PVC (polyvinyl chloride) resin, preparation method and application thereof, raw material composition of PVC film for gluing and ink jetting, PVC film and preparation method of PVC film

Abstract

The invention 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 gluing and ink jetting, a PVC film and a preparation method of the PVC film. The PVC resin is a cross-linked copolymer containing a structural unit a provided by vinyl chloride, a structural unit b provided by diallyl maleate and a structural unit c provided by pentaerythritol triacrylate; the mass ratio of the structural unit a to the structural unit b to the structural unit c is 1: (0.0004-0.0008): (0.002-0.005), the PVC resin has the advantages of proper surface roughness and good high temperature resistance, when the PVC resin is used in a PVC film for gluing and ink jetting, the roughness of the prepared PVC film is suitable for surface gluing and ink jetting, and the bonding force between a gluing layer and the film and between pigment and the film can be increased; and the PVC film has good high temperature resistance, and is suitable for rapid curing of a glue coating layer at high temperature after the surface of the film is coated with glue.

Description

Technical Field

[0001] The invention belongs to the field of synthetic resin preparation, and specifically relates to a PVC resin and a preparation method and application thereof, a PVC film raw material composition for glue coating and inkjet, and a PVC film and a preparation method thereof. Background Art

[0002] PVC resin is a polar non-crystalline polymer with strong interaction between molecules. It is a hard and brittle material with low impact strength.

[0003] CN201811177892.7 provides a method for preparing a vinyl chloride-based resin composition and a vinyl chloride-based resin composition prepared thereby. 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 provides a method for preparing a vinyl chloride graft copolymer. The present invention relates to a method for preparing a vinyl chloride graft copolymer, which can easily obtain a large-particle latex from a small-particle acrylate latex, simplify the large-particle latex production process, and improve production efficiency. After the large-particle latex is suspended and grafted with vinyl chloride, the impact resistance of the resin is significantly improved, and the use efficiency of the acrylate latex is also improved.

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

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

[0007] The purpose of the present invention is to provide a new PVC resin and its preparation method and application, a PVC film raw material composition for glue-coated inkjet, and a PVC film and its preparation method. The PVC resin has a specific structure and high temperature resistance. When the PVC resin is used in the PVC film for glue-coated inkjet, the rough surface of the PVC film is suitable for surface glue coating, which can increase the bonding force between the glue coating layer and the film, and the high temperature resistance is good, which is suitable for the rapid maturation of the glue coating layer under high temperature conditions after the film surface is glued.

[0008] In order to achieve the above-mentioned object, the first aspect of the present invention provides a new PVC resin, which is a cross-linked 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 the structural unit a, the structural unit b and the 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 preparation method comprises: (1) subjecting a raw material mixture containing diallyl maleate, pentaerythritol triacrylate, vinyl chloride monomer, a dispersant and water to an aqueous suspension copolymerization reaction in the presence of an initiator; (2) terminating a copolymerization product obtained by the aqueous suspension copolymerization reaction; and (3) treating the terminated product to obtain the PVC resin.

[0010] The third aspect of the present invention provides the use of the PVC resin of the present invention in a PVC film for glue-coating inkjet.

[0011] The fourth aspect of the present invention provides a PVC film raw material composition for glue coating inkjet, comprising: the PVC resin of the present invention, and optionally a processing aid, a plasticizer, a stabilizer and a lubricant.

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

[0013] The sixth aspect of the present invention provides a glue-coated PVC film for inkjet prepared by the method for preparing the glue-coated PVC film for inkjet 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 the present invention has the advantages of suitable surface roughness and good high temperature resistance. When it is used in a PVC film for glue coating and inkjet, the roughness of the prepared PVC film is suitable for surface glue coating and inkjet, and can increase the adhesion between the glue coating layer and the pigment and the film; and the PVC film has good high temperature resistance and is suitable for the curing of the glue coating layer under high temperature conditions after the film surface is glued. DETAILED DESCRIPTION

[0016] The endpoints and any values ​​of the ranges disclosed in this article 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 each range, the endpoint values ​​of each range and the individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed in this article.

