Disclosure of Invention
Based on the above, the invention aims to provide the matting film containing the base coat, and through optimizing the formulation components of the matting film containing the base coat, the quality problems of scalding and sticking rollers of the matting film at the height Wen Ganggun are improved, the temperature resistance of the base coat and the matting layer is improved, the matting effect of the matting film is improved, and the matting film has a better industrial application prospect.
The technical scheme of the invention is realized by the following steps:
A matting film containing a prime coat comprises a prime coat layer, a core layer and a matting layer which are sequentially arranged, wherein the prime coat layer comprises 80-89.9wt% of ethylene-octene copolymer and 10-20wt% of propylene-butene copolymer, the melting point of the ethylene-octene copolymer is 75-95 ℃, the melting point of the propylene-butene copolymer is 80-95 ℃, the core layer comprises homopolypropylene, the matting layer comprises random copolymerized polypropylene, 40-50wt% of high-density polyethylene and 15-35wt% of propylene-based copolymer, the melting point of the propylene-based copolymer is 140-160 ℃, and the crystallinity of the propylene-based copolymer is 5-10%.
According to the primer-containing extinction film, through optimizing the formula components of the primer-containing extinction layer, the quality problems of scalding and sticking of the extinction film at the height Wen Ganggun are solved, the temperature resistance of the primer layer and the extinction layer is improved, the extinction effect of the extinction film is improved, and the primer-containing extinction film has a good industrial application prospect.
The primer layer containing the primer extinction film takes the ethylene-octene copolymer as a main raw material, 10-20wt% of propylene-butene copolymer is added into the primer layer to improve the interface compatibility of the primer layer and the core layer, if the addition amount of the propylene-butene copolymer is less than 10wt%, the bonding force between the primer layer and the core layer is lower, the effect of improving the two-phase interface bonding force is not obvious, and if the addition amount of the propylene-butene copolymer is more than 20wt%, the compatibility of the primer layer and the EVA hot melt adhesive layer is poor, and the bonding force between the primer layer and the EVA hot melt adhesive layer is not facilitated. The invention limits that the melting point of the ethylene-octene copolymer is 75-95 ℃, if the melting point of the ethylene-octene copolymer is less than 75 ℃, the bottom coating is easy to stick to a roller when being stretched longitudinally, so that defects are easy to be generated on the surface of a film, the film is easy to adhere and even can not be unwound when being rolled under larger tension, if the melting point of the ethylene-octene copolymer is more than 95 ℃, the compatibility and interlayer bonding force of the bottom coating and the EVA hot melt adhesive coated later are reduced, and further limits that the melting point of the propylene-butene copolymer is 80-95 ℃, if the melting point of the propylene-butene copolymer is less than 80 ℃, the problem that the bottom coating is not easy to stretch to stick to the roller longitudinally is easy to burn at high temperature, and if the melting point of the propylene-butene copolymer is more than 95 ℃, the melting point of the propylene-butene copolymer and the melting point of the ethylene-octene copolymer are too different, the interlayer bonding force of the bottom coating and the EVA hot melt adhesive coated later is not easy.
In order to improve the temperature resistance of the extinction layer, the high-melting-point, low-crystallization and transparent propylene-based copolymer is added into the extinction layer, the high-melting-point propylene-based copolymer is used for replacing low-melting-point random copolymer polypropylene, the extinction layer high-density polyethylene phase is partially coated, the high-temperature scalding quality problem generated by the extinction layer in longitudinal stretching is reduced, in addition, the melting point of the propylene-based copolymer is higher than that of the high-density polyethylene and the random copolymer polypropylene, the temperature resistance of the extinction layer is improved, specifically, the melting point of the propylene-based copolymer is 140-160 ℃, if the melting point of the propylene-based copolymer is lower than 140 ℃, the problem that the extinction layer is scalded at high temperature in longitudinal stretching can not be effectively improved, and if the melting point of the propylene-based copolymer is higher than 160 ℃, the melting point difference among components of the extinction layer is too large, and poor stretching of the extinction layer is easy to cause. In the invention, the propylene-based copolymer is added into the extinction layer to be used as a continuous phase, the crystallinity of the propylene-based copolymer is 5-10%, the low crystallinity characteristic of the propylene-based copolymer is favorable for stretching bulges of a high-density polyethylene phase, the extinction effect of the whole extinction film is improved, particularly, when the crystallinity of the propylene-based copolymer is lower than 5%, the melt viscosity is very low, certain difficulties are caused to production, processing and feeding, and when the crystallinity of the propylene-based copolymer is higher than 10%, the total crystal enthalpy of the continuous phase can be obviously reduced only by larger addition amount, and the cost is high. Meanwhile, the propylene copolymer is transparent, has good compatibility with the random copolymer polypropylene and the high-density polyethylene, and does not influence the transparency of the film. The extinction layer is added with 15-35wt% of propylene copolymer, the extinction effect of the extinction layer is improved while the temperature resistance of the extinction layer is improved, if the addition amount of the propylene copolymer is lower than 15wt%, although the total crystallization enthalpy value of the continuous phase is reduced, the haze of the extinction film is improved to a certain extent, but the addition amount of the propylene copolymer is lower, the propylene copolymer is insufficient to form a continuous amorphous continuous phase after shearing and dispersing, the effect of improving the temperature resistance of the extinction layer is not obvious, and if the addition amount of the propylene copolymer is higher than 35wt%, the tensile strength of the extinction film containing the base coat is obviously reduced, and the heat shrinkage proportion of the film is increased. The invention further defines that the high density polyethylene content in the matting layer is 40-50 wt.%, the random copolymer polypropylene content is 17-50 wt.%, in favor of obtaining more desirable matting effect, preferably the random copolymer polypropylene content in the matting layer of the invention is 17-37 wt.%.
