CN114316479A - Environment-friendly tracing type PVC heat-shrinkable label film and preparation method thereof - Google Patents
Environment-friendly tracing type PVC heat-shrinkable label film and preparation method thereof Download PDFInfo
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- CN114316479A CN114316479A CN202210168646.5A CN202210168646A CN114316479A CN 114316479 A CN114316479 A CN 114316479A CN 202210168646 A CN202210168646 A CN 202210168646A CN 114316479 A CN114316479 A CN 114316479A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 11
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- 239000000700 radioactive tracer Substances 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims description 17
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- 239000002002 slurry Substances 0.000 claims description 16
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- 235000012239 silicon dioxide Nutrition 0.000 claims description 15
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- 239000004014 plasticizer Substances 0.000 claims description 10
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- 239000011347 resin Substances 0.000 claims description 9
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- LFKMKZZIPDISEK-UHFFFAOYSA-L magnesium;4-carboxy-2,6-dihydroxyphenolate Chemical compound [Mg+2].OC1=CC(C([O-])=O)=CC(O)=C1O.OC1=CC(C([O-])=O)=CC(O)=C1O LFKMKZZIPDISEK-UHFFFAOYSA-L 0.000 claims description 3
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- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 claims description 3
- 229910000391 tricalcium phosphate Inorganic materials 0.000 claims description 3
- XSMMCTCMFDWXIX-UHFFFAOYSA-N zinc silicate Chemical compound [Zn+2].[O-][Si]([O-])=O XSMMCTCMFDWXIX-UHFFFAOYSA-N 0.000 claims description 3
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- YAHBZWSDRFSFOO-UHFFFAOYSA-L dimethyltin(2+);2-(2-ethylhexoxy)-2-oxoethanethiolate Chemical group CCCCC(CC)COC(=O)CS[Sn](C)(C)SCC(=O)OCC(CC)CCCC YAHBZWSDRFSFOO-UHFFFAOYSA-L 0.000 claims description 2
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Abstract
The invention belongs to the technical field of high polymer material processing, and particularly relates to an environment-friendly tracing type PVC heat-shrinkable label film and a preparation method thereof. The invention prepares the silica powder containing fluorescent components by combining the environment-friendly rare earth inorganic fluorescent tracer material and the silica used as the opening agent in the PVC formula, and then adds the powder into the PVC heat-shrinkable label film formula system, and the PVC heat-shrinkable label film with the environment-friendly fluorescent tracer function is prepared by mixing and processing. The heat-shrinkable label film disclosed by the invention has no environmental protection hazard and risk, and the defects that the continuous tracing effect cannot be achieved due to uneven dispersion because the rare earth inorganic fluorescent tracing material is less added, and the rare earth inorganic fluorescent tracing material is more added, so that the high cost and the light transmittance of the film are influenced are avoided by synthesizing the silicon dioxide powder containing the fluorescent component.
Description
Technical Field
The invention belongs to the technical field of high polymer material processing, and particularly relates to an environment-friendly tracing type PVC heat-shrinkable label film and a preparation method thereof.
Background
The heat-shrinkable label film obtains exquisite patterns and colors through printing, the propaganda effect of the label is highlighted, the heat-shrinkable label film is usually printed by adopting a gravure, and eight to ten complicated chromatic sets are used, so that the heat-shrinkable label film has high requirements on chromatic alignment. With the rapid increase of printing speed, full-automatic computer register sets have been commonly used in intaglio printing production lines. Under the automatic plate aligning mode, the computer can automatically track, and can automatically send out a deviation correcting signal when finding a deviation problem, so that the plate roller or the base material moves and is aligned again, and the printing color registering quality is ensured. In order to accurately and timely find the offset condition of a base material film in printing, the full-automatic computer register device mainly tracks and monitors the running tracks of two side edges of the advancing film in the printing process, and (ultraviolet) fluorescence tracing is a convenient and common tracking and monitoring mode. The method is that a small amount of fluorescent whitening agent is added into a base film, the edge part of the film is irradiated by ultraviolet light, the fluorescent whitening agent in the film absorbs the ultraviolet light and emits visible light, and the part without the film has no change. The side position of the film can be accurately displayed and determined through the light change difference after the ultraviolet light irradiation, whether the film generates the offset in the operation process is judged, and the tracing function of tracking monitoring is realized.
