PVC resins, methods of making and using the same, and PVC film compositions for inkjet coating and methods of making the same

Abstract

The application belongs to the field of synthetic resin preparation, and particularly relates to PVC resin and a preparation method and application thereof, a PVC film raw material composition for glue coating and ink jet, and a PVC film and a preparation method thereof; the PVC resin is a crosslinked copolymer containing structural unit a provided by chloroethylene, structural unit b provided by maleic acid diallyl ester, and structural unit c provided by pentaerythritol triacrylate; the mass ratio of the structural unit a, the structural unit b and the structural unit c is 1:(0.0004-0.0008):(0.002-0.005); the PVC resin in the application has the advantages of suitable surface roughness and good high-temperature resistance; when the PVC resin is used in the PVC film for glue coating and ink jet, the rough and suitable surface of the prepared PVC film is suitable for glue coating and ink jet, and the adhesion between the glue coating layer and the pigment and the film can be increased; and the PVC film has good high-temperature resistance, and the glue coating layer after the film surface is coated with glue can be quickly cured under high-temperature conditions.

Description

Technical Field

[0001] This invention belongs to the field of synthetic resin preparation, specifically relating to a PVC resin and its preparation method and application, a raw material composition for PVC film for inkjet coating, and a PVC film and its preparation method. Background Technology

[0002] PVC resin is a polar, non-crystalline polymer with strong intermolecular forces, making it a hard but brittle material with low impact resistance.

[0003] CN201811177892.7 provides a method for preparing a vinyl chloride-based resin composition and the vinyl chloride-based resin composition prepared therefrom, wherein the vinyl chloride-based resin composition has the effect of improving the gloss of the coating film, but has problems such as low vinyl chloride monomer conversion and low apparent density.

[0004] CN201811177890.8 discloses a method for preparing a vinyl chloride graft copolymer. This invention relates to a method for preparing a vinyl chloride graft copolymer, which allows for the easy conversion of small-particle-size acrylate latex into large-particle-size latex, simplifying the production process of large-particle-size latex and improving production efficiency. Furthermore, after suspension graft copolymerization with vinyl chloride, the impact resistance of the resin is significantly improved, thus increasing the utilization efficiency of the acrylate latex.

[0005] CN201780075005.2 provides a method for preparing a vinyl chloride-based resin composition and the vinyl chloride-based resin composition prepared therefrom, wherein the vinyl chloride-based resin composition can be used as an adhesive or ink adhesive due to its excellent solubility in solvents, excellent solution transparency and long-term storage stability, and when used as an ink adhesive, it has improved coating gloss.

[0006] 201410037898.X relates to the field of PVC film preparation technology for furniture decoration, specifically to high-definition transparent PVC film and its preparation method. The PVC film is prepared from the following raw materials in parts by weight: 100 parts PVC resin, 1-4 parts PVC stabilizer, 1-4 parts non-toxic plasticizer, 30-50 parts plasticizer, 0-6 parts liquid flame retardant, 0-10 parts cold resistant agent, and 0.01-0.02 parts ultramarine powder. The above materials are added to a high-speed mixer and mixed thoroughly. The mixed material is sent to a planetary mill for pre-plasticization, and then sent to a filter for repeated plasticizing and filtration. The plasticized material is then sent to a calender for calendering. The calendered PVC film is cooled and degreased in a water tank. The resulting PVC film has high gloss, high transparency, good temperature resistance, high tensile strength, and good chemical stability. Summary of the Invention

[0007] The purpose of this invention is to provide a new PVC resin, its preparation method and application, a raw material composition for PVC film used in inkjet printing, and a PVC film and its preparation method. This PVC resin has a specific structure and high-temperature resistance. When used in PVC film for inkjet printing, the rough surface of the PVC film is suitable for surface coating, which increases the adhesion between the coating layer and the film. Furthermore, its good high-temperature resistance makes it suitable for rapid curing of the coating layer under high-temperature conditions after surface coating.

[0008] To achieve the above objectives, the first aspect of the present invention provides a novel PVC resin, wherein the PVC resin is a crosslinked copolymer containing structural unit a provided by vinyl chloride, structural unit b provided by diallyl maleate, and structural unit c provided by pentaerythritol triacrylate; wherein the mass ratio of structural unit a, structural unit b, and structural unit c is 1:(0.0004-0.0008):(0.002-0.005).

[0009] The second aspect of the present invention provides a method for preparing the PVC resin of the present invention, wherein the method comprises: (1) subjecting a raw material mixture containing diallyl maleate, pentaerythritol triacrylate, vinyl chloride monomer, dispersant and water to an aqueous suspension copolymerization reaction in the presence of an initiator; (2) terminating the copolymerization product obtained from the aqueous suspension copolymerization reaction; and (3) processing the terminated product to obtain the PVC resin.

[0010] A third aspect of the present invention provides the application of the PVC resin described herein in PVC films for inkjet coating.

[0011] A fourth aspect of the present invention provides a PVC film raw material composition for inkjet coating, comprising: the PVC resin described in the present invention, and optionally processing aids, plasticizers, stabilizers and lubricants.