[0017] As mentioned above, the first aspect of the present invention provides a new PVC resin, wherein the PVC resin contains a cross-linked 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 the structural unit a, structural unit b and structural unit c is 1: (0.0004-0.0008): (0.002-0.005).

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

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

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

[0021] In the present invention, the weight average molecular weight can be measured by conventional physical chemistry, such as gel chromatography.

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

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

[0024] In the present invention, diallyl maleate mainly extends the molecular chain of the DAM / PETA / VCM copolymer, and pentaerythritol triacrylate mainly forms a dense three-dimensional network structure between the molecular chains of the DAM / PETA / VCM copolymer. The specific content of diallyl maleate and pentaerythritol triacrylate synergistically obtain a three-dimensional network macromolecular chain copolymer structure of DAM / PETA / VCM. In the preparation process of the present invention, due to the high VCM content, the VCM homopolymer (PVC) is a continuous phase, and these three-dimensional network macromolecular chain copolymer structures of DAM / PETA / VCM are uniformly distributed in the VCM homopolymer, thereby obtaining a PVC resin capable of making the surface of a product present an appropriate roughness. The prepared PVC resin is used in a PVC film for glue-coating inkjet, and the obtained PVC film has good high temperature resistance and is suitable for rapid maturation of the glue layer under high temperature conditions after the film surface is glued.

[0025] According to the present invention, as long as the aqueous phase suspension copolymerization reaction can be ensured to proceed smoothly, in some embodiments, the ratio of the mass of the water to the total mass of diallyl maleate, pentaerythritol triacrylate, and vinyl chloride monomer is 1.6-2.2: 1. By adopting the above-mentioned embodiment, a better three-dimensional network macromolecular chain copolymer structure can be obtained, the high temperature resistance of the PVC resin can be increased, and it can be used in the preparation of PVC film, which is suitable for the rapid maturation of the coating layer under high temperature conditions after the film surface is coated with glue, and the surface of the PVC film product can present suitable roughness and good peel strength and maintain 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 adopting the above-mentioned embodiment, the self-polymerization of the monomers in the system can be effectively reduced, the copolymerization efficiency of diallyl maleate, pentaerythritol triacrylate and vinyl chloride can be improved, and a PVC resin with better performance can be obtained. When the system is unevenly dispersed, the surface roughness of the PVC film prepared by using the PVC resin is reduced, and the peel strength is low.

[0027] According to the present invention, in some embodiments, the mass of the initiator is 0.06wt%-0.08wt% of the mass of the vinyl chloride monomer. By adopting the above-mentioned embodiment, a PVC resin with excellent quality can be obtained. When the PVC resin is used for a PVC film, the PVC film has excellent roughness and peel strength. In the experiment, it was found that when the amount of the initiator is too much, the reaction will be too fast, resulting in poor quality of the PVC resin. The surface of the PVC film prepared by using the resin has large and uneven pitting, and the roughness is low at the surface without pitting, and the peel strength is also low.

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

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

[0030] According to the present invention, in some preferred embodiments, the initiator is cumyl peroxyneodecanoate (initiator CNP) and bis(2-ethylhexyl) peroxydicarbonate (initiator EHP). By adopting the above-mentioned embodiment, a faster reaction speed and a stable reaction process can be ensured.

[0031] According to the present invention, in a preferred embodiment, 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 reaction rate can be increased, the storage life of the product can be extended, and a PVC resin with better performance can be obtained.