At present, the PVC heat shrinkable label substrate film mostly adopts fluorescent whitening agents, so that on one hand, the white brightness of the film can be improved, and the tracing effect can also be achieved. The fluorescent whitening agent is firstly mixed with the plasticizer and then is uniformly mixed with the PVC resin and other additives. However, optical brighteners are a class of fluorescent dyes, a generic term for a class of compounds. Its property is to excite incident light to generate fluorescence, so that the colored matter can emit the flash luminous effect similar to fluorite, and the matter seen by naked eyes is whiter, its whitening property is determined by its special structure in its molecule, its chromophoric group has conjugated system capable of producing pi → pi jumping, and the most common of these systems are benzene ring, naphthalene ring, triazine ring, vinyl group, five-membered heterocyclic ring and some other condensed ring systems. Fluorescent whitening agents have a potential risk of carcinogenesis and can accumulate in the human viscera. Therefore, the varieties of fluorescent whitening agents OB-1 and the like have been drawn high attention by European regulations, and a series of regulations are promulgated in many countries such as European Union, Japan and the like to limit the range of the fluorescent whitening agents. In addition to the limited use of optical brighteners themselves, products in the industries of plastics, chemical fibers and the like also impose more severe requirements on the application of optical brighteners, i.e. they must also meet the environmental protection restrictions on the relevant structural components such as "phenol, nonylphenol, bisphenol a, phthalates, polycyclic aromatic hydrocarbons, heavy metals, aromatic amines, formaldehyde, octylphenol, vinyl chloride, antioxidants BHT, disperse dyes, pentachlorophenol and the like".
Therefore, due to the environmental protection defect of the fluorescent whitening agent, the fluorescent whitening agent is not used in the heat shrinkable label substrate film in the current heat shrinkable label film industry, thereby limiting the fluorescent tracing function of the PVC heat shrinkable label film in the market.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides an environment-friendly tracing type PVC heat-shrinkable label film and a preparation method thereof, aiming at solving the technical problem that the fluorescent tracing function of the PVC heat-shrinkable label film is limited due to the use of a fluorescent whitening agent caused by the environment-friendly defect of the fluorescent whitening agent in the heat-shrinkable label film industry.
The invention provides an environment-friendly tracing type PVC heat-shrinkable label film, which has the following specific technical scheme:
the environment-friendly tracing type PVC heat-shrinkable label film comprises the following components in parts by weight: 100 parts of PVC resin, 1.6-2 parts of stabilizer, 4-5 parts of plasticizer, 2-2.4 parts of processing aid, 3.5-4.5 parts of reinforcing agent, 0.8-1.2 parts of internal lubricant, 0.4-1 part of external lubricant and 1-3 parts of tracer-opener, wherein the tracer-opener is silicon dioxide powder containing fluorescent component.
In some embodiments, the silica powder containing a fluorescent component is prepared from the following raw materials: water glass, phosphoric acid, rare earth oxide ultraviolet fluorescent powder, a silane coupling agent and water. The specific component of the water glass is sodium silicate; the rare earth oxide ultraviolet fluorescent powder can be selected from the following varieties: calcium orthophosphate [ (Ca, Zn)3(PO4)2:Tl]Strontium pyrophosphate (Sr)2P2O7Eu), zinc silicate (Zn)2SiO4Mn), magnesium gallate (MgGa)2O4Mn), and the like. The silane coupling agent modifies the surface of the silicon dioxide, reduces the agglomeration phenomenon of the silicon dioxide, and improves the interface bonding property of the silicon dioxide and PVC resin. The selected varieties comprise KH550, KH570 and the like.
In certain embodiments, the stabilizer is methyltin mercaptide 181, the plasticizer DOP, the processing aid is ACR, the transport enhancer is MBS, the internal lubricant is RGH-4, and the external lubricant is AC-316A.
The invention also provides another technical scheme, namely a preparation method of the environment-friendly tracing type PVC heat shrinkable label film, which is used for the method of the heat shrinkable label film and comprises the following steps:
s1, preparing silicon dioxide powder containing fluorescent components;
s2, mixing the PVC resin, the stabilizer, the plasticizer, the processing aid, the reinforcing agent, the internal lubricant, the external lubricant and the silica powder containing the fluorescent component in the step S1 to obtain a mixture;
and S3, plasticizing the mixture obtained in the step S2 by an extruder, molding by a film blowing machine head, carrying out secondary heating, secondary blowing, cooling and shaping to obtain the environment-friendly tracing type PVC heat-shrinkable label film.