[0012] The fifth aspect of the present invention provides a method for preparing a PVC film for inkjet printing with adhesive coating, the method comprising: mixing the raw material composition for PVC film for inkjet printing with adhesive coating of the present invention and then calendering it.

[0013] The sixth aspect of the present invention provides a coated inkjet PVC film prepared by the method for preparing the coated inkjet PVC film of the present invention.

[0014] Compared with the prior art, the present invention has at least the following beneficial effects:

[0015] The PVC resin in this invention has the advantages of suitable surface roughness and good high temperature resistance. When it is used in PVC film for coating and inkjet printing, the roughness of the prepared PVC film is suitable for surface coating and inkjet printing, which can increase the adhesion between the coating layer and the pigment and the film. In addition, the PVC film has good high temperature resistance, which is suitable for the curing of the coating layer under high temperature conditions after coating the film surface. Detailed Implementation

[0016] The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0017] As mentioned above, the first aspect of the present invention provides a novel PVC resin, wherein the PVC resin contains a crosslinked copolymer of structural unit a provided by vinyl chloride (VCM), structural unit b provided by diallyl maleate (DAM), and structural unit c provided by pentaerythritol triacrylate (PETA); the mass ratio of structural unit a, structural unit b, and structural unit c is 1:(0.0004-0.0008):(0.002-0.005).

[0018] In this invention, it is understood that the structure of structural unit a provided by vinyl chloride (VCM) is as follows: The structure of structural unit b provided by diallyl maleate (DAM) is as follows: The structure of structural unit c provided by pentaerythritol triacrylate (PETA) is as follows: In this context, the mass ratios of structural unit a, structural unit b, and structural unit c are all the mass ratios of their corresponding raw materials.

[0019] In this invention, the PVC resin has a three-dimensional network of macromolecular chain cross-linked copolymer structure of DAM / PETA / VCM, which enables the corresponding product surface to exhibit a suitable roughness. The PVC film obtained by using this PVC resin in PVC film for inkjet coating has good high temperature resistance and is suitable for rapid curing of the coating layer under high temperature conditions after coating the film surface.

[0020] According to some preferred embodiments of the present invention, the weight-average molecular weight of the PVC resin is 24 × 10⁻⁶. 4 -36×10 4 g / mol.

[0021] In this invention, the weight-average molecular weight can be determined using conventional physicochemical methods, such as gel chromatography.

[0022] The second aspect of the present invention provides a method for preparing the PVC resin of the present invention, the method comprising: (1) in the presence of an initiator, carrying out an aqueous suspension copolymerization reaction of a raw material mixture containing diallyl maleate, pentaerythritol triacrylate, vinyl chloride monomer, dispersant and water; (2) terminating the copolymerization product obtained by the aqueous suspension copolymerization reaction; and (3) processing the terminated product to obtain the PVC resin.

[0023] In this invention, the amounts of diallyl maleate, pentaerythritol triacrylate, and vinyl chloride monomer can be selected according to the required content of structural unit a, structural unit b, and structural unit c in the PVC resin.

[0024] In this invention, diallyl maleate mainly extends the molecular chains of the DAM / PETA / VCM copolymer, while pentaerythritol triacrylate mainly enables the formation of a dense three-dimensional network structure between the molecular chains of the DAM / PETA / VCM copolymer. The specific amounts of diallyl maleate and pentaerythritol triacrylate work synergistically to obtain a three-dimensional network macromolecular chain copolymer structure of DAM / PETA / VCM. Furthermore, due to the high VCM content during the preparation process of this invention, the VCM homopolymer (PVC) is a continuous phase. These three-dimensional network macromolecular chain copolymer structures of DAM / PETA / VCM are uniformly distributed in the VCM homopolymer, resulting in a PVC resin that can give the product surface a suitable roughness. The PVC resin obtained is used in the PVC film for inkjet coating, and the resulting PVC film has good high-temperature resistance, making it suitable for rapid curing of the coating layer under high-temperature conditions after coating the film surface.

[0025] According to the present invention, provided that the aqueous suspension copolymerization reaction proceeds smoothly, in some embodiments, the mass ratio of the water to the total mass of diallyl maleate, pentaerythritol triacrylate, and vinyl chloride monomer is 1.6-2.2:1. Using the aforementioned embodiments, a better three-dimensional network macromolecular chain copolymer structure can be obtained, increasing the high-temperature resistance of the PVC resin. When used in the preparation of PVC films, it is suitable for the adhesive layer to rapidly cure under high-temperature conditions after coating the film surface, enabling the PVC film product to exhibit suitable surface roughness and good peel strength while maintaining good light transmittance.

[0026] According to the present invention, in some embodiments, the mass of the dispersant is 0.1wt%-0.2wt% of the mass of the vinyl chloride monomer. By employing the aforementioned embodiments, the self-polymerization of monomers in the system can be effectively reduced, the copolymerization efficiency of diallyl maleate, pentaerythritol triacrylate, and vinyl chloride can be improved, resulting in a PVC resin with superior performance. When the system is unevenly dispersed, the surface roughness of the PVC film prepared using this PVC resin decreases, and the peel strength is lower.

