix at a speed of 1100 r / min for 25 minutes to obtain a mixture, use a two-roll mill to mix the mixture at 170° C. for 10 minutes, and after mixing, process it into a 0.03 mm thick film, form the film by static molding, and press it on a small tablet press. The specific conditions are hot pressing at 167° C. and 5 MPa for 3 minutes, hot pressing at 10 MPa for 5 minutes, then taking it out and cold pressing it at room temperature and 5 MPa to obtain a lightweight soft label film.

[0043] Example 3

[0044] A preparation process of a lightweight soft label film comprises the following preparation steps:

[0045] (1) 10-(2,5-dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide, p-fluoronitrobenzene, cesium fluoride and N,N-dimethylacetamide were mixed in a mass ratio of 1:3.5:3.5:30, stirred for reaction for 9 h at 150°C under nitrogen protection, and the stirring speed was 300 r / min. The filtrate was filtered and poured into an ethanol aqueous solution, wherein the volume ratio of anhydrous ethanol to pure water in the ethanol aqueous solution was 1:2. The precipitate was washed 3 times with the ethanol aqueous solution, and dried at 110°C for 6 h to obtain aminated DOPO. 3-chloropropionyl chloride, 2,2',4,4'-tetrahydroxybenzophenone, triethylamine and dichloromethane were mixed in a mass ratio of 2 :1:1:200, mix evenly, stir at 0°C for 20min, stirring speed 300r / min, heat to 20°C and continue stirring for 5h, add pure water with the same volume as dichloromethane, separate and collect the lower organic phase, continue to add methanol with the same volume as dichloromethane at 50°C, cool to room temperature and filter, dry at 50°C for 6h to obtain benzophenone derivatives; mix polyvinyl chloride, aminated DOPO, benzophenone derivatives and N,N-dimethylacetamide at a mass ratio of 1:30:40:150, stir at 80°C for 3h, add pure water with 4 times the volume of N,N-dimethylacetamide, filter and wash 3 times with pure water, dry at 50°C for 6h to obtain modified polyvinyl chloride;

[0046] (2) 2,4,6,8-tetramethyltetravinylcyclotetrasiloxane, 4-(dimethylamino)benzene-1-thiol, azobisisobutyronitrile and anhydrous toluene were mixed in a mass ratio of 1:4.2:0.3:12, and degassed by three consecutive freeze-vacuum-thaw cycles under sealed conditions. Then, the mixture was heated to 100° C. in an argon atmosphere and reacted for 2 h. After cooling to room temperature, a 1 mol / L sodium bicarbonate aqueous solution with a volume of 5 times that of anhydrous toluene was added, and extracted with ethyl acetate. The organic phase was washed 3-4 times with a 1 mol / L sodium bicarbonate aqueous solution, and then washed 4 times with pure water. Finally, the functionalized cyclosiloxane monomer was obtained by rotary evaporation at 80° C. for 5 min.

[0047] (3) octamethylcyclotetrasiloxane and functionalized cyclosiloxane monomers were mixed at a mass ratio of 1:1.7, stirred and mixed for 20 min at 90° C. under nitrogen protection, with a stirring speed of 300 r / min, and then heated to 100° C., and a 25 wt % aqueous solution of tetramethylammonium hydroxide (0.03% by mass of octamethylcyclotetrasiloxane) was added, and pure water (0.4% by mass of octamethylcyclotetrasiloxane) was added, and the reaction was continued for 2 h, and then the temperature was continued to be raised to 150° C. and reacted for 2 h to obtain functionalized polysiloxane;

[0048] (4) Succinic acid and hexylene glycol were mixed in a molar ratio of 1:1.2, tetrabutyl titanate (0.5% by weight of succinic acid) was added at 120°C in a nitrogen atmosphere, the temperature was raised to 170°C for reaction for 4 hours, and the temperature was further raised to 190°C for reaction for 2 hours to obtain polyester; polyester and functionalized polysiloxane were mixed in a mass ratio of 1:0.05, dibutyltin dilaurate (0.7% by weight of polyester) was added under nitrogen protection, the temperature was raised to 170°C for reaction for 2 hours to obtain silicone-modified polyester;

