CN115401968A - Ultraviolet-resistant PVC (polyvinyl chloride) film and preparation process thereof - Google Patents
Ultraviolet-resistant PVC (polyvinyl chloride) film and preparation process thereof Download PDFInfo
- Publication number
- CN115401968A CN115401968A CN202211115130.0A CN202211115130A CN115401968A CN 115401968 A CN115401968 A CN 115401968A CN 202211115130 A CN202211115130 A CN 202211115130A CN 115401968 A CN115401968 A CN 115401968A
- Authority
- CN
- China
- Prior art keywords
- pvc film
- film
- ultraviolet
- resistant
- parts
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920000915 polyvinyl chloride Polymers 0.000 title claims abstract description 243
- 239000004800 polyvinyl chloride Substances 0.000 title claims abstract description 243
- 238000002360 preparation method Methods 0.000 title claims abstract description 49
- 239000004065 semiconductor Substances 0.000 claims abstract description 63
- 239000003607 modifier Substances 0.000 claims abstract description 41
- 239000000463 material Substances 0.000 claims abstract description 32
- 239000011347 resin Substances 0.000 claims abstract description 32
- 229920005989 resin Polymers 0.000 claims abstract description 32
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(III) oxide Inorganic materials O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000002250 absorbent Substances 0.000 claims abstract description 19
- 230000002745 absorbent Effects 0.000 claims abstract description 19
- 239000000945 filler Substances 0.000 claims abstract description 16
- 239000004014 plasticizer Substances 0.000 claims abstract description 13
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 12
- GEYXPJBPASPPLI-UHFFFAOYSA-N manganese(iii) oxide Chemical compound O=[Mn]O[Mn]=O GEYXPJBPASPPLI-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 239000004925 Acrylic resin Substances 0.000 claims description 47
- 229920000178 Acrylic resin Polymers 0.000 claims description 47
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 claims description 34
- 239000001509 sodium citrate Substances 0.000 claims description 30
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 30
- 238000001816 cooling Methods 0.000 claims description 28
- 239000000243 solution Substances 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 22
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 20
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 10
- 238000004140 cleaning Methods 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- 238000001125 extrusion Methods 0.000 claims description 7
- 235000012424 soybean oil Nutrition 0.000 claims description 7
- 239000003549 soybean oil Substances 0.000 claims description 7
- 239000006097 ultraviolet radiation absorber Substances 0.000 claims description 6
- 238000003490 calendering Methods 0.000 claims description 5
- 238000002844 melting Methods 0.000 claims description 4
- 230000008018 melting Effects 0.000 claims description 4
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims description 2
- 239000003063 flame retardant Substances 0.000 claims description 2
- 230000000087 stabilizing effect Effects 0.000 abstract description 7
- 230000007547 defect Effects 0.000 abstract description 4
- 230000002195 synergetic effect Effects 0.000 abstract description 3
- 230000002035 prolonged effect Effects 0.000 abstract description 2
- 239000000805 composite resin Substances 0.000 abstract 1
- 230000032683 aging Effects 0.000 description 48
- 230000000052 comparative effect Effects 0.000 description 38
- 238000004383 yellowing Methods 0.000 description 19
- 238000005452 bending Methods 0.000 description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 12
- 230000006750 UV protection Effects 0.000 description 9
- 150000003254 radicals Chemical class 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- 238000010521 absorption reaction Methods 0.000 description 6
- 229920003023 plastic Polymers 0.000 description 6
- 239000004033 plastic Substances 0.000 description 6
- 239000011358 absorbing material Substances 0.000 description 5
- 239000012153 distilled water Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 239000005909 Kieselgur Substances 0.000 description 4
- PXIPVTKHYLBLMZ-UHFFFAOYSA-N Sodium azide Chemical compound [Na+].[N-]=[N+]=[N-] PXIPVTKHYLBLMZ-UHFFFAOYSA-N 0.000 description 4
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Natural products OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 4
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- -1 packaging Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 239000006096 absorbing agent Substances 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 229910000416 bismuth oxide Inorganic materials 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 2
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 238000009740 moulding (composite fabrication) Methods 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 238000006479 redox reaction Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000002313 adhesive film Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000012271 agricultural production Methods 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000012668 chain scission Methods 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000007542 hardness measurement Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004643 material aging Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012768 molten material Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000002468 redox effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000010074 rubber mixing Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 239000012801 ultraviolet ray absorbent Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