[0027] According to the present invention, in some embodiments, the initiator is 0.06wt%-0.08wt% of the mass of the vinyl chloride monomer. Using the aforementioned embodiments, a high-quality PVC resin can be obtained. When this PVC resin is used in PVC films, the PVC films exhibit excellent roughness and peel strength. Experiments have shown that excessive initiator leads to an overly rapid reaction, resulting in poor PVC resin quality. PVC films prepared using this resin have large and uneven surface pitting, while the roughness and peel strength are lower on the pit-free surfaces.

[0028] According to the present invention, in some embodiments, the initiator includes peroxide initiators and / or azo initiators.

[0029] According to some preferred embodiments of the present invention, the initiator is at least one selected from cumyl peroxyneodecanate, bis(2-ethylhexyl) peroxydicarbonate, dicyclohexyl peroxydicarbonate, tert-butyl peroxyneodecanate, and tert-amyl peroxypentanoate.

[0030] According to the present invention, in some preferred embodiments, the initiator is cumyl peroxyneodecanate (initiator CNP) and bis(2-ethylhexyl) peroxydicarbonate (initiator EHP). Using the aforementioned embodiments ensures a faster reaction rate and a more stable reaction process.

[0031] According to a preferred embodiment of the present invention, the mass ratio of the initiator CNP to the initiator EHP is 1:(0.88-1.15).

[0032] According to the present invention, in some embodiments, the dispersant is selected from polyvinyl alcohol dispersants and / or modified cellulose ether dispersants. By adopting the aforementioned embodiments, the polymerization reaction can proceed more smoothly, the polymerization rate can be increased, the shelf life of the product can be extended, and a PVC resin with better performance can be obtained.

[0033] According to some embodiments of the present invention, the dispersant is a polyvinyl alcohol dispersant.

[0034] According to the present invention, in some embodiments, the dispersant is a polyvinyl alcohol dispersant with a degree of hydrolysis of 78.5-81.5 mol%, a polyvinyl alcohol dispersant with a degree of hydrolysis of 59.5-72.5 mol%, and a polyvinyl alcohol dispersant with a degree of hydrolysis of 35-55 mol%.

[0035] According to the present invention, to achieve the purpose of the invention, the amounts of polyvinyl alcohol dispersants with a degree of hydrolysis of 78.5-81.5 mol%, 59.5-72.5 mol%, and 35-55 mol% are not particularly limited. In some preferred embodiments, the mass ratio of the polyvinyl alcohol dispersants with a degree of hydrolysis of 78.5-81.5 mol%, 59.5-72.5 mol%, and 35-55 mol% is (1-1.5):(1.7-2.4):1. By employing the aforementioned embodiments, the polymerization reaction can proceed more smoothly, the polymerization rate can be increased, the shelf life of the product can be extended, and a PVC resin with superior performance can be obtained.

[0036] In this invention, polyvinyl alcohol dispersants can be obtained commercially, such as dispersant KH-20 with a degree of hydrolysis of 78.5-81.5 mol%, dispersant L-9 with a degree of hydrolysis of 59.5-72.5 mol%, and dispersant S202 with a degree of hydrolysis of 35-55 mol%. In some particularly preferred embodiments, the dispersants are dispersant KH-20, dispersant L-9, and dispersant S202 in a mass ratio of (1-1.5):(1.7-2.4):1.

[0037] According to a preferred embodiment of the present invention, the dispersant is preferably a mixture of KH-20, L-9 and S202, and the weight ratio of KH-20, L-9 and S202 is (1-1.3):(1.9-2.3):1.

[0038] According to the present invention, in some embodiments, the conditions for the aqueous suspension copolymerization reaction include: a reaction temperature of 54-60°C. By adopting the aforementioned embodiments, the self-polymerization of monomers in the reaction system can be effectively reduced, and the copolymerization efficiency of diallyl maleate, pentaerythritol triacrylate and vinyl chloride can be improved.

[0039] According to the present invention, in some embodiments, the termination process is as follows: when the pressure in the aqueous suspension copolymerization reaction system decreases by 0.10-0.15 MPa, the copolymer obtained from the aqueous suspension copolymerization reaction is subjected to a termination reaction with a terminating agent.

[0040] In this invention, it is understood that the aqueous suspension copolymerization reaction is terminated after completion, and the termination is marked by a pressure drop of 0.10-0.15 MPa in the aqueous suspension copolymerization reaction system.

[0041] According to the present invention, as long as the purpose of the present invention can be achieved, there are no special restrictions on the type and amount of the terminating agent used when terminating the reaction, such as acetone thiourea and / or diethylhydroxylamine; preferably, the amount of the terminating agent is 0.008%-0.012% of the mass of vinyl chloride monomer.

[0042] According to the present invention, the terminated product still contains water, and in some embodiments, the treatment method includes: dehydrating and drying the terminated product.