[0049] (5) Weigh 100 parts of modified polyvinyl chloride, 40 parts of silicone modified polyester, and 3 parts of calcium zinc stabilizer by mass, add the modified polyvinyl chloride, silicone modified polyester, and calcium zinc stabilizer into a high-speed mixer, mix at a speed of 1000 r / min for 20 minutes to obtain a mixture, use a two-roll mill to mix the mixture at 170° C. for 10 minutes, and after mixing, process it into a 0.03 mm thick film, form the film by static molding, and press it on a small tablet press. The specific conditions are hot pressing at 165° C. and 5 MPa for 3 minutes, hot pressing at 10 MPa for 5 minutes, then taking it out and cold pressing it at room temperature and 5 MPa to obtain a lightweight soft label film.

[0050] Comparative Example 1

[0051] The difference between the preparation process of the lightweight soft label film of Comparative Example 1 and Example (2) is that step (1) is modified as follows: (1) 10-(2,5-dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide, p-fluoronitrobenzene, cesium fluoride and N,N-dimethylacetamide are uniformly mixed in a mass ratio of 1:3.2:3.3:27, and stirred for 9.5 hours at a temperature of 155° C. under nitrogen protection, and a stirring speed of 350 r / min, and the filtrate is filtered and poured into ethanol. The aqueous solution, wherein the volume ratio of anhydrous ethanol to pure water in the ethanol aqueous solution is 1:2, is filtered and the precipitate is washed 3 times with the ethanol aqueous solution, and is dried at 115°C for 7 hours to obtain aminated DOPO; polyvinyl chloride, aminated DOPO and N,N-dimethylacetamide are uniformly mixed in a mass ratio of 1:25:120, stirred at 85°C for 3.5 hours, pure water 4.5 times the volume of N,N-dimethylacetamide is added, filtered, washed 4 times with pure water, and dried at 55°C for 7 hours to obtain modified polyvinyl chloride.

[0052] Comparative Example 2

[0053] The preparation process of the lightweight soft label film of Comparative Example 2 is different from that of Example (2) in that step (5) is modified to weigh 100 parts of modified polyvinyl chloride and 2 parts of calcium zinc stabilizer by mass, add the modified polyvinyl chloride, silicone modified polyester and calcium zinc stabilizer into a high-speed mixer, mix at a speed of 1100 r / min for 25 min to obtain a mixture, mix the mixture at 170° C. for 10 min using a two-roll mill, and after mixing, process it into a 0.03 mm thick film, form the film by static molding, and press it on a small tablet press. The specific conditions are hot pressing at 167° C. and 5 MPa for 3 min, hot pressing at 10 MPa for 5 min, then taking it out and cold pressing it at room temperature and 5 MPa to obtain a lightweight soft label film.

[0054] Comparative Example 3

[0055] The preparation process of the lightweight soft label film of Comparative Example 3 is different from that of Example (2) in that steps (2) and (3) are not performed, and step (4) is modified to mix succinic acid and hexylene glycol in a molar ratio of 1:1.15, add tetrabutyl titanate with a mass percentage of 0.4% of succinic acid at 120° C. in a nitrogen atmosphere, heat to 170° C. for reaction for 3.5 h, and continue to heat to 190° C. for reaction for 2 h to obtain polyester;

[0056] Step (5) is modified as follows: 100 parts of modified polyvinyl chloride, 35 parts of polyester and 2 parts of calcium zinc stabilizer are weighed in parts by mass; the modified polyvinyl chloride, polyester and calcium zinc stabilizer are added into a high-speed mixer; mixed at a speed of 1100 r / min for 25 min to obtain a mixture; the mixture is kneaded at 170° C. for 10 min using a two-roll mill; after kneading, the mixture is processed into a 0.03 mm thick film; the film is formed by static molding and pressed on a small tablet press; the specific conditions are hot pressing at 167° C. and 5 MPa for 3 min, hot pressing at 10 MPa for 5 min, then taking out and cold pressing at room temperature and 5 MPa to obtain a lightweight soft label film.