Further, the propylene-based copolymer in the extinction layer is propylene-1-butene copolymerized polypropylene, and in the propylene-1-butene copolymerized polypropylene, the isotacticity of a propylene sequence is 90-93%, and the isotacticity of a 1-butene sequence is 87-90%. As is well known to those skilled in the art, in general for propylene-1-butene copolymerized polypropylene, the introduction of butene units breaks the sequence structure of the molecular chains of the polypropylene chains, causing the crystallinity of the copolymer to decrease, the melting temperature decreasing significantly with increasing butene-1. However, the propylene-1-butene copolymer polypropylene selected by the invention is synthesized by adopting an optimized catalytic system for stereospecific polymerization, specifically, an alkylaluminum or alkylaluminum hydride, an external electron donor, a supported titanium catalyst and hydrogen are used as a catalyst system for isotactic polymerization, and bulk copolymerization is carried out to obtain the propylene-1-butene copolymer polypropylene, the isotacticity of a 1-butene sequence and a propylene sequence in the obtained propylene-1-butene copolymer polypropylene is more than 85%, and the melting temperature of the copolymer is obviously increased along with the increase of the 1-butene content, so that the propylene-1-butene copolymer polypropylene has a relatively high melting point, and meanwhile, the relatively low crystallinity is maintained. The propylene-1-butene copolymer polypropylene with 90-93% isotacticity and 87-90% isotacticity is selected, if the isotacticity of the propylene sequence is too low, the melting point of the propylene-1-butene copolymer polypropylene is too low, the propylene-1-butene copolymer polypropylene is added into the extinction layer, the extinction layer cannot be effectively and temperature-resistant and protected, the high-temperature scalding for improving the extinction layer is not obvious enough, if the isotacticity of the propylene sequence is too high, the crystallinity of the propylene-1-butene copolymer polypropylene is increased, the haze of an extinction film is not good, if the isotacticity of the 1-butene sequence is too low, the melting point of the 1-butene sequence in the propylene-1-butene copolymer polypropylene is too low, the propylene-1-butene copolymer polypropylene with relatively high melting point is not good for being obtained, the propylene-1-butene copolymer polypropylene with relatively high melting point is added into the extinction layer, and if the isotacticity of the 1-butene sequence is too high, the propylene-1-butene copolymer polypropylene is possibly caused to be too stiff and the bidirectional stretching is not good.
Further, the propylene-1-butene copolymer polypropylene in the matting layer has a 1-butene monomer content of 15 to 35wt%. If the 1-butene content is less than 15wt%, the randomness of the propylene-1-butene copolymer is reduced, the crystallinity is increased, the matting effect for improving the matting layer is not obvious enough, and if the 1-butene content is more than 35wt%, the internal stress of the propylene-1-butene copolymer is easily released when the temperature is increased due to the low crystallization characteristic of the propylene-1-butene copolymer, so that the heat shrinkage rate of the primer-containing matting film is increased when the downstream film is coated.
Further, the ethylene-octene copolymer has an octene content of 5 to 20wt%. By controlling the content of octene in the ethylene-octene copolymer, the compatibility and affinity between the primer layer and the EVA hot-melt adhesive layer can be improved on the basis of ensuring the melting performance and the like of the film, if the content of octene is too high, the melting point of the ethylene-octene copolymer is reduced, the phenomena of sticking to rollers and the like occur in the stretching process, and if the content of octene is too low, the compatibility between the primer layer and the EVA is reduced, so that the bonding force between the primer layer and the EVA hot-melt adhesive layer is not facilitated.
Further, the melt index of the propylene-butene copolymer in the primer layer and the propylene-1-butene copolymer in the matting layer is 5 to 10g/10min at 230 ℃ and 2.16 kg. The propylene-butene copolymer in the primer layer is controlled to be 5-10g/10min, which is favorable for matching the melt index of the ethylene-octene copolymer, and can be dispersed more uniformly. The melt index of the propylene-1-butene copolymer polypropylene in the extinction layer is controlled to be 5-10g/10min, when the melt index of the propylene-1-butene copolymer polypropylene is lower than 5g/10min, the fluidity of the extinction layer is not beneficial to improving the extinction uniformity of the edge part of a film, and when the melt index of the propylene-1-butene copolymer polypropylene is higher than 10g/10min, the difference between the melt viscosity and the disperse phase is too large, the shearing dispersion is not beneficial to maintaining the mechanical strength of a system.
Further, the melt index of the random copolymer polypropylene in the matt layer is 7 to 12g/10min at 230 ℃ and 2.16kg, and the melt index of the high density polyethylene is 8 to 14g/10min measured at 190 ℃ and 21.6 kg. If the melt index of the random copolymer polypropylene is lower than 7g/10min, the viscosity difference between the high-density polyethylene phase and the random copolymer polypropylene phase is low, which is unfavorable for the phase-separation size of the high-density polyethylene phase and deteriorates the fluidity, and if the melt index of the random copolymer polypropylene is higher than 12g/10min, the viscosity difference between the high-density polyethylene phase and the random copolymer polypropylene phase is too large, and the high-density polyethylene phase with high viscosity is difficult to disperse effectively in the random copolymer polypropylene phase with low viscosity. The invention also defines that the melt index of the high-density polyethylene measured at 190 ℃ and 21.6kg is 8-14g/10min, if the melt index of the high-density polyethylene is lower than 8g/10min, the molecular weight of the high-density polyethylene is too large, film surface impurity points are easy to appear, and if the melt index of the high-density polyethylene is higher than 14g/10min, the melt viscosity is lower, the viscosity difference with the random copolymer polypropylene is smaller, the phase separation size of the high-density polyethylene in a extinction layer is smaller, and the extinction effect is poor.
Further, the primer layer also comprises 0.1-0.3wt% of an antioxidant, wherein the antioxidant is prepared by compounding an antioxidant 1010 and an antioxidant 168 according to a ratio of 1:2. The addition of 0.1 to 0.3 weight percent of antioxidant in the primer layer is beneficial to reducing the thermal oxygen degradation and the generation of cross-linked matters generated in the high-temperature extrusion process of the polyolefin resin with low melting point in the primer layer and reducing the quality problem of uneven stretching of the film.
Further, the random copolymer polypropylene in the matt layer is selected from one or two of ethylene-propylene copolymer polypropylene or ethylene-propylene-butene copolymer polypropylene.