[0043] In this invention, the dehydration and drying method can be a conventional method in the art, such as centrifuging the terminated product to dehydrate it, and then drying the dehydrated wet material in an oven at 60-80°C.

[0044] In this invention, the PVC resin after final processing is in powder form. When used as an upstream product, the solid product obtained by dehydration and drying can be sieved as needed, for example, through a 40-100 mesh sieve to obtain PVC resin.

[0045] A third aspect of the present invention provides the application of the PVC resin described herein in PVC films for inkjet coating.

[0046] In this invention, the PVC resin of this invention is used in PVC films for inkjet printing to obtain PVC films with suitable rough surfaces for coating and inkjet printing, which increases the adhesion between the coating layer and the pigment to the film, and the PVC films for inkjet printing can also maintain good light transmittance.

[0047] A fourth aspect of the present invention provides a PVC film raw material composition for inkjet coating, comprising: the PVC resin described in the present invention, and optionally processing aids, plasticizers, stabilizers and lubricants.

[0048] In this invention, "optionally" means that processing aids, plasticizers, stabilizers and lubricants may be added or not added as needed. In some embodiments, the PVC film raw material composition includes the PVC resin described in this invention.

[0049] According to the present invention, the type of processing aid is not particularly limited as long as the purpose of the present invention can be achieved. In the present invention, the advantages of the present invention are illustrated by taking the transparent processing aid MBS B-513 as an example, but the present invention is not limited thereto.

[0050] According to the present invention, the type of plasticizer is not particularly limited as long as the purpose of the present invention can be achieved. In the present invention, the migration-resistant plasticizer TOTM is used as an example to illustrate the advantages of the present invention, but the present invention is not limited thereto.

[0051] According to the present invention, the type of stabilizer is not particularly limited as long as the purpose of the present invention can be achieved. In the present invention, mechanical tin heat stabilizers are used as an example to illustrate the advantages of the present invention, but the present invention is not limited thereto.

[0052] According to the present invention, the type of lubricant is not particularly limited as long as the purpose of the present invention can be achieved. In the present invention, oxidized polyethylene wax lubricant and polyester wax lubricant are used as examples to illustrate the advantages of the present invention, but the present invention is not limited thereto.

[0053] According to the present invention, the amount of the processing aid is not particularly limited as long as the purpose of the present invention can be achieved. For example, the amount of the processing aid is 3-5% of the weight of the PVC resin.

[0054] According to the present invention, the amount of plasticizer used is not particularly limited as long as the purpose of the present invention can be achieved. For example, the amount of plasticizer used is 20-40% by weight of the PVC resin.

[0055] According to the present invention, the amount of stabilizer used is not particularly limited as long as the purpose of the present invention can be achieved. For example, the amount of stabilizer used is 1.5-2.5% by weight of the PVC resin.

[0056] According to the present invention, the amount of lubricant used is not particularly limited as long as the purpose of the present invention can be achieved, and the amount of lubricant used is 0.7-1.2% of the weight of the PVC resin.

[0057] According to some preferred embodiments of the present invention, the PVC film raw material composition for inkjet printing comprises, by weight: 100 parts of the resin, 3-5 parts of organotin heat stabilizer, 20-40 parts of migration-resistant plasticizer TOTM, 0.3-0.5 parts of oxidized polyethylene wax lubricant, 0.4-0.7 parts of polyester wax lubricant, and 3-5 parts of transparent processing aid MBS B-513.

[0058] The fifth aspect of the present invention provides a method for preparing a PVC film for inkjet printing with adhesive coating, the method comprising: mixing the raw material composition for PVC film for inkjet printing with adhesive coating of the present invention and then calendering it.

[0059] According to the present invention, there is no particular limitation on the mixing method of the PVC film raw material composition. For example, the PVC film raw material composition can be mixed at 80-120°C, as long as it can be mixed evenly. The present invention has no particular limitation in this regard.

[0060] According to the present invention, the calendering conditions are not particularly limited as long as the purpose of the present invention can be achieved. For example, the calendering conditions include: a calendering temperature of 180-200°C and / or a draw ratio of 1.1-1.3.

[0061] The sixth aspect of the present invention provides a coated inkjet PVC film prepared by the method for preparing the coated inkjet PVC film of the present invention.

[0062] In this invention, the rough surface of the PVC film for inkjet printing prepared by this invention is suitable for coating and inkjet printing, which increases the adhesion between the coating layer and the pigment and the film; the PVC film has good high temperature resistance, which is suitable for the coating layer to be rapidly cured under high temperature conditions after coating on the film surface.

[0063] According to some embodiments of the present invention, the thickness of the PVC film for inkjet printing is 65-70 mm.

[0064] According to some embodiments of the present invention, the light transmittance of the PVC film for inkjet printing is 80-88%.

[0065] In this invention, transparency is tested in accordance with GB / T 2410-2008.

[0066] According to some embodiments of the present invention, the peel strength of the PVC film for inkjet printing is 4-10 N / cm.

[0067] In this invention, the peel strength between the PVC film and the adhesive layer for inkjet printing is tested according to GB / T 2792-2014.