[0057] Test Example 1

[0058] Tensile properties testing

[0059] Test method: The label films prepared in all embodiments and comparative examples were cut into 50 mm × 120 mm specimens and subjected to a tensile performance test. The elongation at break of the film was tested using a Z010 universal material testing machine from the German Zwick / Roell company in accordance with the standard GB / T1040.1-2018.

[0060] Test of anti-ultraviolet aging performance

[0061] Test method: All the label films prepared in the examples and comparative examples were cut into 50 mm × 120 mm samples and placed in an aging box for aging for 168 h. The light source was a fluorescent ultraviolet lamp, and the lamp type was 1A. The peak wavelength of the ultraviolet lamp was 340 nm, and the average radiation intensity of the lamp tube was 0.76 W / m 2 The temperature in the box was controlled at 60°C; the distance between the film surface and the light source was 30 mm. The film before and after aging was tested for tensile strength using the Z010 universal material testing machine of the German Zwick / Roell company in accordance with the standard GB / T1040.1-2018, and the change rate of tensile strength before and after aging was calculated. The results are shown in Table 1.

[0062] Table 1

[0063] Elongation at break (%) Tensile strength change rate (%) Example 1 175.37 98.4 Example 2 169.49 97.3 Example 3 170.38 96.9 Comparative Example 1 173.69 60.4 Comparative Example 2 120.46 96.8 Comparative Example 3 103.52 97.1

[0064] From the comparison of the experimental data of Examples 1-3 and Comparative Examples 1-4 in Table 1, it can be found that the lightweight soft label film prepared in the present invention has good anti-ultraviolet aging performance and plasticity.

[0065] By comparing the elongation at break of Examples 1-3 to that of Comparative Examples 2-3, it is shown that the organosilicon-modified polyester and the modified polyvinyl chloride have good compatibility, which can not only break the interaction between the molecular chains of the modified polyvinyl chloride, but also increase the plasticity and flexibility of the modified polyvinyl chloride;

[0066] By comparison, the change rate of tensile strength of Examples 1-3 is greater than that of Comparative Example 1, indicating that modified polyvinyl chloride is prepared from polyvinyl chloride, aminated DOPO, and benzophenone derivatives, and the hydroxyl and carbonyl groups on the benzophenone derivatives interact to absorb ultraviolet rays, giving the polyvinyl chloride film excellent anti-ultraviolet aging properties.

[0067] Test Example 2

[0068] Heat resistance test

[0069] Test method: Cut the films made in each embodiment and comparative example into disc samples with a diameter of 16 mm, heat treat them at 170°C for 0.5 h, and calculate the thermal shrinkage (η) of the diaphragm at the corresponding temperature. The calculation formula of the thermal shrinkage is η(%) = (S0-S) / S0×100%; where η is the thermal shrinkage of the film, S0 is the initial area of ​​the film, and S is the final area of ​​the film after heat treatment. The results are shown in Table 2.

[0070] Table 2

[0071] Thermal shrinkage (%) Thermal shrinkage (%) Example 1 2.3％ Comparative Example 1 2.5％ Example 2 3.1％ Comparative Example 2 2.4％ Example 3 2.7％ Comparative Example 3 10.6％

[0072] From the comparison of the experimental data of Examples 1-3 and Comparative Examples 1-3 in Table 2, it can be found that the lightweight soft label film prepared in the present invention has good heat resistance.