Further, the core layer comprises 99wt% of homopolypropylene and 1wt% of antistatic master batch, the melt index of the homopolypropylene is 3-4g/10min, the carrier of the antistatic master batch is the homopolypropylene, and the effective concentration of the antistatic agent in the antistatic master batch is 40wt%.
The invention also provides a preparation method of the extinction film containing the bottom coating, which comprises the following steps of uniformly mixing all the raw materials through a high-speed mixer, then feeding the raw materials into a screw extruder through a proportioning device, converging melt of each extruder into thick sheets in a T-shaped die after metering by a metering pump, cooling the thick sheets through a chilling roller, feeding the thick sheets into a chilling water tank, longitudinally stretching the thick sheets through a water blowing chamber, transversely stretching the thick sheets, shaping, carrying out corona treatment, then rolling the thick sheets into an aging frame, cutting and packaging the thick sheets to obtain finished products.
The invention is described in detail below for a better understanding and implementation.
Detailed Description
It should be understood that the described embodiments are merely some, but not all embodiments of the present application. All other embodiments, which can be made by one of ordinary skill in the art without undue burden from the application, are intended to be within the scope of the embodiments of the present application.
The terminology used in the embodiments of the application is for the purpose of describing particular embodiments only and is not intended to be limiting of embodiments of the application. As used in this application and the appended claims, the singular forms "a," "an," and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise. It should also be understood that the term "and/or" as used herein refers to and encompasses any or all possible combinations of one or more of the associated listed items.
The implementations described in the following exemplary examples do not represent all implementations consistent with the application. Rather, they are merely examples of apparatus and methods consistent with certain aspects of the application as detailed in the accompanying claims. In the description of the present application, it should be understood that the terms "first," "second," "third," and the like are used merely to distinguish between similar objects and are not necessarily used to describe a particular order or sequence, nor should they be construed to indicate or imply relative importance. The specific meaning of the above terms in the present application can be understood by those of ordinary skill in the art according to the specific circumstances.
Furthermore, in the description of the present application, unless otherwise indicated, "a plurality" means two or more. "and/or" describes an association relationship of an association object, and indicates that there may be three relationships, for example, a and/or B, and may indicate that there are three cases of a alone, a and B together, and B alone. The character "/" generally indicates that the context-dependent object is an "or" relationship.
It is to be understood that the embodiments of the application are not limited to the precise arrangements and instrumentalities described above, and that various modifications and changes may be made without departing from the scope thereof. The scope of embodiments of the application is limited only by the appended claims.
As one embodiment of the present invention, the primer-containing matting film of this example. By optimizing the formula components of the extinction layer containing the base coat, the quality problems of scalding and sticking of the extinction film at the height of Wen Ganggun are improved, the temperature resistance of the base coat and the extinction layer is improved, the extinction effect of the extinction film is improved, and the extinction film has a good industrial application prospect.
Further, the propylene-based copolymer in the extinction layer is propylene-1-butene copolymerized polypropylene, and in the propylene-1-butene copolymerized polypropylene, the isotacticity of a propylene sequence is 90-93%, and the isotacticity of a 1-butene sequence is 87-90%. As is well known to those skilled in the art, in general for propylene-1-butene copolymerized polypropylene, the introduction of butene units breaks the sequence structure of the molecular chains of the polypropylene chains, causing the crystallinity of the copolymer to decrease, the melting temperature decreasing significantly with increasing butene-1. However, the propylene-1-butene copolymer polypropylene selected by the invention is synthesized by adopting an optimized catalytic system for stereospecific polymerization, specifically, an alkylaluminum or alkylaluminum hydride, an external electron donor, a supported titanium catalyst and hydrogen are used as a catalyst system for isotactic polymerization, and bulk copolymerization is carried out to obtain the propylene-1-butene copolymer polypropylene, the isotacticity of a 1-butene sequence and a propylene sequence in the obtained propylene-1-butene copolymer polypropylene is more than 85%, and the melting temperature of the copolymer is obviously increased along with the increase of the 1-butene content, so that the propylene-1-butene copolymer polypropylene has a relatively high melting point, and meanwhile, the relatively low crystallinity is maintained. The propylene-1-butene copolymer polypropylene with 90-93% isotacticity and 87-90% isotacticity is selected, if the isotacticity of the propylene sequence is too low, the melting point of the propylene-1-butene copolymer polypropylene is too low, the propylene-1-butene copolymer polypropylene is added into the extinction layer, the extinction layer cannot be effectively and temperature-resistant and protected, the high-temperature scalding for improving the extinction layer is not obvious enough, if the isotacticity of the propylene sequence is too high, the crystallinity of the propylene-1-butene copolymer polypropylene is increased, the haze of an extinction film is not good, if the isotacticity of the 1-butene sequence is too low, the melting point of the 1-butene sequence in the propylene-1-butene copolymer polypropylene is too low, the propylene-1-butene copolymer polypropylene with relatively high melting point is not good for being obtained, the propylene-1-butene copolymer polypropylene with relatively high melting point is added into the extinction layer, and if the isotacticity of the 1-butene sequence is too high, the propylene-1-butene copolymer polypropylene is possibly caused to be too stiff and the bidirectional stretching is not good.
Further, the propylene-1-butene copolymer polypropylene in the matting layer has a 1-butene monomer content of 15 to 35wt%. If the 1-butene content is less than 15wt%, the randomness of the propylene-1-butene copolymer is reduced, the crystallinity is increased, the matting effect for improving the matting layer is not obvious enough, and if the 1-butene content is more than 35wt%, the internal stress of the propylene-1-butene copolymer is easily released when the temperature is increased due to the low crystallization characteristic of the propylene-1-butene copolymer, so that the heat shrinkage rate of the primer-containing matting film is increased when the downstream film is coated.