- B32B27/304—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl halide (co)polymers, e.g. PVC, PVDC, PVF, PVDF
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
- B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/12—Chemical modification
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2250/00—Layers arrangement
- B32B2250/02—2 layers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2327/00—Polyvinylhalogenides
- B32B2327/06—PVC, i.e. polyvinylchloride
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2333/00—Polymers of unsaturated acids or derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
- C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2327/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08J2327/06—Homopolymers or copolymers of vinyl chloride
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2491/00—Characterised by the use of oils, fats or waxes; Derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
- C08K2003/3045—Sulfates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
- C08K7/26—Silicon- containing compounds
Landscapes
- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
The invention relates to the technical field of PVC films, and particularly discloses an ultraviolet-resistant PVC film and a preparation process thereof. The ultraviolet-resistant PVC film comprises a modified PVC film and a stable film, wherein the stable film is covered on the surface of the modified PVC film, and the modified PVC film is prepared from the following raw materials in parts by weight: the polyvinyl chloride resin composite material comprises 100-140 parts of polyvinyl chloride resin, 50-70 parts of semiconductor ultraviolet absorbent, 40-60 parts of heat-resistant modifier, 30-50 parts of plasticizer and 2-15 parts of filler, wherein the semiconductor ultraviolet absorbent comprises at least one of bismuth trioxide, aluminum oxide and manganese trioxide. The heat-resistant modifier, the semiconductor ultraviolet absorbent and the stabilizing film are mutually synergistic, and can effectively help the PVC film to resist ultraviolet rays, so that the defect that the PVC film absorbs ultraviolet rays and is aged is obviously overcome, and the service life of the PVC film is prolonged.
Description
Technical Field
The invention relates to the technical field of PVC films, in particular to an anti-ultraviolet PVC film and a preparation process thereof.
Background
PVC, one of the most used plastics in the world, has advantages such as low cost, flame resistance and corrosion resistance, and is widely used in various fields such as industrial and agricultural production. The modifier for improving the ductility and toughness of the PVC plastic is added into the PVC plastic, and the synthesized PVC film can be used as a decorative film and an adhesive film to be applied to industries such as building materials, packaging, medicines and the like.
Although the PVC film is a resin film with wide application, the PVC film is very sensitive to ultraviolet rays under sunlight, and is easy to turn yellow and lose mechanical properties when meeting the ultraviolet rays. The main component of the PVC film is polyvinyl chloride, and the molecular chain of the polyvinyl chloride has chlorine atoms with strong electronegativity, so that the polyvinyl chloride is easy to oxidize and degrade after absorbing ultraviolet light under the irradiation of the ultraviolet light to generate hydrochloric acid, and the hydrochloric acid can further catalyze and degrade the PVC.
Therefore, the inventor believes that the irradiation of the PVC film with ultraviolet light causes the aging and discoloration of the PVC material substrate, thereby shortening the service life of the PVC film. Therefore, it is necessary to invent a PVC film having an anti-UV effect.
Disclosure of Invention
In order to overcome the defect that a PVC film is easy to absorb ultraviolet rays and age, the application provides an ultraviolet-resistant PVC film and a preparation process thereof.
In a first aspect, the present application provides an ultraviolet resistant PVC film, which adopts the following technical scheme:
the ultraviolet-resistant PVC film comprises a modified PVC film and a stable film, wherein the stable film is covered on the surface of the modified PVC film, and the modified PVC film is prepared from the following raw materials in parts by weight: the flame-retardant polyvinyl chloride wire and cable material comprises 100-140 parts of polyvinyl chloride resin, 50-70 parts of semiconductor ultraviolet absorbent, 40-60 parts of heat-resistant modifier, 30-50 parts of plasticizer and 2-15 parts of filler, wherein the semiconductor ultraviolet absorbent comprises at least one of bismuth trioxide, aluminum oxide and manganese trioxide.