[0068] According to some embodiments of the present invention, the arithmetic mean deviation Ra of the profile of the PVC film for inkjet printing is 0.2-0.8.

[0069] In this invention, surface roughness is measured using a roughness tester and expressed as the arithmetic mean deviation Ra of the profile.

[0070] The present invention will be described in detail below through embodiments.

[0071] In the following examples and comparative examples:

[0072] Transparency was tested according to GB / T 2410-2008; peel strength between the film and the coating layer was tested according to GB / T2792-2014; surface roughness was tested using a roughness tester and expressed as the arithmetic mean deviation Ra of the profile.

[0073] Example 1

[0074] Weigh the materials according to the composition in Table 1. By mass, add 1300 parts of vinyl chloride monomer (VCM monomer), 2085 parts of deionized water, 0.52 parts of diallyl maleate (DAM), 2.60 parts of pentaerythritol triacrylate (PETA), and three dispersants (KH-20 0.39 parts, L-9 0.65 parts, S202 0.33 parts) to a 5-liter polymerization reactor and stir at room temperature for 20 minutes. Then add two initiators (CNP 0.39 parts and EHP 0.39 parts), stir for another 15 minutes, and then raise the temperature to 54°C to start the polymerization reaction. When the pressure in the reactor drops to 0.13 MPa, add the terminator (diethylhydroxylamine, 0.13 parts) to terminate the reaction. Discharge the material into a centrifuge for centrifugation and dehydration. Dry the dehydrated wet material in a 60°C oven. After drying, pass the resin through a 60-mesh sieve to obtain PVC resin.

[0075] The weight-average molecular weight of PVC resin is 36 × 10⁻⁶. 4 g / mol.

[0076] Example 2

[0077] Weigh the materials according to the composition in Table 1. By mass, add 1300 parts of vinyl chloride monomer (VCM monomer), 2877 parts of deionized water, 1.04 parts of diallyl maleate (DAM), 6.5 parts of pentaerythritol triacrylate (PETA), and three dispersants (KH-20 0.65 parts, L-9 0.91 parts, S202 0.52 parts) to a 5-liter polymerization reactor and stir at room temperature for 20 minutes. Then add two initiators (CNP 0.52 parts, EHP 0.52 parts), stir for another 15 minutes, and then raise the temperature to 60°C to start the polymerization reaction. When the pressure in the reactor drops to 0.13 MPa, add the terminator (diethylhydroxylamine, 0.13 parts) to terminate the reaction. Discharge the material into a centrifuge for centrifugation and dehydration. Dry the dehydrated wet material in a 60°C oven. After drying, pass the resin through a 60-mesh sieve to obtain PVC resin.

[0078] The weight-average molecular weight of PVC resin is 24 × 10⁻⁶. 4 g / mol.

[0079] Example 3

[0080] Weigh the materials according to the composition in Table 1. By mass, add 1300 parts of vinyl chloride monomer (VCM monomer), 2481 parts of deionized water, 0.78 parts of diallyl maleate (DAM), 4.55 parts of pentaerythritol triacrylate (PETA), and three dispersants (KH-20 0.52 parts, L-9 0.78 parts, S202 0.43 parts) to a 5-liter polymerization reactor and stir at room temperature for 20 minutes. Then add two initiators (CNP 0.46 parts, EHP 0.46 parts), stir for another 15 minutes, and then raise the temperature to 57°C to start the polymerization reaction. When the pressure in the reactor drops to 0.13 MPa, add the terminator (diethylhydroxylamine, 0.13 parts) to terminate the reaction. Discharge the material into a centrifuge for centrifugation and dehydration. Dry the dehydrated wet material in a 60°C oven. After drying, pass the resin through a 60-mesh sieve to obtain PVC resin.

[0081] The weight-average molecular weight of PVC resin is 30 × 10⁻⁶. 4 g / mol.

[0082] Example 4

[0083] Weigh the materials according to the composition in Table 1. By mass, add 1300 parts of vinyl chloride monomer (VCM monomer), 2680 parts of deionized water, 0.52 parts of diallyl maleate (DAM), 6.5 parts of pentaerythritol triacrylate (PETA), and three dispersants (KH-20 0.55 parts, L-9 0.83 parts, S202 0.37 parts) to a 5-liter polymerization reactor and stir at room temperature for 20 minutes. Then add two initiators (CNP 0.46 parts and EHP 0.52 parts), stir for another 15 minutes, and raise the temperature to 58°C to start the polymerization reaction. When the pressure in the reactor drops to 0.13 MPa, add the terminator (diethylhydroxylamine, 0.13 parts) to stop the reaction. Discharge the material into a centrifuge for centrifugation and dehydration. Dry the dehydrated wet material in a 60°C oven. After drying, pass the resin through a 60-mesh sieve to obtain PVC resin.

[0084] The weight-average molecular weight of PVC resin is 28 × 10⁻⁶. 4 g / mol.