Further, the ethylene-octene copolymer has an octene content of 5 to 20wt%. By controlling the content of octene in the ethylene-octene copolymer, the compatibility and affinity between the primer layer and the EVA hot-melt adhesive layer can be improved on the basis of ensuring the melting performance and the like of the film, if the content of octene is too high, the melting point of the ethylene-octene copolymer is reduced, the phenomena of sticking to rollers and the like occur in the stretching process, and if the content of octene is too low, the compatibility between the primer layer and the EVA is reduced, so that the bonding force between the primer layer and the EVA hot-melt adhesive layer is not facilitated.
Further, the melt index of the propylene-butene copolymer in the primer layer and the propylene-1-butene copolymer in the matting layer is 5 to 10g/10min at 230 ℃ and 2.16 kg. The propylene-butene copolymer in the primer layer is controlled to be 5-10g/10min, which is favorable for matching the melt index of the ethylene-octene copolymer, and can be dispersed more uniformly. The melt index of the propylene-1-butene copolymer polypropylene in the extinction layer is controlled to be 5-10g/10min, when the melt index of the propylene-1-butene copolymer polypropylene is lower than 5g/10min, the fluidity of the extinction layer is not beneficial to improving the extinction uniformity of the edge part of a film, and when the melt index of the propylene-1-butene copolymer polypropylene is higher than 10g/10min, the difference between the melt viscosity and the disperse phase is too large, the shearing dispersion is not beneficial to maintaining the mechanical strength of a system.
Further, the melt index of the random copolymer polypropylene in the matt layer is 7 to 12g/10min at 230 ℃ and 2.16kg, and the melt index of the high density polyethylene is 8 to 14g/10min measured at 190 ℃ and 21.6 kg. If the melt index of the random copolymer polypropylene is lower than 7g/10min, the viscosity difference between the high-density polyethylene phase and the random copolymer polypropylene phase is low, which is unfavorable for the phase-separation size of the high-density polyethylene phase and deteriorates the fluidity, and if the melt index of the random copolymer polypropylene is higher than 12g/10min, the viscosity difference between the high-density polyethylene phase and the random copolymer polypropylene phase is too large, and the high-density polyethylene phase with high viscosity is difficult to disperse effectively in the random copolymer polypropylene phase with low viscosity.
Further, the primer layer also comprises 0.1-0.3wt% of an antioxidant, wherein the antioxidant is prepared by compounding an antioxidant 1010 and an antioxidant 168 according to a ratio of 1:2. The addition of 0.1 to 0.3 weight percent of antioxidant in the primer layer is beneficial to reducing the thermal oxygen degradation and the generation of cross-linked matters generated in the high-temperature extrusion process of the polyolefin resin with low melting point in the primer layer and reducing the quality problem of uneven stretching of the film.
Further, the random copolymer polypropylene in the matt layer is selected from one or two of ethylene-propylene copolymer polypropylene or ethylene-propylene-butene copolymer polypropylene.
Further, the core layer comprises 99wt% of homopolypropylene and 1wt% of antistatic master batch, the melt index of the homopolypropylene is 3-4g/10min, the carrier of the antistatic master batch is the homopolypropylene, and the effective concentration of the antistatic agent in the antistatic master batch is 40wt%.
Further, the total thickness of the matting film containing the priming coat is 14-25 mu m, the thickness of the priming coat is 1-2 mu m, and the thickness of the matting layer is 1.6-2.0 mu m.
The invention also provides a preparation method of the extinction film containing the bottom coating, which comprises the following steps of uniformly mixing all the raw materials through a high-speed mixer, then feeding the raw materials into a screw extruder through a proportioning device, merging melt of the extruder into thick sheets in a T-shaped die after metering by a metering pump, cooling the thick sheets through a chilling roller, feeding the thick sheets into a chilling water tank, longitudinally stretching the thick sheets through a water blowing chamber, transversely stretching the thick sheets, shaping, corona treating, rolling the thick sheets into an aging frame, and cutting and packaging the thick sheets to obtain finished products.
It should be noted that the random copolymer polypropylene in the matting layers of the examples and comparative examples of the present invention was ethylene propylene binary copolymer polypropylene having a melt index of 8g/10min (230 ℃ C., 2.16 kg) and a melt index of 11g/10min (190 ℃ C., 21.6 kg) of high-density polyethylene. The antioxidants in the core layers of the examples and comparative examples of the present invention were a mixture of basf 1010 and 168, where 1010:168=1:2, and the carrier resin was an ethylene-octene copolymer having a melting point of 85 ℃.
The physical property indexes of the embodiment or the comparative example and the testing method thereof are specifically as follows:
The melting point and the crystallinity are detected by DSC, the glossiness test is carried out according to the GB/T8807-1988 standard, the haze test is carried out according to the GB/T2410-2008 standard, and the mechanical property test is carried out according to the GB/T1040.3-2006 standard.
Heat shrinkage in the heat shrinkage test, film samples were taken at 10 x 10cm, placed in a 110 ℃ oven for 120 seconds, and then tested for film shrinkage in the machine and transverse directions at room temperature cooling.
And detecting flaw points, namely taking the rolling accumulation of an online detector of 1 ten thousand meters as a statistical period, wherein the size of the particle size of the counted flaw points is 1mm < 2> or more.
And (3) evaluating the binding force between the bottom coating and the hot melt adhesive layer, namely coating EVA hot melt adhesive (with the VA content of 18wt% and the melt index of 15g/10 min) on the surface of the bottom coating-containing extinction film prepared by the method, wherein the coating thickness is 8 mu M, and using a 3M adhesive tape to carry out interlayer peeling test after coating so as to observe whether the EVA hot melt adhesive layer is peeled or not.
Example 1
The embodiment provides a matting film containing a priming coat, which comprises a priming coat, a core layer and a matting layer which are sequentially arranged. The preparation method of the resin containing the bottom coating extinction film comprises the following steps:
The primer resin was prepared by mixing 84.7wt% of an ethylene-octene copolymer (octene content: 18wt%, melt index: 6.5g/10min, melting point: 85 ℃) 15wt% of a propylene-butene copolymer (butene content: 33wt%, melt index: 7g/10min, melting point: 75 ℃) and 0.3wt% of an antioxidant uniformly by a high-speed mixer to obtain the primer resin.