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

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

[0035] According to the present invention, only the purpose of the present invention can be achieved, and the amount of the polyvinyl alcohol dispersant with an alcoholysis degree of 78.5-81.5mol%, the polyvinyl alcohol dispersant with an alcoholysis degree of 59.5-72.5mol% and the polyvinyl alcohol dispersant with an alcoholysis degree of 35-55mol% is not particularly limited. In some preferred embodiments, the mass ratio of the polyvinyl alcohol dispersant with an alcoholysis degree of 78.5-81.5mol%, the polyvinyl alcohol dispersant with an alcoholysis degree of 59.5-72.5mol% and the polyvinyl alcohol dispersant with an alcoholysis degree of 35-55mol% is (1-1.5): (1.7-2.4): 1. By adopting the above-mentioned embodiment, the polymerization reaction can be carried out more smoothly, the polymerization reaction rate can be increased, the shelf life of the product can be extended, and a PVC resin with better performance can be obtained.

[0036] In the present invention, the polyvinyl alcohol dispersant can be obtained from the market, for example, the polyvinyl alcohol dispersant with an alcoholysis degree of 78.5-81.5 mol% includes dispersant KH-20, the polyvinyl alcohol dispersant with an alcoholysis degree of 59.5-72.5 mol% includes dispersant L-9, and the polyvinyl alcohol dispersant with an alcoholysis degree of 35-55 mol% includes dispersant S202. That is, 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 of the aqueous suspension copolymerization reaction include: the reaction temperature is 54-60°C. By adopting the aforementioned embodiment, the self-polymerization of the 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: when the pressure in the aqueous suspension copolymerization reaction system decreases by 0.10-0.15 MPa, the copolymerization product obtained by the aqueous suspension copolymerization reaction is subjected to a termination reaction with a terminator.

[0040] In the present invention, it is understood that the aqueous suspension copolymerization reaction is terminated after completion, and the sign of the start of termination is that the pressure in the aqueous suspension copolymerization reaction system decreases by 0.10-0.15 MPa.

[0041] According to the present invention, as long as the purpose of the present invention can be achieved, when performing the termination reaction, the type and amount of the terminator used are not particularly limited, for example, acetone thiosemicarbazone and / or diethylhydroxylamine; preferably, the amount of the terminator is 0.008%-0.012% of the mass of the vinyl chloride monomer.

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

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

[0044] The PVC resin finally treated in the present invention is in powder form. When it is 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 the PVC resin.

[0045] The third aspect of the present invention provides the use of the PVC resin of the present invention in a PVC film for glue-coating inkjet.

[0046] In the present invention, the PVC resin of the present invention is used in a PVC film for glue-coating inkjet, so that a PVC film for glue-coating inkjet having a rough surface suitable for glue-coating and inkjet can be obtained, and the bonding force between the glue coating layer and the pigment and the film can be increased. Moreover, the PVC film for glue-coating inkjet can also maintain good light transmittance.

[0047] The fourth aspect of the present invention provides a PVC film raw material composition for glue coating inkjet, comprising: the PVC resin of the present invention, and optionally a processing aid, a plasticizer, a stabilizer and a lubricant.

[0048] In the present 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 the present invention.

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

[0050] According to the present invention, as long as the purpose of the present invention can be achieved, the type of the plasticizer is not particularly limited. 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, as long as the purpose of the present invention can be achieved, the type of the stabilizer is not particularly limited. In the present invention, organic tin heat stabilizer is 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, as long as the purpose of the present invention can be achieved, the type of lubricant is not particularly limited. 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, as long as the purpose of the present invention can be achieved, the amount of the processing aid is not particularly limited, for example, the amount of the processing aid is 3-5% by weight of the weight of the PVC resin.

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

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

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

[0057] According to the present invention, in some preferred embodiments, the PVC film raw material composition for glue-coated inkjet includes, by mass: 100 parts of the resin, 3 to 5 parts of an organic tin heat stabilizer, 20 to 40 parts of a migration-resistant plasticizer TOTM, 0.3 to 0.5 parts of an oxidized polyethylene wax lubricant, 0.4 to 0.7 parts of a polyester wax lubricant, and 3 to 5 parts of a transparent grade processing aid MBS B-513.