[0085] Example 5

[0086] Weigh the materials according to the composition in Table 1. By mass, add 1300 parts of vinyl chloride monomer (VCM monomer), 2510 parts of deionized water, 1.04 parts of diallyl maleate (DAM), 2.60 parts of pentaerythritol triacrylate (PETA), and three dispersants (KH-20 0.46 parts, L-9 0.70 parts, S202 0.36 parts) to a 5-liter polymerization reactor and stir at room temperature for 18 minutes. Then add two initiators (CNP 0.52 parts and EHP 0.46 parts), stir for another 15 minutes, and then raise the temperature to 55°C to start the polymerization reaction. When the pressure in the reactor drops to 0.13 MPa, add the terminator (diethylhydroxylamine, 0.13 parts) to terminate the reaction. Discharge the material into a centrifuge for centrifugation and dehydration. Dry the dehydrated wet material in a 60°C oven. After drying, pass the resin through a 60-mesh sieve to obtain PVC resin.

[0087] The weight-average molecular weight of PVC resin is 32 × 10⁻⁶. 4 g / mol.

[0088] Example 6

[0089] Weigh the materials according to the composition in Table 1. By mass, add 1300 parts of vinyl chloride monomer (VCM monomer), 2481 parts of deionized water, 0.78 parts of diallyl maleate (DAM), 4.55 parts of pentaerythritol triacrylate (PETA), and 1.73 parts of dispersant KH-20 to a 5-liter polymerization reactor and stir at room temperature for 20 minutes. Then add two initiators (0.46 parts of CNP and 0.46 parts of EHP), stir for another 15 minutes, and then raise the temperature to 57°C to start the polymerization reaction. When the pressure in the reactor drops to 0.13 MPa, add the terminator (0.13 parts of diethylhydroxylamine) to terminate the reaction. Discharge the material into a centrifuge for centrifugation and dehydration. Dry the dehydrated wet material in a 60°C oven. After drying, pass the resin through a 60-mesh sieve to obtain PVC resin.

[0090] The weight-average molecular weight of PVC resin is 29 × 10⁻⁶. 4 g / mol.

[0091] Example 7

[0092] Weigh the materials according to the composition in Table 1. By mass, add 1300 parts of vinyl chloride monomer (VCM monomer), 2481 parts of deionized water, 0.78 parts of diallyl maleate (DAM), 4.55 parts of pentaerythritol triacrylate (PETA), and three dispersants (0.52 parts of KH-20, 0.78 parts of L-9, and 0.43 parts of S202) to a 5-liter polymerization reactor and stir at room temperature for 20 minutes. Then add 0.92 parts of initiator CNP and stir for another 15 minutes. Raise the temperature to 57°C to start the polymerization reaction. When the pressure in the reactor drops to 0.13 MPa, add the terminator (0.13 parts of diethylhydroxylamine) to terminate the reaction. Discharge the material into a centrifuge for centrifugation and dehydration. Dry the dehydrated wet material in a 60°C oven. After drying, pass the resin through a 60-mesh sieve to obtain PVC resin.

[0093] The weight-average molecular weight of PVC resin is 31 × 10⁻⁶. 4 g / mol.

[0094] Comparative Example 1

[0095] Weigh the materials according to the composition in Table 2. By mass, add 1300 parts of vinyl chloride monomer (VCM monomer), 2085 parts of deionized water, 0.26 parts of diallyl maleate (DAM), 0.91 parts of pentaerythritol triacrylate (PETA), and three dispersants (KH-20 0.39 parts, L-9 0.65 parts, S202 0.33 parts) to a 5-liter polymerization reactor and stir at room temperature for 20 minutes. Then add two initiators (CNP 0.39 parts and EHP 0.39 parts), stir for another 15 minutes, and then raise the temperature to 54°C to start the polymerization reaction. When the pressure in the reactor drops to 0.13 MPa, add the terminator (diethylhydroxylamine, 0.13 parts) to terminate the reaction. Discharge the material into a centrifuge for centrifugation and dehydration. Dry the dehydrated wet material in a 60°C oven. After drying, pass the resin through a 60-mesh sieve to obtain PVC resin.

[0096] The weight-average molecular weight of PVC resin is 33 × 10⁻⁶. 4 g / mol.

[0097] Comparative Example 2

[0098] Weigh the materials according to the composition in Table 2. By mass, add 1300 parts of vinyl chloride monomer (VCM monomer), 2877 parts of deionized water, 1.56 parts of diallyl maleate (DAM), 9.1 parts of pentaerythritol triacrylate (PETA), and three dispersants (KH-20 0.65 parts, L-9 0.91 parts, S202 0.52 parts) to a 5-liter polymerization reactor and stir at room temperature for 20 minutes. Then add two initiators (CNP 0.52 parts, EHP 0.52 parts), stir for another 15 minutes, and then raise the temperature to 60°C to start the polymerization reaction. When the pressure in the reactor drops to 0.13 MPa, add the terminator (diethylhydroxylamine, 0.13 parts) to terminate the reaction. Discharge the material into a centrifuge for centrifugation and dehydration. Dry the dehydrated wet material in a 60°C oven. After drying, sift the resin through a 60-mesh sieve to obtain PVC resin.