The preparation of the core layer resin comprises the steps of taking 99wt% of homopolypropylene (with a melt index of 3.2g/10 min) and 1wt% of antistatic master batch (with a carrier of homopolypropylene and an effective concentration of 40 wt%) and uniformly mixing by a high-speed mixer to obtain the core layer resin.
The extinction layer resin is prepared by mixing 48wt% of high-density polyethylene, 37wt% of ethylene-propylene copolymer and 15wt% of propylene copolymer (propylene-1-butene copolymer with a melt index of 7.1g/10min, wherein the comonomer proportion of 1-butene is 31.3wt%, the crystallinity is 7.46%, the melting point is 160 ℃, and the propylene sequence isotacticity is 93% and the 1-butene sequence isotacticity is 90%) in the propylene-1-butene copolymer uniformly by a high-speed mixer to obtain the extinction layer resin.
The preparation method of the BOPP film of the embodiment comprises the following steps:
the method comprises the steps of respectively conveying each layer of resin to three screw extruders (wherein the bottom coating and the extinction layer are single screw extruders, the core layer is a double screw extruder, the extrusion temperature of the bottom coating is 235 ℃, the extrusion temperature of the extinction layer is 245 ℃, the extrusion temperature of the core layer is 250 ℃, melt of the three extruders is metered by a melt metering pump, and then is converged into thick sheets in a T-shaped die through a long and narrow runner, the thick sheets are cooled by a chilling roller and enter a chilling water tank, then enter a longitudinal stretching area after passing through a water blowing chamber, are longitudinally stretched (the bottom coating is 70 ℃, the stretching area is 60 ℃, the shaping area is 65 ℃, the extinction layer is 135 ℃, the stretching area is 130 ℃, the shaping area is 130 ℃, the longitudinal stretching ratio is 5 times), then enter a transverse stretching area, are transversely stretched (the stretching temperature is 160 ℃, the transverse stretching ratio is 8 times), then are subjected to trimming and corona treatment, and then are rolled into an aging frame treatment, and are cut and packaged into finished products after the treatment is completed.
The total thickness of the primer-containing matting film of this example was 18. Mu.m, in which the thickness of the primer layer was 1.8. Mu.m, and the thickness of the matting layer was 2. Mu.m.
Example 2
The embodiment provides a matting film containing a priming coat, which comprises a priming coat, a core layer and a matting layer which are sequentially arranged. The preparation method of the resin containing the bottom coating extinction film comprises the following steps:
The primer resin was prepared by mixing 84.7wt% of an ethylene-octene copolymer (octene content: 18wt%, melt index: 6.5g/10min, melting point: 85 ℃) 15wt% of a propylene-butene copolymer (butene content: 33wt%, melt index: 7g/10min, melting point: 75 ℃) and 0.3wt% of an antioxidant uniformly by a high-speed mixer to obtain the primer resin. The preparation of the core layer resin comprises the steps of taking 99wt% of homopolypropylene (with a melt index of 3.2g/10 min) and 1wt% of antistatic master batch (with a carrier of homopolypropylene and an effective concentration of 40 wt%) and uniformly mixing by a high-speed mixer to obtain the core layer resin.
The extinction layer resin is prepared by mixing 48wt% of high-density polyethylene, 27wt% of ethylene-propylene copolymer and 25wt% of propylene copolymer (propylene-1-butene copolymer with a melt index of 7.1g/10min, wherein the comonomer proportion of 1-butene is 31.3wt%, the crystallinity is 7.46%, the melting point is 160 ℃, and the propylene sequence isotacticity is 93% and the 1-butene sequence isotacticity is 90%) in the propylene-1-butene copolymer uniformly by a high-speed mixer to obtain the extinction layer resin.
The preparation method of the matting film containing the primer in this embodiment is the same as that in embodiment 1, so that a description thereof will be omitted.
The total thickness of the primer-containing matting film of this example was 18. Mu.m, in which the thickness of the primer layer was 1.8. Mu.m, and the thickness of the matting layer was 2. Mu.m.
Example 3
The embodiment provides a matting film containing a priming coat, which comprises a priming coat, a core layer and a matting layer which are sequentially arranged. The preparation method of the resin containing the bottom coating extinction film comprises the following steps:
The primer resin was prepared by mixing 84.7wt% of an ethylene-octene copolymer (octene content: 18wt%, melt index: 6.5g/10min, melting point: 85 ℃) 15wt% of a propylene-butene copolymer (butene content: 33wt%, melt index: 7g/10min, melting point: 75 ℃) and 0.3wt% of an antioxidant uniformly by a high-speed mixer to obtain the primer resin. The preparation of the core layer resin comprises the steps of taking 99wt% of homopolypropylene (with a melt index of 3.2g/10 min) and 1wt% of antistatic master batch (with a carrier of homopolypropylene and an effective concentration of 40 wt%) and uniformly mixing by a high-speed mixer to obtain the core layer resin.
The extinction layer resin is prepared by mixing 48wt% of high-density polyethylene, 22wt% of ethylene-propylene copolymer and 30wt% of propylene copolymer (propylene-1-butene copolymer with a melt index of 7.1g/10min, wherein the comonomer proportion of 1-butene is 31.3wt%, the crystallinity is 7.46%, the melting point is 160 ℃, and the propylene sequence isotacticity is 93% and the 1-butene sequence isotacticity is 90%) in the propylene-1-butene copolymer uniformly by a high-speed mixer to obtain the extinction layer resin.
The preparation method of the matting film containing the primer in this embodiment is the same as that in embodiment 1, so that a description thereof will be omitted.
The total thickness of the primer-containing matting film of this example was 18. Mu.m, in which the thickness of the primer layer was 1.8. Mu.m, and the thickness of the matting layer was 2. Mu.m.