In some embodiments, in step S1, the preparation of the silica powder containing fluorescent components comprises the following steps:
s11, heating the solid water glass to 40-48 ℃ to dissolve the solid water glass into liquid water glass;
s12, adding 80% phosphoric acid into the water glass in the step S11 according to the mass ratio of 3:2.5, heating to 80-85 ℃, and reacting for 60-70 minutes to obtain silicon dioxide slurry;
s13, performing filter pressing treatment on the silicon dioxide slurry obtained in the step S12, recycling the filtrate, washing the filter cake to be neutral, adding water into the filter cake, and pulping to prepare new silicon dioxide slurry with the silicon content of 50%;
s14, adding rare earth oxide ultraviolet fluorescent powder accounting for 2-3% of the weight of the new silicon dioxide slurry in the step S13, stirring and mixing for 5-10 minutes, then adding silane coupling agent accounting for 2% of the weight of the new silicon dioxide slurry, and continuing stirring and mixing for 15-20 minutes to obtain mixed slurry; dissolving the silane coupling agent with a small amount of water, and adding the silane coupling agent into the new slurry;
s15, spray drying the mixed slurry obtained in the step S14 to obtain the silica powder containing the fluorescent component with the grain diameter of 3-5 microns.
Further, the rare earth oxide ultraviolet fluorescent powder is selected from one or more of calcium orthophosphate, strontium pyrophosphate, zinc silicate and magnesium gallate; in step S15, spray drying was performed by a spray dryer at 220 ℃ with a feed pump at 350 rpm.
In certain embodiments, in step S2, the mixing includes the steps of:
s21, adding PVC resin, a stabilizer and a plasticizer in the rotating process of the high-speed mixer;
s22, adding a processing aid, a reinforcing agent and an internal lubricant when the temperature of the quick mixer is raised to 75-80 ℃;
s23, when the temperature of the high-speed mixer rises to 95-100 ℃, adding an external lubricant and the silicon dioxide powder containing the fluorescent components in the step S1;
and S24, when the temperature of the high-speed mixer rises to about 125 ℃, putting the high-temperature mixture into a cooling mixer, stirring and cooling, and discharging when the temperature of the cooling mixer is below 45 ℃.
In certain embodiments, in step S3, the extruder is a single screw extruder with a screw diameter of 65mm, a screw length to diameter ratio of 29.5:1, and a compression ratio of 2.8: 1; extruder temperature: 140-: 175-180 ℃; temperature of the die: 190 ℃ at 180 ℃ and 200 ℃ at 190 ℃. Heating in water bath at 78-81 deg.C; the diameter of the mouth mold of the film blowing mold is 130mm, the gap of the mouth mold is 0.9mm, and the double-air-port air ring is arranged.
The invention has the following beneficial effects: the environment-friendly tracing type PVC heat-shrinkable label film provided by the invention is prepared by combining an environment-friendly rare earth inorganic fluorescent tracing material and silicon dioxide serving as a shedding agent in a PVC formula to prepare silicon dioxide powder containing fluorescent components, then adding the powder into a PVC heat-shrinkable label film formula system, mixing and processing to prepare the PVC heat-shrinkable label film with an environment-friendly fluorescent tracing function. The rare earth oxide ultraviolet fluorescent powder is an inorganic rare earth material, has a different fluorescence mechanism from a fluorescent whitening agent, has no environmental protection hazard and risk, and can be used as an environmental protection tracer for a PVC heat-shrinkable label film. The rare earth oxide ultraviolet fluorescent powder is powder and can be directly added into a PVC shrink film formula system for mixing use, but considering the high price of the tracer and the use requirements of small using amount and uniform dispersion of the tracer, the problem that the continuous tracing effect cannot be achieved due to uneven dispersion due to less addition and more addition are avoided by synthesizing the silicon dioxide powder containing the fluorescent component, so that the cost is high, and the light transmittance of the film is influenced.
Drawings
FIG. 1 is a flow chart of a method for preparing an environmentally friendly tracer PVC heat shrinkable label film according to the present invention;
FIG. 2 is a flow chart of the preparation of the silica powder containing a fluorescent component according to the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings 1-2 in conjunction with specific embodiments.
Preparation of silicon dioxide powder containing fluorescent component
The fluorescent material is prepared from water glass, phosphoric acid, rare earth oxide ultraviolet fluorescent powder, a silane coupling agent, water and the like.
(1) Solid water glass (sodium silicate) is heated to 40-48 ℃ to be dissolved into liquid water glass.