[0073] By comparison, the heat shrinkage of Examples 1-3 is less than that of Comparative Example 3, indicating that 2,4,6,8-tetramethyltetravinylcyclotetrasiloxane and 4-(dimethylamino)benzene-1-thiol are reacted to obtain a functionalized cyclosiloxane monomer, the functionalized cyclosiloxane monomer is reacted with octamethylcyclotetrasiloxane to obtain a functionalized polysiloxane, the polyester obtained by reacting succinic acid and hexanediol is reacted with the functionalized polysiloxane to obtain a modified polyester, and the functionalized polysiloxane is obtained by ring-opening octamethylcyclotetrasiloxane and the functionalized cyclosiloxane monomer, and then using water as a capping agent to obtain a double-terminal hydroxyl-containing tertiary amine linear polysiloxane, the double-terminal hydroxyl linear polysiloxane can react with the polyester, and the presence of the polysiloxane can provide good heat resistance for the polyvinyl chloride film;

[0074] The specific implementation methods described above further illustrate the objectives, technical solutions and beneficial effects of the present invention in detail. It should be understood that the above description is only a specific implementation method of the present invention and is not intended to limit the scope of protection of the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention should be included in the scope of protection of the present invention.

Claims

1. A process for preparing a lightweight soft label film, characterized in that: The preparation process is to mix modified polyvinyl chloride, silicone-modified polyester and calcium-zinc stabilizer to prepare a light and soft label film; The modified polyvinyl chloride is prepared from polyvinyl chloride, aminated DOPO and benzophenone derivatives; the aminated DOPO is prepared by reacting 10-(2,5-dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide and p-fluoronitrobenzene through a hydroxyl group and a fluorine group; the benzophenone derivative is prepared by reacting 3-chloropropionyl chloride and 2,2',4,4'-tetrahydroxybenzophenone through a hydroxyl group and an acyl chloride group; The organosilicon-modified polyester is obtained by reacting a polyester obtained by reacting succinic acid and hexanediol with a functionalized polysiloxane; The functionalized polysiloxane is obtained by reacting a functionalized polysiloxane monomer obtained by reacting 2,4,6,8-tetramethyltetravinylcyclotetrasiloxane and 4-(dimethylamino)benzene-1-thiol with octamethylcyclotetrasiloxane.

2. The process for preparing a lightweight soft label film according to claim 1, characterized in that: The preparation process comprises the following steps: (1) Mix polyvinyl chloride, aminated DOPO, benzophenone derivative and N,N-dimethylacetamide in a mass ratio of 1:20-30:30-40:100-150, stir at 80-90°C for 3-4 hours, add pure water 4-5 times the volume of N,N-dimethylacetamide, filter and wash with pure water for 3-5 times, and dry at 50-60°C for 6-8 hours to obtain modified polyvinyl chloride; (2) 2,4,6,8-tetramethyltetravinylcyclotetrasiloxane, 4-(dimethylamino)benzene-1-thiol, azobisisobutyronitrile and anhydrous toluene are mixed in a mass ratio of 1:4.1-4.2:0.1-0.3:10-12, and degassed by three consecutive freeze-vacuum-thaw cycles under sealed conditions. Then, the mixture is heated to 100°C in an argon atmosphere and reacted for 2 hours. After cooling to room temperature, a 1 mol / L sodium bicarbonate aqueous solution of 4-5 times the volume of anhydrous toluene is added, and the mixture is extracted with ethyl acetate. The organic phase is washed 3-4 times with a 1 mol / L sodium bicarbonate aqueous solution, and then washed 3-4 times with pure water. Finally, the functionalized cyclosiloxane monomer is obtained by rotary evaporation at 80°C for 5-10 minutes. (3) octamethylcyclotetrasiloxane and functionalized cyclosiloxane monomer are mixed in a mass ratio of 1:1.5-1.7, and stirred for 20-30 min at 90°C under nitrogen protection at a stirring speed of 300-400 r / min, and the temperature is continuously raised to 100-110°C, and a 25wt% aqueous solution of tetramethylammonium hydroxide with a mass of 0.02%-0.03% of octamethylcyclotetrasiloxane is added, and pure water with a mass of 0.3%-0.4% of octamethylcyclotetrasiloxane is added, and the reaction is continued for 2-3h, and the temperature is continuously raised to 150°C, and the reaction is continued for 2-3h to obtain functionalized polysiloxane; (4) The polyester and the functionalized polysiloxane are mixed in a mass ratio of 1:0.03-0.05, and 0.5%-0.7% of dibutyltin dilaurate by mass of the polyester is added under nitrogen protection, and the temperature is raised to 170-180° C. and reacted for 2-3 hours to obtain a silicone-modified polyester; (5) Add modified polyvinyl chloride, silicone modified polyester and calcium zinc stabilizer into a high-speed mixer, mix at a speed of 1000-1200 r / min for 20-30 min to obtain a mixture, use a double-roll mill to mix the mixture at 170°C for 10 min, and after mixing, process it into a 0.03 mm thick film, form the film by static molding, and press it on a small tablet press. The specific conditions are hot pressing at 165-170°C and 5 MPa for 3 min, hot pressing at 10 MPa for 5 min, then taking it out and cold pressing it at room temperature and 5 MPa to obtain a lightweight soft label film.