Example 4
The embodiment provides a matting film containing a priming coat, which comprises a priming coat, a core layer and a matting layer which are sequentially arranged. The preparation method of the resin containing the bottom coating extinction film comprises the following steps:
The primer resin was prepared by mixing 84.7wt% of an ethylene-octene copolymer (octene content: 18wt%, melt index: 6.5g/10min, melting point: 85 ℃) 15wt% of a propylene-butene copolymer (butene content: 33wt%, melt index: 7g/10min, melting point: 75 ℃) and 0.3wt% of an antioxidant uniformly by a high-speed mixer to obtain the primer resin. The preparation of the core layer resin comprises the steps of taking 99wt% of homopolypropylene (with a melt index of 3.2g/10 min) and 1wt% of antistatic master batch (with a carrier of homopolypropylene and an effective concentration of 40 wt%) and uniformly mixing by a high-speed mixer to obtain the core layer resin.
The extinction layer resin is prepared by mixing 48wt% of high-density polyethylene, 17wt% of ethylene-propylene copolymer and 35wt% of propylene-based copolymer (propylene-1-butene copolymer in the embodiment has a melt index of 8.3g/10min, wherein the comonomer proportion of 1-butene is 23.5wt%, the crystallinity is 6.1%, the melting point is 140 ℃, and the propylene sequence isotacticity is 90% and the 1-butene sequence isotacticity is 87%) in the propylene-1-butene copolymer by a high-speed mixer to obtain the extinction layer resin.
The preparation method of the matting film containing the primer in this embodiment is the same as that in embodiment 1, so that a description thereof will be omitted.
The total thickness of the primer-containing matting film of this example was 18. Mu.m, in which the thickness of the primer layer was 1.8. Mu.m, and the thickness of the matting layer was 2. Mu.m.
Comparative example 1
This comparative example provides a matting film comprising a primer layer, a core layer and a matting layer, which are sequentially arranged. The preparation method of the resin containing the bottom coating extinction film of the comparative example comprises the following steps:
The primer resin was prepared by mixing 84.7wt% of an ethylene-octene copolymer (octene content: 18wt%, melt index: 6.5g/10min, melting point: 85 ℃) 15wt% of a propylene-butene copolymer (butene content: 33wt%, melt index: 7g/10min, melting point: 75 ℃) and 0.3wt% of an antioxidant uniformly by a high-speed mixer to obtain the primer resin.
The preparation of the core layer resin comprises the steps of taking 99wt% of homopolypropylene (with a melt index of 3.2g/10 min) and 1wt% of antistatic master batch (with a carrier of homopolypropylene and an effective concentration of 40 wt%) and uniformly mixing by a high-speed mixer to obtain the core layer resin.
The preparation of the extinction layer resin comprises the steps of taking 48 weight percent of high-density polyethylene and 52 weight percent of ethylene-propylene copolymer, and uniformly mixing the high-density polyethylene and the 52 weight percent of ethylene-propylene copolymer by a high-speed mixer to obtain the extinction layer resin.
The preparation method of the primer-containing matting film of this comparative example is the same as that of example 1, and thus a description thereof will be omitted.
The total thickness of the primer-containing matting film of this comparative example was 18 μm, in which the thickness of the primer layer was 1.8 μm and the thickness of the matting layer was 2. Mu.m.
Comparative example 2
This comparative example provides a matting film comprising a primer layer, a core layer and a matting layer, which are sequentially arranged. The preparation method of the resin containing the bottom coating extinction film of the comparative example comprises the following steps:
The primer resin was prepared by mixing 84.5wt% of an ethylene-octene copolymer (octene content: 18wt%, melt index: 6.5g/10min, melting point: 85 ℃) 15wt% of a propylene-butene copolymer (butene content: 33wt%, melt index: 7g/10min, melting point: 75 ℃) and 0.5wt% of an antioxidant uniformly by a high-speed mixer to obtain the primer resin.
The preparation of the core layer resin comprises the steps of taking 99wt% of homopolypropylene (with a melt index of 3.2g/10 min) and 1wt% of antistatic master batch (with a carrier of homopolypropylene and an effective concentration of 40 wt%) and uniformly mixing by a high-speed mixer to obtain the core layer resin.
The extinction layer resin is prepared by mixing 48wt% of high-density polyethylene, 47wt% of ethylene-propylene copolymer and 5wt% of propylene copolymer (propylene-1-butene copolymer with a melt index of 7.1g/10min, wherein the comonomer proportion of 1-butene is 31.3wt%, the crystallinity is 7.46%, the melting point is 160 ℃, and the propylene sequence isotacticity is 93% and the 1-butene sequence isotacticity is 90%) in the propylene-1-butene copolymer uniformly by a high-speed mixer to obtain the extinction layer resin.
The preparation method of the primer-containing matting film of this comparative example is the same as that of example 1, and thus a description thereof will be omitted.
The total thickness of the primer-containing matting film of this comparative example was 18 μm, in which the thickness of the primer layer was 5.5 μm and the thickness of the matting layer was 2 μm.
Comparative example 3
This comparative example provides a matting film comprising a primer layer, a core layer and a matting layer, which are sequentially arranged. The preparation method of the resin containing the bottom coating extinction film of the comparative example comprises the following steps:
The primer resin was prepared by mixing 84.7wt% of an ethylene-octene copolymer (octene content: 18wt%, melt index: 6.5g/10min, melting point: 85 ℃) 15wt% of a propylene-butene copolymer (butene content: 33wt%, melt index: 7g/10min, melting point: 75 ℃) and 0.3wt% of an antioxidant uniformly by a high-speed mixer to obtain the primer resin.
The preparation of the core layer resin comprises the steps of taking 99wt% of homopolypropylene (with a melt index of 3.2g/10 min) and 1wt% of antistatic master batch (with a carrier of homopolypropylene and an effective concentration of 40 wt%) and uniformly mixing by a high-speed mixer to obtain the core layer resin.
The extinction layer resin is prepared by mixing 48wt% of high-density polyethylene, 14wt% of ethylene-propylene copolymer and 38wt% of propylene copolymer (propylene-1-butene copolymer with a melt index of 7.1g/10min, wherein the comonomer proportion of 1-butene is 31.3wt%, the crystallinity is 7.46%, the melting point is 160 ℃, and the propylene sequence isotacticity is 93% and the 1-butene sequence isotacticity is 90%) in the propylene-1-butene copolymer uniformly by a high-speed mixer to obtain the extinction layer resin.