[0099] The weight-average molecular weight of PVC resin is 31 × 10⁻⁶. 4 g / mol.

[0100] Comparative Example 3

[0101] Weigh the materials according to the composition in Table 2. By mass, add 1300 parts of vinyl chloride monomer (VCM monomer), 2481 parts of deionized water, 0.78 parts of diallyl maleate (DAM), 4.55 parts of pentaerythritol triacrylate (PETA), three dispersants (KH-20 0.52 parts, L-9 0.78 parts, S202 0.43 parts), plasticizer (DAP 0.78 parts), and co-crosslinking agent (TAIC 4.55 parts) to a 5-liter polymerization reactor and stir at room temperature for 20 minutes. Then add two initiators (CNP... Add 0.46 parts of EHP and stir for 15 minutes. Then heat to 57°C to start the polymerization reaction. When the pressure in the reactor drops to 0.13 MPa, add the terminator (diethylhydroxylamine, 0.13 parts) to stop the reaction. Discharge the material into a centrifuge for centrifugation and dehydration. Dry the dehydrated wet material in a 60°C oven. After drying, pass the resin through a 60-mesh sieve to obtain PVC resin.

[0102] The weight-average molecular weight of PVC resin is 31 × 10⁻⁶. 4 g / mol.

[0103] Comparative Example 4

[0104] Weigh the materials according to the composition in Table 2. By mass, add 1300 parts of vinyl chloride monomer (VCM monomer), 2481 parts of deionized water, 0.78 parts of diallyl maleate (DAM), crosslinking agent (TAIC), and three dispersants (KH-20 0.52 parts, L-9 0.78 parts, S202 0.43 parts) to a 5-liter polymerization reactor and stir at room temperature for 20 minutes. Then add two initiators (CNP 0.46 parts and EHP 0.46 parts), stir for another 15 minutes, and then raise the temperature to 57°C to start the polymerization reaction. When the pressure in the reactor drops to 0.13 MPa, add the terminator (diethylhydroxylamine, 0.13 parts) to terminate the reaction. Discharge the material into a centrifuge for centrifugation and dehydration. Dry the dehydrated wet material in a 60°C oven. After drying, pass the resin through a 60-mesh sieve to obtain PVC resin.

[0105] The weight-average molecular weight of PVC resin is 31 × 10⁻⁶. 4 g / mol.

[0106] Comparative Example 5

[0107] Weigh the materials according to the composition in Table 2. By mass, add 1300 parts of vinyl chloride monomer (VCM monomer), 2481 parts of deionized water, 4.55 parts of pentaerythritol triacrylate (PETA), and three dispersants (KH-20 0.52 parts, L-9 0.78 parts, S202 0.43 parts) to a 5-liter polymerization reactor and stir at room temperature for 20 minutes. Then add two initiators (CNP 0.46 parts, EHP 0.46 parts), stir for another 15 minutes, and then raise the temperature to 57°C to start the polymerization reaction. When the pressure in the reactor drops to 0.13 MPa, add a terminator (diethylhydroxylamine 0.13 parts) to terminate the reaction. Discharge the material into a centrifuge for centrifugation and dehydration. Dry the dehydrated wet material in a 60°C oven. After drying, pass the resin through a 60-mesh sieve to obtain PVC resin.

[0108] The weight-average molecular weight of PVC resin is 30 × 10⁻⁶. 4 g / mol.

[0109] Table 1

[0110]

[0111] Table 2

[0112]

[0113]

[0114] Application examples

[0115] Weigh the raw material composition of the PVC film for inkjet printing: by weight, weigh 100 parts of PVC resin, 2.0 parts of organotin heat stabilizer, 30 parts of migration-resistant plasticizer TOTM, 0.4 parts of oxidized polyethylene wax lubricant, 0.5 parts of polyester wax lubricant, and 4 parts of transparent processing aid MBS B-513.

[0116] Preparation of PVC film for inkjet printing with adhesive coating: The above raw material composition is mixed at 100°C and then calendered to obtain a transparent film with a thickness of 65-70μm. The calendering temperature is 190°C and the draw ratio is 1.2.

[0117] Samples were taken from the PVC film used for inkjet printing and tested for transparency, peel strength, and surface roughness. The results are shown in Table 3.

[0118] Table 3

[0119]

[0120]

[0121] As can be seen from the results in the examples and comparative examples, the transparent PVC composition prepared by using the PVC resin of the present invention as a raw material has better light transmittance, higher peel strength, and more uniform contour.

[0122] As can be seen from the examples and comparative examples, diallyl maleate (DAM), pentaerythritol triacrylate (PETA), and vinyl chloride (VCM) can form a three-dimensional network macromolecular chain copolymer structure of DAM / PETA / VCM, which enables the product surface to exhibit suitable roughness and good peel strength while maintaining good light transmittance. Comparative Examples 1 and 2 show that when the amount of diallyl maleate and pentaerythritol triacrylate is too low, the film surface roughness of the composition is low, and the peel strength with the adhesive is low; when the amount of diallyl maleate and pentaerythritol triacrylate is too high, the processability of the composition is poor, the surface is uneven, and the peel strength with the coating layer is also reduced. Comparative Examples 3, 4, and 5, using DAP and TAIC, are not as effective as DAM / PETA.