In the semiconductor ultraviolet material, a low-energy band valence band and a high-energy band conduction band exist, and because an energy difference exists between the low-energy band valence band and the high-energy band conduction band, namely a forbidden band with a certain width, the forbidden band can absorb energy higher than the forbidden band. The semiconductor material is used as an ultraviolet absorber and can absorb light having high energy and a short wavelength, such as ultraviolet light. After the semiconductor ultraviolet absorbent absorbs ultraviolet rays, the semiconductor ultraviolet absorbent has high energy, wherein a part of the energy is converted into heat energy and is transmitted to polyvinyl chloride resin, and after the heat-resistant modifier is added into the polyvinyl chloride resin, the polyvinyl chloride resin has good thermal stability, and the material aging caused by bond breakage is not easy to occur.
Meanwhile, the other part of energy enables the photogenerated electrons in the semiconductor to jump from a low valence band to a high conduction band, holes and the photogenerated electrons on the low valence band have redox property, oxygen and water in air can be subjected to redox to generate free radicals, and the free radicals can further undergo free radical degradation with the polyvinyl chloride resin. However, the surface of the modified PVC film is covered with the stable film, so that the contact of free radicals with air and water can be isolated, the degradation of the polyvinyl chloride resin is prevented, and the effect of improving the ageing resistance of the PVC film is achieved.
Therefore, bismuth oxide, aluminum oxide, manganese oxide and the like are used as ultraviolet absorbers and introduced into the PVC film, so that the ultraviolet absorption of the PVC film can be effectively prevented, and the ageing resistance of the PVC film is greatly improved. When the polyvinyl chloride resin is mixed with the semiconductor ultraviolet absorbent, the heat-resistant modifier, the plasticizer, the filler and the stabilizing film to prepare the PVC film, the heat-resistant modifier, the semiconductor ultraviolet absorbent and the stabilizing film have mutual synergistic action, and the PVC film can be effectively helped to resist ultraviolet rays, so that the defect that the PVC film absorbs ultraviolet rays to age is obviously improved, and the service life of the PVC film is prolonged.
In a specific embodiment, the modified PVC film comprises 120-130 parts of polyvinyl chloride resin, 45-65 parts of semiconductor ultraviolet absorbent, 45-55 parts of heat-resistant modifier, 35-45 parts of plasticizer and 5-10 parts of filler, based on the total weight of the modified PVC film.
Under the proportion of the components, the prepared PVC film has higher ultraviolet absorption capacity and better aging resistance.
In a specific possible embodiment, the heat-resistant modifier is prepared from the following raw materials in parts by weight: 60-80 parts of water, 10-20 parts of N, N dimethylformamide and 30-40 parts of p-aminophenol.
In water, the para-aminophenol and the PVC resin film generate substitution reaction under the catalysis of N, N dimethyl formamide to remove unstable chloride ions on the polyvinyl chloride. Because the p-aminophenol contains benzene ring, the stability of the PVC film is increased after the p-aminophenol is introduced to the polyvinyl chloride, and the problem that the PVC film is easy to decompose when meeting ultraviolet light or heat is solved. The inventors have also found that the unexpected effect of further improving the aging resistance of a PVC film is also obtained by using a film made of p-aminophenol and a polyvinyl chloride resin. The reason for this is probably that the energy of C-Cl bond in the PVC structure is low, and after absorbing ultraviolet light, the energy is increased to generate bond chain scission, so as to generate hydrochloric acid, thereby accelerating the aging speed of the PVC film. The p-aminophenol is introduced into the PVC film, so that the formation of hydrochloric acid can be reduced, and the problem of decomposition of the PVC film due to hydrochloric acid oxidation is solved.