[0058] A fifth aspect of the present invention provides a method for preparing a PVC film for glue-coating inkjet, the method comprising: mixing the PVC film raw material composition for glue-coating inkjet 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 is mixed at 80-120° C. As long as it can be mixed uniformly, the present invention has no particular limitation on this.

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

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

[0062] In the present invention, the rough surface of the PVC film for glue coating and inkjet prepared by the present invention is suitable for glue coating and inkjet, and increases the adhesion between the glue coating layer and the pigment and the film; the PVC film has good high temperature resistance and is suitable for the rapid maturation of the glue coating layer under high temperature conditions after glue coating on the film surface.

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

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

[0065] In the present invention, the transparency is tested according to GB / T 2410-2008.

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

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

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

[0069] In the present invention, the surface roughness is tested by a roughness tester and is expressed as the arithmetic mean deviation Ra of the profile.

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

[0071] In the following examples and comparative examples:

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

[0073] Example 1

[0074] According to the material components in Table 1, 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 (0.39 parts of KH-20, 0.65 parts of L-9, and 0.33 parts of S202) were weighed in parts by mass. The mixture was stirred at room temperature for 20 minutes, and then two initiators (0.39 parts of CNP and 0.39 parts of EHP) were added. After stirring for another 15 minutes, the mixture was heated to 54°C to start the polymerization reaction. When the pressure in the reactor dropped by 0.13 MPa, a terminator (0.13 parts of diethylhydroxylamine) was added to terminate the reaction. The mixture was discharged into a centrifuge for centrifugal dehydration. The dehydrated wet material was dried in an oven at 60°C. After drying, the resin was sieved through a 60-mesh sieve to obtain a PVC resin.

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

[0076] Example 2

[0077] According to the material components in Table 1, 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 (0.65 parts of KH-20, 0.91 parts of L-9, and 0.52 parts of S202) were weighed in parts by mass. The mixture was stirred at room temperature for 20 minutes, and then two initiators (0.52 parts of CNP and 0.52 parts of EHP) were added. After stirring for another 15 minutes, the mixture was heated to 60°C to start the polymerization reaction. When the pressure in the reactor dropped by 0.13 MPa, a terminator (0.13 parts of diethylhydroxylamine) was added to terminate the reaction. The mixture was discharged into a centrifuge for centrifugal dehydration. The dehydrated wet material was dried in an oven at 60°C. After drying, the resin was sieved through a 60-mesh sieve to obtain a PVC resin.

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

[0079] Example 3

[0080] According to the material components in Table 1, 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) were weighed in parts by mass. The mixture was stirred at room temperature for 20 minutes, and then two initiators (0.46 parts of CNP and 0.46 parts of EHP) were added. After stirring for another 15 minutes, the temperature was raised to 57°C to start the polymerization reaction. When the pressure in the kettle dropped by 0.13 MPa, a terminator (0.13 parts of diethylhydroxylamine) was added to terminate the reaction. The material was discharged into a centrifuge for centrifugal dehydration. The dehydrated wet material was dried in an oven at 60°C. After drying, the resin was sieved through a 60-mesh sieve to obtain a PVC resin.

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

[0082] Example 4

[0083] According to the material components in Table 1, 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 (0.55 parts of KH-20, 0.83 parts of L-9, and 0.37 parts of S202) were added to a 5-liter polymerization kettle and stirred at room temperature for 20 minutes. Then two initiators (0.46 parts of CNP and 0.52 parts of EHP) were added, and the temperature was raised to 58°C after stirring for another 15 minutes to start the polymerization reaction. When the pressure in the kettle dropped by 0.13 MPa, a terminator (0.13 parts of diethylhydroxylamine) was added to terminate the reaction, and the material was discharged into a centrifuge for centrifugal dehydration. The dehydrated wet material was dried in an oven at 60°C. After drying, the resin was sieved through a 60-mesh sieve to obtain a PVC resin.