[0123] The preferred embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combinations of various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. The application of a PVC resin in PVC film for inkjet printing, characterized in that, The PVC resin is a crosslinked copolymer containing structural unit a provided by vinyl chloride, structural unit b provided by diallyl maleate, and structural unit c provided by pentaerythritol triacrylate; the mass ratio of structural unit a, structural unit b, and structural unit c is 1:(0.0004-0.0008):(0.002-0.005).

2. The application according to claim 1, wherein, The weight-average molecular weight of the PVC resin is 24 × 10⁻⁶. 4 -36×10 4 g / mol.

3. An application according to claim 1 or 2, wherein, The method for preparing the PVC resin includes: (1) In the presence of an initiator, a mixture of raw materials containing diallyl maleate, pentaerythritol triacrylate, vinyl chloride monomer, dispersant and water undergoes an aqueous suspension copolymerization reaction. (2) Termination of the copolymerization reaction obtained by aqueous suspension copolymerization; (3) The PVC resin is obtained by processing the product after termination.

4. The application according to claim 3, wherein, The mass ratio of the water to the total mass of diallyl maleate, pentaerythritol triacrylate, and vinyl chloride monomer is 1.6-2.2:1; and / or The mass of the dispersant is 0.1wt%-0.2wt% of the mass of the vinyl chloride monomer; and / or The mass of the initiator is 0.06wt%-0.08wt% of the mass of the vinyl chloride monomer.

5. The application according to claim 3, wherein, The initiator includes peroxide initiators and / or azo initiators; and / or The dispersant is selected from polyvinyl alcohol dispersants and / or modified cellulose ether dispersants.

6. The application according to claim 5, wherein, The initiator is at least one selected from the following: cumyl peroxynedecanoate, bis(2-ethylhexyl) peroxydicarbonate, dicyclohexyl peroxydicarbonate, tert-butyl peroxynedecanoate, and tert-amyl peroxytert-pentanoate; and / or The dispersant is a polyvinyl alcohol dispersant.

7. The application according to claim 6, wherein, The initiator is cumyl peroxyneodecanate and bis(2-ethylhexyl) peroxydicarbonate; and / or The dispersant is a polyvinyl alcohol dispersant with a degree of alcoholysis of 78.5-81.5 mol%, a polyvinyl alcohol dispersant with a degree of alcoholysis of 59.5-72.5 mol%, and a polyvinyl alcohol dispersant with a degree of alcoholysis of 35-55 mol%.

8. The application according to claim 7, wherein, The mass ratio of cumyl peroxynedecanoate to bis(2-ethylhexyl) peroxydicarbonate is 1:(0.88-1.15); and / or The mass ratio of the polyvinyl alcohol dispersant with a degree of hydrolysis of 78.5-81.5 mol%, the polyvinyl alcohol dispersant with a degree of hydrolysis of 59.5-72.5 mol%, and the polyvinyl alcohol dispersant with a degree of hydrolysis of 35-55 mol% is (1-1.5):(1.7-2.4):

1.

9. The application according to claim 3, wherein, The conditions for the aqueous suspension copolymerization reaction include: a reaction temperature of 54-60℃; and / or The termination process is as follows: when the pressure in the aqueous suspension copolymerization system decreases by 0.10-0.15 MPa, the copolymer obtained from the aqueous suspension copolymerization reaction is reacted with a terminating agent to terminate the reaction; and / or The processing method includes: dehydrating and drying the terminated product.

10. The application according to claim 9, wherein, The amount of the terminator is 0.008-0.012% of the mass of vinyl chloride monomer.

11. A PVC film raw material composition for inkjet printing with adhesive coating, characterized in that, include: The PVC resin according to any one of claims 1-10, optionally comprising processing aids, plasticizers, stabilizers, and lubricants.

12. The PVC film raw material composition for inkjet printing with adhesive coating according to claim 11, wherein, The amount of the processing aid is 3-5% by weight of the PVC resin; and / or The amount of plasticizer used is 20-40% by weight of the PVC resin; and / or The amount of the stabilizer is 1.5-2.5% by weight of the PVC resin; and / or The amount of lubricant used is 0.7-1.2 times the weight of the PVC resin.

13. A method for preparing a PVC film for inkjet printing with adhesive coating, characterized in that, The preparation method includes: mixing the PVC film raw material composition for inkjet coating as described in claim 11 or 12 and then calendering it.

14. A coated inkjet PVC film prepared by the preparation method of claim 13.

15. The PVC film for inkjet printing with adhesive coating according to claim 14, wherein, The thickness of the PVC film is 65-70 μm; and / or The light transmittance of the PVC film is 80-88%; and / or The peel strength of the PVC film is 4-10 N / cm; and / or The arithmetic mean deviation Ra of the PVC film profile is 0.2-0.8.

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