In a specific embodiment, the semiconductor ultraviolet absorber further comprises an aqueous solution of sodium citrate.
Since the bismuth trioxide, the aluminum oxide and the manganese trioxide have high specific surface area and surface energy, agglomeration is likely to occur due to van der waals force or electrostatic force between the interiors during use, resulting in a decrease in the efficiency of the bismuth trioxide, the aluminum oxide and the manganese trioxide in absorbing ultraviolet rays. When at least one of bismuth trioxide, aluminum oxide and manganese trioxide is mixed with the sodium citrate solution, the sodium citrate can selectively adsorb the semiconductor material in the solution, thereby promoting the dispersibility of the semiconductor material and improving the ultraviolet absorption efficiency of the semiconductor material. Meanwhile, the sodium citrate is negatively charged in the solution, and the PVC resin modified by the p-aminophenol is provided with the positively charged amino group, so the negatively charged sodium citrate can be assembled on the surface of the PVC resin modified by the p-aminophenol through electrostatic adsorption, and a semiconductor material adsorbed on the sodium citrate is fixedly attached to the surface of the PVC resin, thereby effectively improving the anti-ultraviolet performance of the PVC film and improving the problem that the PVC film is easy to absorb ultraviolet light and age.
In a specific embodiment, the stabilizing film is an acrylic film.
After the semiconductor material absorbs ultraviolet light, photo-generated electrons can transit from a low valence band to a high conduction band, and the photo-generated electrons and the low valence band with holes have oxidation-reduction property. Free radicals are formed when air and water vapor are encountered, and the free radicals degrade the PVC film. Transparent and colorless acrylic resin is coated on the PVC film, the acrylic resin has water resistance and does not change color at high temperature, so that the semiconductor material can be effectively prevented from contacting air and water vapor to generate redox reaction, and the aging resistance of the modified PVC film is further improved.
In a specific possible embodiment, the plasticizer is epoxidized soybean oil.
The epoxidized soybean oil has excellent heat resistance and light resistance, has the effect of crosslinking and toughening on the polyvinyl chloride resin, can improve the mechanical strength and weather resistance of the polyvinyl chloride resin, and further improves the aging resistance of the PVC film.
In a specific possible embodiment, the filler is at least one of calcium carbonate, diatomaceous earth, and barium sulfate.
When the PVC film is prepared, the filler is added, which is beneficial to improving the mechanical strength performance of PVC, so that the PVC film has better fluidity and toughness, and the dimensional stability of the PVC film is improved.
In a second aspect, the application provides a preparation method of an ultraviolet-resistant PVC film, which adopts the following technical scheme: a preparation method of an anti-ultraviolet PVC film comprises the following steps,
s1, mixing, banburying, plasticizing, calendering, cooling and slitting polyvinyl chloride resin, a semiconductor ultraviolet absorbent, a plasticizer and a filler to prepare a semiconductor PVC film; cleaning a semiconductor PVC film, immersing the semiconductor PVC film in a heat-resistant modifier, heating to 50-60 ℃, preserving heat for 6 hours, cooling to room temperature, cleaning and drying to obtain a modified PVC film;
and S2, melting the acrylic resin, transferring the acrylic resin into a mold, cooling to normal temperature, keeping for 0.5h to obtain an acrylic resin film in a surface dry state, covering the surface of the modified PVC film with the acrylic resin film, and performing bubble removal, extrusion and cooling to obtain the ultraviolet-resistant PVC film.