The preparation method of the primer-containing matting film of this comparative example is the same as that of example 1, and thus a description thereof will be omitted.
The total thickness of the primer-containing matting film of this comparative example was 18 μm, in which the thickness of the primer layer was 1.8 μm and the thickness of the matting layer was 2. Mu.m.
Comparative example 4
This comparative example provides a matting film comprising a primer layer, a core layer and a matting layer, which are sequentially arranged. The preparation method of the resin containing the bottom coating extinction film of the comparative example comprises the following steps:
The primer resin was prepared by mixing 84.7wt% of an ethylene-octene copolymer (octene content: 18wt%, melt index: 6.5g/10min, melting point: 85 ℃) 15wt% of a propylene-butene copolymer (butene content: 33wt%, melt index: 7g/10min, melting point: 75 ℃) and 0.3wt% of an antioxidant uniformly by a high-speed mixer to obtain the primer resin.
The preparation of the core layer resin comprises the steps of taking 99wt% of homopolypropylene (with a melt index of 3.2g/10 min) and 1wt% of antistatic master batch (with a carrier of homopolypropylene and an effective concentration of 40 wt%) and uniformly mixing by a high-speed mixer to obtain the core layer resin.
The extinction layer resin is prepared by mixing 48wt% of high-density polyethylene, 37wt% of ethylene-propylene copolymer and 15wt% of propylene copolymer (propylene-1-butene copolymer with a melt index of 7.1g/10min, wherein the comonomer proportion of 1-butene is 31.3wt%, the crystallinity is 4.1%, the melting point is 120 ℃, and the propylene sequence isotacticity is 70% and the 1-butene sequence isotacticity is 80%) in the propylene-1-butene copolymer uniformly by a high-speed mixer to obtain the extinction layer resin.
The preparation method of the primer-containing matting film of this comparative example is the same as that of example 1, and thus a description thereof will be omitted.
The total thickness of the primer-containing matting film of this comparative example was 18 μm, in which the thickness of the primer layer was 1.8 μm and the thickness of the matting layer was 2. Mu.m.
Comparative example 5
This comparative example provides a matting film comprising a primer layer, a core layer and a matting layer, which are sequentially arranged. The preparation method of the resin containing the bottom coating extinction film of the comparative example comprises the following steps:
The primer resin was prepared by mixing 84.7wt% of an ethylene-octene copolymer (octene content: 18wt%, melt index: 6.5g/10min, melting point: 85 ℃) 15wt% of a propylene-butene copolymer (butene content: 33wt%, melt index: 7g/10min, melting point: 75 ℃) and 0.3wt% of an antioxidant uniformly by a high-speed mixer to obtain the primer resin.
The preparation of the core layer resin comprises the steps of taking 99wt% of homopolypropylene (with a melt index of 3.2g/10 min) and 1wt% of antistatic master batch (with a carrier of homopolypropylene and an effective concentration of 40 wt%) and uniformly mixing by a high-speed mixer to obtain the core layer resin.
The extinction layer resin is prepared by mixing 48wt% of high-density polyethylene, 37wt% of ethylene-propylene copolymer and 15wt% of propylene copolymer (propylene-1-butene copolymer with a melt index of 7.1g/10min, wherein the comonomer proportion of 1-butene is 31.3wt%, the crystallinity is 40%, the melting point is 165 ℃, and the propylene sequence isotacticity is 97% and the 1-butene sequence isotacticity is 93%) in the propylene-1-butene copolymer uniformly by a high-speed mixer.
The preparation method of the primer-containing matting film of this comparative example is the same as that of example 1, and thus a description thereof will be omitted.
The total thickness of the primer-containing matting film of this comparative example was 18 μm, in which the thickness of the primer layer was 1.8 μm and the thickness of the matting layer was 2. Mu.m.
Comparative example 6
This comparative example provides a matting film comprising a primer layer, a core layer and a matting layer, which are sequentially arranged. The preparation method of the resin containing the bottom coating extinction film of the comparative example comprises the following steps:
The primer resin was prepared by mixing 99.7wt% of an ethylene-octene copolymer (octene content: 18wt%, melt index: 6.5g/10min, melting point: 85 ℃ C.) and 0.3wt% of an antioxidant uniformly by a high-speed mixer to obtain a primer resin.
The preparation of the core layer resin comprises the steps of taking 99wt% of homopolypropylene (with a melt index of 3.2g/10 min) and 1wt% of antistatic master batch (with a carrier of homopolypropylene and an effective concentration of 40 wt%) and uniformly mixing by a high-speed mixer to obtain the core layer resin.
The extinction layer resin is prepared by mixing 48wt% of high-density polyethylene, 37wt% of ethylene-propylene copolymer and 15wt% of propylene copolymer (propylene-1-butene copolymer with a melt index of 7.1g/10min, wherein the comonomer proportion of 1-butene is 31.3wt%, the crystallinity is 7.46%, the melting point is 160 ℃, and the propylene sequence isotacticity is 93% and the 1-butene sequence isotacticity is 90%) in the propylene-1-butene copolymer uniformly by a high-speed mixer to obtain the extinction layer resin.
The preparation method of the primer-containing matting film of this comparative example is the same as that of example 1, and thus a description thereof will be omitted.
The total thickness of the primer-containing matting film of this comparative example was 18 μm, in which the thickness of the primer layer was 1.8 μm and the thickness of the matting layer was 2. Mu.m.
In this comparative example, the film production process was not smooth enough, and a delamination phenomenon occurred.
Comparative example 7
This comparative example provides a matting film comprising a primer layer, a core layer and a matting layer, which are sequentially arranged. The preparation method of the resin containing the bottom coating extinction film of the comparative example comprises the following steps:
The primer resin was prepared by mixing 69.7wt% of an ethylene-octene copolymer (octene content: 18wt%, melt index: 6.5g/10min, melting point: 85 ℃) and 30wt% of a propylene-butene copolymer (butene content: 33wt%, melt index: 7g/10min, melting point: 75 ℃) and 0.3wt% of an antioxidant uniformly by a high-speed mixer to obtain the primer resin.