(2) 80% phosphoric acid was added in a mass ratio (water glass: 80% phosphoric acid: 3:2.5), heated to 80 to 85 ℃, and reacted for 60 to 70 minutes to obtain silica slurry.
(3) And (4) carrying out filter pressing treatment on the slurry, and recycling the filtrate. The filter cake is washed to neutrality.
(4) Adding water into the filter cake and pulping to prepare new silicon dioxide slurry with the silicon content of 50 percent.
(5) And (3) adding the rare earth oxide ultraviolet fluorescent powder accounting for 2-3% of the weight of the new slurry into the new slurry, stirring and mixing for 5-10 minutes, then adding the silane coupling agent accounting for 2% of the weight of the new slurry, continuously stirring and mixing for 15-20 minutes, and uniformly mixing.
(6) Spray-drying with a spray dryer (spray-drying temperature 220 deg.C, feed pump 350rpm) to obtain silica powder containing fluorescent component with particle size of 3-5 μm.
Preparation of PVC heat-shrinkable label film with environment-friendly tracing function
A single-layer PVC heat-shrinkable label film is prepared by adopting a traditional two-bubble method film blowing machine set.
1. Formulation of
The specific embodiment is as follows:
2. kneading process
The components in the formula are mixed into a uniform dry mixture in a form of matching a high-speed mixer and a cooling (low-speed) mixer.
The feeding sequence in the mixing process is as follows:
firstly, adding PVC resin, a stabilizer and a plasticizer in the rotating process of a high-speed mixer;
② when the temperature of the high-speed mixer rises to 75-80 ℃, MBS, ACR and RGH-4 are added;
thirdly, when the temperature of the high-speed mixer is increased to 95-100 ℃, adding the silicon dioxide powder containing the fluorescent component and AC-316A;
fourthly, when the temperature of the high-speed mixer rises to about 125 ℃, the mixture is put into a cooling mixer to be stirred and cooled;
cooling the mixer to 45 deg.c and discharging for further use.
3. Blow molding
The same equipment and process as those of the common PVC heat-shrinkable label film are adopted.
The process flow comprises the following steps: dry mixing, extruder plasticizing, film blowing head forming, secondary heating, secondary blowing, cooling and shaping, curling, slitting, packaging and obtaining finished products.
The secondary heating can be water bath heating.
Extrusion and film blowing:
equipment: the single-screw extruder has a screw diameter of 65mm, a screw length-diameter ratio of 29.5:1 and a compression ratio of 2.8: 1.
The diameter of a mouth mold of the film blowing mold is 130mm, the gap of the mouth mold is 0.9mm, and the double-air-port air ring is arranged.
Extruder temperature: 140 ℃ to 150 ℃, 150 ℃ to 155 ℃, 160 ℃ to 165 ℃, 175 ℃ to 185 ℃, 175 ℃ to 180 ℃. Temperature of the connection section: 175 ℃ and 180 ℃. The temperature of the mold is 180 ℃ to 190 ℃ and 190 ℃ to 200 ℃. The heating temperature of the water bath is 78-81 ℃.
4. PVC heat-shrinkable label film-related properties
Table 1 comparison of test Properties of Heat-shrinkable label films
Note: 【1】 Fluorescence detection: the ultraviolet lamp irradiation qualitative determination and detection method for the fluorescent whitening agent in the paper is specified in GB/T5009.78-2003 and GB/T27741-. Namely: in a dark room or a dark box, turning on a power switch of an ultraviolet lamp, selecting 365nm of detection wavelength, and making into 100cm2The sample was placed about 20cm under an ultraviolet lamp source and observed for significant blue or violet fluorescence.
As can be seen from Table 1, the environmental-friendly tracing type PVC heat-shrinkable label film provided by the invention has the advantages that the shrinkage, tensile strength, elongation at break, light transmittance, palm folding property, printability and other properties are not influenced by a tracer, the properties are consistent with those of a common PVC heat-shrinkable label film, and meanwhile, the environmental-friendly tracing type PVC heat-shrinkable label film has good ultraviolet irradiation fluorescence display performance.
The above description is only for the purpose of illustrating preferred embodiments of the present invention and is not to be construed as limiting the invention, and the present invention is not limited to the above examples, and those skilled in the art should also be able to make various changes, modifications, additions or substitutions within the spirit and scope of the present invention.