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

[0085] Example 5

[0086] According to the material components in Table 1, 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 (0.46 parts of KH-20, 0.70 parts of L-9, and 0.36 parts of S202) were weighed in parts by mass. The mixture was stirred at room temperature for 18 minutes, and then two initiators (0.52 parts of CNP and 0.46 parts of EHP) were added. After stirring for another 15 minutes, the mixture was heated to 55°C to start the polymerization reaction. When the pressure in the reactor dropped by 0.13 MPa, a terminator (0.13 parts of diethylhydroxylamine) was added to terminate the reaction. The mixture was discharged into a centrifuge for centrifugal dehydration. The dehydrated wet material was dried in an oven at 60°C. After drying, the resin was sieved through a 60-mesh sieve to obtain a PVC resin.

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

[0088] Example 6

[0089] According to the material components in Table 1, 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 were weighed, by mass, into a 5-liter polymerization kettle, stirred at room temperature for 20 minutes, and then two initiators (0.46 parts of CNP and 0.46 parts of EHP) were added. After stirring for another 15 minutes, the temperature was raised to 57° C. to start the polymerization reaction. When the pressure in the kettle dropped by 0.13 MPa, a terminator (diethylhydroxylamine, in an amount of 0.13 parts) was added to terminate the reaction, and the material was discharged into a centrifuge for centrifugal dehydration. The dehydrated wet material was dried in an oven at 60° C. After drying, the resin was sieved through a 60-mesh sieve to obtain a PVC resin.

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

[0091] Example 7

[0092] According to the material components in Table 1, 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) were weighed in parts by mass. The mixture was stirred at room temperature for 20 minutes, and then 0.92 parts of initiator CNP was added. After stirring for another 15 minutes, the temperature was raised to 57°C to start the polymerization reaction. When the pressure in the kettle dropped by 0.13 MPa, a terminator (diethylhydroxylamine, in an amount of 0.13 parts) was added to terminate the reaction. The material was discharged into a centrifuge for centrifugal dehydration. The dehydrated wet material was dried in an oven at 60°C. After drying, the resin was sieved through a 60-mesh sieve to obtain a PVC resin.

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

[0094] Comparative Example 1

[0095] According to the material components in Table 2, 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 (0.39 parts of KH-20, 0.65 parts of L-9, and 0.33 parts of S202) were weighed in parts by mass. The mixture was stirred at room temperature for 20 minutes, and then two initiators (0.39 parts of CNP and 0.39 parts of EHP) were added. After stirring for another 15 minutes, the mixture was heated to 54°C to start the polymerization reaction. When the pressure in the reactor dropped by 0.13 MPa, a terminator (0.13 parts of diethylhydroxylamine) was added to terminate the reaction. The mixture was discharged into a centrifuge for centrifugal dehydration. The dehydrated wet material was dried in an oven at 60°C. After drying, the resin was sieved through a 60-mesh sieve to obtain a PVC resin.

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

[0097] Comparative Example 2

[0098] According to the material components in Table 2, 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 (0.65 parts of KH-20, 0.91 parts of L-9, and 0.52 parts of S202) were weighed in parts by mass. The mixture was stirred at room temperature for 20 minutes, and then two initiators (0.52 parts of CNP and 0.52 parts of EHP) were added. After stirring for another 15 minutes, the mixture was heated to 60°C to start the polymerization reaction. When the pressure in the reactor dropped by 0.13 MPa, a terminator (0.13 parts of diethylhydroxylamine) was added to terminate the reaction. The mixture was discharged into a centrifuge for centrifugal dehydration. The dehydrated wet material was dried in an oven at 60°C. After drying, the resin was passed through 60 mesh to obtain PVC resin.