The preparation of the core layer resin comprises the steps of taking 99wt% of homopolypropylene (with a melt index of 3.2g/10 min) and 1wt% of antistatic master batch (with a carrier of homopolypropylene and an effective concentration of 40 wt%) and uniformly mixing by a high-speed mixer to obtain the core layer resin.
The extinction layer resin is prepared by mixing 48wt% of high-density polyethylene, 37wt% of ethylene-propylene copolymer and 15wt% of propylene copolymer (propylene-1-butene copolymer with a melt index of 7.1g/10min, wherein the comonomer proportion of 1-butene is 31.3wt%, the crystallinity is 7.46%, the melting point is 160 ℃, and the propylene sequence isotacticity is 93% and the 1-butene sequence isotacticity is 90%) in the propylene-1-butene copolymer uniformly by a high-speed mixer to obtain the extinction layer resin.
The preparation method of the primer-containing matting film of this comparative example is the same as that of example 1, and thus a description thereof will be omitted.
The total thickness of the primer-containing matting film of this comparative example was 18 μm, in which the thickness of the primer layer was 1.8 μm and the thickness of the matting layer was 2. Mu.m.
The performance test results of the primed extinction films of examples 1-4 and comparative examples 1-7 are shown in Table 1 below.
TABLE 1
Because BOPP extinction film is stretched from the middle generally when transversely stretching, after reaching a certain tensile stress, the BOPP extinction film is gradually stretched to two sides, so the BOPP extinction film has the problem that the stretching of the middle of the film is better than that of the two sides, and the extinction effect is poor and even uneven.
As is apparent from the analysis of the above test results, the haze data of the matt film of the present invention is significantly improved in both examples 1 to 4 and comparative examples 1 to 3 with an increase in the amount of propylene-based copolymer added to the matt layer, and particularly, the effect of improving the matt and uneven dispersion on both sides of the film is significantly improved when the amount of propylene-based copolymer added to the matt layer is 15wt% or more, because the propylene-based copolymer added is a low crystalline material having a crystallinity far lower than that of the random copolymer polypropylene and the high-density polyethylene, the propylene-based copolymer forms a low crystalline continuous phase, and the presence of the low crystalline continuous phase makes the rapidly crystallized high-density polyethylene phase more easily protrude during high-speed stretching production, thereby effectively improving the problem of uneven edge matting and improving the overall matt effect.
In addition, because binary random copolymer polypropylene is used as a conventional heat sealing material, the initial heat sealing temperature is generally between 120 and 125 ℃, after a part of random copolymer polypropylene is replaced by propylene copolymer with high melting point, the heat resistance of a extinction layer can be improved, the problem of scalding or sticking the extinction layer under a high-temperature roller is reduced, the defect data is reduced more obviously along with the increase of the addition amount of the propylene copolymer, when the content of the propylene copolymer reaches more than 30wt%, the better extinction effect can be obtained, low defects can be realized, the quality of an extinction film is ensured, the punctiform or sesame-shaped appearance problem is reduced when paper plastic is covered with dark background, but when the content of the propylene copolymer is increased again, the defect data change of a film surface is not large, and the defect data is possibly related to high-temperature scalding of a high-density polyethylene phase in the extinction layer. It is also clear from the data of example 4 that the propylene-based copolymer having a melting point of 140℃is inferior to the propylene-based copolymer having a melting point of 160℃in improving the film surface scalding effect, but is also superior to that of comparative example 1 in which the propylene-based copolymer was not added.
In addition, because the crystallinity of the propylene-based copolymer is low, the stretching orientation of a polymer chain segment is an unstable state after the film is stretched into a film and shaped and cut, the existence of internal stress of the chain segment has a tendency to return to random coils, the tendency is particularly obvious at a certain heating temperature, and the crystallinity of a heat shrinkage system is generally in inverse proportion, so that the larger the addition amount of the propylene-based copolymer is, the lower the crystallinity of a continuous phase of a extinction layer is, the larger the heat shrinkage ratio is, when the transverse heat shrinkage ratio exceeds 4.5%, the edge warping phenomenon of a paper plastic film is obvious, even the phenomenon of upper UV gloss oil is influenced or printing overprinting is caused, and the ratio of the propylene-based copolymer is kept within 35wt% more suitable.
In comparative example 4, isotacticity of propylene sequence and 1-butene sequence in propylene copolymer is too low, so that melting point and crystallinity of propylene copolymer are reduced, flaw point of extinction surface of prepared film is obviously increased, that is, effective temperature-resistant protection of extinction layer cannot be achieved, heat shrinkage rate is increased, film surface curling can occur in film coating of downstream manufacturer, overprinting positioning deviation is large, and other serious quality problems are solved, but since crystallinity of propylene copolymer is further reduced, total crystal enthalpy value of continuous phase is reduced more obviously, and extinction effect of comparative example 4 is improved.
In comparative example 5, the isotacticity of the propylene sequence and the 1-butene sequence in the propylene-based copolymer is too high, so that the melting point and the crystallinity of the propylene-based copolymer are both increased, the compatibility of the propylene-based copolymer and other materials of the extinction layer is not facilitated, the thick sheet is incompatible, poor extinction surface stretching is caused, the extinction uniformity is poor, and the appearance of the film is affected.
In comparative example 6, the primer layer was not added with the propylene-butene copolymer, resulting in poor compatibility between the primer layer and the core layer, and delamination occurred during the production process, and in comparative example 7, the addition of an excessive amount of the propylene-butene copolymer reduced the bonding force between the primer layer and the hot melt adhesive layer, and interlayer delamination occurred during the peeling test.
The above examples illustrate only a few embodiments of the invention, which are described in detail and are not to be construed as limiting the scope of the invention. It should be noted that modifications and improvements can be made by those skilled in the art without departing from the spirit of the invention, and the invention is intended to encompass such modifications and improvements.