3. The process for preparing a lightweight soft label film according to claim 2, characterized in that: The preparation method of the aminated DOPO in step (1) is as follows: 10-(2,5-dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide, p-fluoronitrobenzene, cesium fluoride and N,N-dimethylacetamide are uniformly mixed in a mass ratio of 1:3-3.5:3-3.5:25-30, and the mixture is stirred for reaction for 9-10 hours at a temperature of 150-160° C. under nitrogen protection at a stirring speed of 300-400 r / min, and the filtrate is filtered and poured into an ethanol aqueous solution, wherein the volume ratio of anhydrous ethanol to pure water in the ethanol aqueous solution is 1:2, and the precipitate is filtered and washed 3-4 times with the ethanol aqueous solution, and dried at 110-120° C. for 6-8 hours to obtain the aminated DOPO.

4. The process for preparing a lightweight soft label film according to claim 2, characterized in that: The preparation method of the benzophenone derivative in step (1) is as follows: 3-chloropropionyl chloride, 2,2',4,4'-tetrahydroxybenzophenone, triethylamine and dichloromethane are uniformly mixed in a mass ratio of 2:1:1:200, stirred at 0-4°C for 20-30min at a stirring speed of 300-400r / min, heated to 20-25°C and continued to stir for 5-6h, added with pure water in an amount equal to the volume of dichloromethane, separated and collected the lower organic phase, continued to add methanol in an amount equal to the volume of dichloromethane at 50°C, cooled to room temperature and filtered, and dried at 50-60°C for 6-8h to obtain the benzophenone derivative.

5. The process for preparing a lightweight soft label film according to claim 2, characterized in that: The preparation method of the polyester in step (4) is as follows: succinic acid and hexylene glycol are mixed in a molar ratio of 1:1.1-1.2, tetrabutyl titanate with a mass ratio of 0.3%-0.5% of succinic acid is added at 120° C. in a nitrogen atmosphere, the temperature is raised to 170° C. for reaction for 3-4 hours, and the temperature is further raised to 190° C. for reaction for 2 hours to obtain polyester.

6. The process for preparing a lightweight soft label film according to claim 2, characterized in that: The weighed amounts of the modified polyvinyl chloride, silicone-modified polyester and calcium-zinc stabilizer in step (5) are, by mass, 100 parts of modified polyvinyl chloride, 30-40 parts of silicone-modified polyester and 2-3 parts of calcium-zinc stabilizer, wherein the model of the calcium-zinc stabilizer is P1129-1.

7. The process for preparing a lightweight soft label film according to claim 2, characterized in that: The polyvinyl chloride model described in step (1) is SG5.