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

[0100] Comparative Example 3

[0101] According to the material components in Table 2, 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 (0.52 parts of KH-20, 0.78 parts of L-9, 0.43 parts of S202), a plasticizer (0.78 parts of DAP), and a co-crosslinking agent (4.55 parts of TAIC) were added into a 5-liter polymerization kettle and stirred at room temperature for 20 minutes. Then, two initiators (CNP) were added. 0.46 parts, EHP0.46 parts), and then stirred for 15 minutes and then heated to 57°C to start the polymerization reaction. When the pressure in the kettle dropped by 0.13MPa, a terminator (diethylhydroxylamine, used in an amount of 0.13 parts) was added to terminate the reaction. The material was discharged into a centrifuge for centrifugal dehydration. The dehydrated wet material was dried in an oven at 60°C. After drying, the resin was sieved through a 60-mesh sieve to obtain PVC resin.

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

[0103] Comparative Example 4

[0104] According to the material components in Table 2, 1300 parts of vinyl chloride monomer (VCM monomer), 2481 parts of deionized water, 0.78 parts of diallyl maleate (DAM), a cross-linking agent (TAIC), and three dispersants (0.52 parts of KH-20, 0.78 parts of L-9, and 0.43 parts of S202) were weighed in parts by mass. They were added to a 5-liter polymerization kettle and stirred at room temperature for 20 minutes. Then two initiators (0.46 parts of CNP and 0.46 parts of EHP) were added. After stirring for another 15 minutes, the temperature was raised to 57°C to start the polymerization reaction. When the pressure in the kettle dropped by 0.13 MPa, a terminator (0.13 parts of diethylhydroxylamine) was added to terminate the reaction. The material was discharged into a centrifuge for centrifugal dehydration. The dehydrated wet material was dried in an oven at 60°C. After drying, the resin was sieved through a 60-mesh sieve to obtain PVC resin.

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

[0106] Comparative Example 5

[0107] According to the material components in Table 2, 1300 parts of vinyl chloride monomer (VCM monomer), 2481 parts of deionized water, 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) were weighed in parts by mass. They were added into a 5-liter polymerization kettle and stirred at room temperature for 20 minutes. Then two initiators (0.46 parts of CNP and 0.46 parts of EHP) were added. After stirring for another 15 minutes, the temperature was raised to 57°C to start the polymerization reaction. When the pressure in the kettle dropped by 0.13 MPa, a terminator (0.13 parts of diethylhydroxylamine) was added to terminate the reaction. The material was discharged into a centrifuge for centrifugal dehydration. The dehydrated wet material was dried in an oven at 60°C. After drying, the resin was sieved through a 60-mesh sieve to obtain a PVC resin.

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

[0109] Table 1

[0110]

[0111] Table 2

[0112]

[0113]

[0114] Application Examples

[0115] Weigh the raw material composition of PVC film for glue-coated inkjet: weigh, by mass, 100 parts of PVC resin in the embodiment and the comparative example; 2.0 parts of organic tin heat stabilizer; 30 parts of migration-resistant plasticizer TOTM; 0.4 parts of oxidized polyethylene wax lubricant; 0.5 parts of polyester wax lubricant; 4 parts of transparent grade processing aid MBS B-513;

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

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

[0118] Table 3

[0119]

[0120]

[0121] It can be seen from the results in the examples and comparative examples that 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 profile.

[0122] It can be seen from the examples and comparative examples that diallyl maleate (DAM), pentaerythritol triacrylate (PETA) and vinyl chloride (VCM) can obtain a three-dimensional network of macromolecular chain copolymer structures of DAM / PETA / VCM, which can make the surface of the product present suitable roughness and good peel strength and maintain 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 processing performance of the composition is poor, the surface is uneven, and the peel strength with the adhesive layer is also reduced. Comparative Examples 3, 4, and 5 use DAP and TAIC, and the effect is not as good as DAM / PETA.