Claims (8)
1. The environment-friendly tracing type PVC heat-shrinkable label film is characterized by comprising the following components in parts by weight: 100 parts of PVC resin, 1.6-2 parts of stabilizer, 4-5 parts of plasticizer, 2-2.4 parts of processing aid, 3.5-4.5 parts of reinforcing agent, 0.8-1.2 parts of internal lubricant, 0.4-1 part of external lubricant and 1-3 parts of tracer-opener, wherein the tracer-opener is silicon dioxide powder containing fluorescent component.
2. The environmentally friendly tracer PVC heat shrink label film according to claim 1, wherein the silica powder containing fluorescent component is made from the following raw materials: water glass, phosphoric acid, rare earth oxide ultraviolet fluorescent powder, a silane coupling agent and water.
3. The environmentally friendly tracer PVC heat shrink label film according to claim 1, wherein the stabilizer is methyltin mercaptide 181, the plasticizer DOP, the processing aid is ACR, the transport enhancer is MBS, the internal lubricant is RGH-4, and the external lubricant is AC-316A.
4. A method for producing an environmentally friendly tracer PVC heat shrinkable label film, for use in the method for producing the heat shrinkable label film of any one of claims 1 to 3, characterized by comprising the steps of:
s1, preparing silicon dioxide powder containing fluorescent components;
s2, mixing the PVC resin, the stabilizer, the plasticizer, the processing aid, the reinforcing agent, the internal lubricant, the external lubricant and the silica powder containing the fluorescent component in the step S1 to obtain a mixture;
and S3, plasticizing the mixture obtained in the step S2 by an extruder, molding by a film blowing machine head, carrying out secondary heating, secondary blowing, cooling and shaping to obtain the environment-friendly tracing type PVC heat-shrinkable label film.
5. The method for preparing an environmentally friendly tracer PVC heat shrinkable label film according to claim 4, wherein in step S1, the preparation steps of the silica powder containing fluorescent components are as follows:
s11, heating the solid water glass to 40-48 ℃ to dissolve the solid water glass into liquid water glass;
s12, adding 80% phosphoric acid into the water glass in the step S11 according to the mass ratio of 3:2.5, heating to 80-85 ℃, and reacting for 60-70 minutes to obtain silicon dioxide slurry;
s13, performing filter pressing treatment on the silicon dioxide slurry obtained in the step S12, recycling the filtrate, washing the filter cake to be neutral, adding water into the filter cake, and pulping to prepare new silicon dioxide slurry with the silicon content of 50%;
s14, adding rare earth oxide ultraviolet fluorescent powder accounting for 2-3% of the weight of the new silicon dioxide slurry in the step S13, stirring and mixing for 5-10 minutes, then adding silane coupling agent accounting for 2% of the weight of the new silicon dioxide slurry, and continuing stirring and mixing for 15-20 minutes to obtain mixed slurry;
s15, spray drying the mixed slurry obtained in the step S14 to obtain the silica powder containing the fluorescent component with the grain diameter of 3-5 microns.
6. The method for preparing an environment-friendly tracer PVC heat-shrinkable label film according to claim 5, wherein the rare earth oxide UV fluorescent powder is selected from one or more of calcium orthophosphate, strontium pyrophosphate, zinc silicate and magnesium gallate; in step S15, spray drying was performed by a spray dryer at 220 ℃ with a feed pump at 350 rpm.
7. The method for preparing an environmentally friendly tracer PVC heat shrinkable label film according to claim 4, wherein the mixing in step S2 includes the steps of:
s21, adding PVC resin, a stabilizer and a plasticizer in the rotating process of the high-speed mixer;
s22, adding a processing aid, a reinforcing agent and an internal lubricant when the temperature of the quick mixer is raised to 75-80 ℃;
s23, when the temperature of the high-speed mixer rises to 95-100 ℃, adding an external lubricant and the silicon dioxide powder containing the fluorescent components in the step S1;
and S24, when the temperature of the high-speed mixer rises to 125 ℃, putting the high-temperature mixture into a cooling mixer, stirring and cooling, and discharging when the temperature of the cooling mixer is below 45 ℃.
8. The method for preparing environment-friendly tracer PVC heat-shrinkable label film according to claim 4, wherein in step S3, the extruder is a single-screw extruder, the screw diameter is 65mm, the screw length-diameter ratio is 29.5:1, and the compression ratio is 2.8: 1; extruder temperature: 140-: 175-180 ℃; temperature of the die: 190 ℃ at 180 ℃ and 200 ℃ at 190 ℃ and 78-81 ℃ in a water bath; the diameter of the mouth mold of the film blowing mold is 130mm, the gap of the mouth mold is 0.9mm, and the double-air-port air ring is arranged.
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