[0123] The preferred embodiments of the present invention are described in detail above, but the present invention is not limited thereto. Within the technical concept of the present invention, the technical solution of the present invention can be subjected to a variety of simple modifications, including the combination of various technical features in any other suitable manner, and these simple modifications and combinations should also be regarded as the contents disclosed by the present invention and belong to the protection scope of the present invention.

Claims

1. A PVC resin, characterized in that: The PVC resin is a cross-linked 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 the structural unit a, structural unit b and structural unit c is 1: (0.0004-0.0008): (0.002-0.005).

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

3. A method for preparing the PVC resin according to claim 1 or 2, characterized in that: The preparation method comprises: (1) in the presence of an initiator, a raw material mixture containing diallyl maleate, pentaerythritol triacrylate, vinyl chloride monomer, a dispersant and water is subjected to an aqueous phase suspension copolymerization reaction; (2) terminating the copolymerization product obtained by the aqueous phase suspension copolymerization reaction; (3) The terminated product is treated to obtain the PVC resin.

4. The preparation method according to claim 3, wherein The ratio of the mass 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 preparation method according to claim 3 or 4, wherein The initiator comprises a peroxide initiator and / or an azo initiator, preferably at least one of cumyl peroxyneodecanoate, bis(2-ethylhexyl peroxydicarbonate), dicyclohexyl peroxydicarbonate, tert-butyl peroxyneodecanoate and tert-amyl peroxypivalate, more preferably cumyl peroxyneodecanoate and bis(2-ethylhexyl peroxydicarbonate), preferably the mass ratio of cumyl peroxyneodecanoate to bis(2-ethylhexyl peroxydicarbonate) is 1:(0.88-1.15); and / or The dispersant is selected from polyvinyl alcohol dispersants and / or modified cellulose ether dispersants, preferably polyvinyl alcohol dispersants, further preferably polyvinyl alcohol dispersants with alcoholysis degrees of 78.5-81.5 mol%, polyvinyl alcohol dispersants with alcoholysis degrees of 59.5-72.5 mol% and polyvinyl alcohol dispersants with alcoholysis degrees of 35-55 mol%, and further preferably, the mass ratio of the polyvinyl alcohol dispersants with alcoholysis degrees of 78.5-81.5 mol%, the polyvinyl alcohol dispersants with alcoholysis degrees of 59.5-72.5 mol% and the polyvinyl alcohol dispersants with alcoholysis degrees of 35-55 mol% is (1-1.5):(1.7-2.4):

1.

6. The preparation method according to any one of claims 3 to 5, wherein: The conditions of the aqueous phase suspension copolymerization reaction include: the reaction temperature is 54-60° C.; and / or The termination process is: when the pressure in the aqueous suspension copolymerization reaction system decreases by 0.10-0.15 MPa, the copolymerization product obtained by the aqueous suspension copolymerization reaction is subjected to a termination reaction with a terminator, wherein the amount of the terminator is preferably 0.008-0.012% of the mass of the vinyl chloride monomer; and / or The treatment method comprises: dehydrating and drying the terminated product.

7. Use of the PVC resin according to any one of claims 1 to 3 in PVC film for glue-coating inkjet.

8. A PVC film raw material composition for glue-coating inkjet, characterized in that: include: The PVC resin according to any one of claims 1 to 3, optionally containing a processing aid, a plasticizer, a stabilizer and a lubricant; Preferably, The amount of the processing aid is 3-5% by weight of the PVC resin; and / or The amount of the plasticizer is 20-40% by weight of the PVC resin; and / or The stabilizer is used in an amount of 1.5-2.5% by weight of the PVC resin; and / or The amount of the lubricant is 0.7-1.2% by weight of the PVC resin.

9. A method for preparing a PVC film for glue-coating inkjet, characterized in that: The preparation method comprises: mixing the PVC film raw material composition for glue-coating inkjet according to claim 8 or 9 and then calendering and molding it.

10. A PVC film for inkjet coating prepared by the preparation method according to claim 9; Preferably, 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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