By adopting the technical scheme, firstly, the polyvinyl chloride resin, the semiconductor ultraviolet absorbent, the plasticizer and the filler are mixed to ensure that the components are uniformly dispersed; heating the mixture to a melting degree through a rubber mixing process; then, extruding the mixed molten material into a film with a certain size by calendering; and finally, cooling, forming and cutting to obtain the semiconductor PVC film with the expected size. The semiconductor PVC film is soaked in the aqueous solution of p-aminophenol and N, N-dimethylformamide, so that the semiconductor PVC film and the p-aminophenol can react in the N, N-dimethylformamide more easily, the substitution reaction efficiency is higher, and the high-yield modified PVC film is obtained. The melted acrylic resin is easier to mold, so that the acrylic resin is melted at high temperature and then transferred into a mold to be made into a film. Because the acrylic resin at high temperature can cause the PVC film to be melted when covering the modified PVC film, the acrylic resin film is cooled to a surface dry state, and the acrylic resin film still has certain adhesive strength and is covered on the modified PVC film. After air bubble removal and extrusion, the acrylic resin film and the modified PVC film are bonded together to obtain the ultraviolet-resistant PVC film with better light transmittance.
In a third aspect, the application provides a preparation method of an ultraviolet-resistant PVC film, which adopts the following technical scheme: a preparation method of an anti-ultraviolet PVC film comprises the following steps,
p1, mixing, banburying, plasticizing, calendering, cooling and slitting the polyvinyl chloride resin, the plasticizer and the filler to prepare a PVC film; cleaning a PVC film, immersing the cleaned PVC film in a heat-resistant modifier, heating to 50-60 ℃, preserving heat for 6 hours, cooling to room temperature, cleaning and drying to obtain a heat-resistant PVC film;
p2, uniformly mixing the semiconductor material and the sodium citrate aqueous solution to obtain a reaction solution;
p3, putting the heat-resistant PVC film into the reaction solution, then taking out, cleaning, drying and cooling to room temperature to obtain a modified PVC film;
and P4, melting the acrylic resin, transferring the acrylic resin into a mold, cooling to normal temperature, keeping for 0.5h to obtain an acrylic resin film in a surface dry state, covering the surface of the modified PVC film with the acrylic resin film, and performing bubble removal, extrusion and cooling to obtain the ultraviolet-resistant PVC film.
By adopting the technical scheme, the PVC film is prepared firstly, impurities and free ions on the surface of the PVC film are cleaned and removed, then the PVC film is soaked in an aqueous solution of p-aminophenol and N, N-dimethylformamide, and the PVC film and the p-aminophenol react to obtain the high-yield heat-resistant PVC film. The sodium citrate and the semiconductor material are placed in a weakly acidic aqueous solution, and the sodium citrate is dissolved in water to form an anionic electrolyte solution under the condition of uniform stirring, so that the semiconductor material is adsorbed on citric acid ions, and the dispersibility of the semiconductor material is improved. When the heat-resistant PVC film is put into the reaction solution, the amino on the surface of the heat-resistant PVC film has positive charges, meanwhile, the activity of the amino is better, the citric acid ions loading the semiconductor material are adsorbed on the surface of the heat-resistant PVC film through the adsorption effect of positive and negative electrons, and after drying, the semiconductor material is fixedly attached to the heat-resistant PVC film, so that the effect of absorbing ultraviolet light is exerted.
In a specific embodiment, in the P2 step, the pH of the reaction solution is adjusted to 3 to 5.
By adopting the technical scheme, the sodium citrate and the semiconductor material are easier to have adsorption reaction in an acidic or weakly acidic environment, and the dispersibility of the semiconductor material is higher.
In summary, the present application includes at least one of the following beneficial technical effects:
1. bismuth trioxide, aluminum oxide and manganese trioxide are selected as semiconductor ultraviolet absorption materials, and forbidden bands exist in the semiconductor materials, so that energy higher than the forbidden bands, such as ultraviolet light energy, can be absorbed. The semiconductor ultraviolet absorbing material is selected to be attached to the PVC film, so that the ultraviolet resistance of the PVC film can be effectively improved;
2. according to the method, the polyvinyl chloride resin is modified by adopting p-aminophenol, and after the p-aminophenol and the polyvinyl chloride resin are subjected to substitution reaction, the carbon-chlorine short bond on the polyvinyl chloride resin is substituted, so that the thermal stability of the polyvinyl chloride is improved, and the possibility that hydrochloric acid is easily formed due to the breakage of the carbon-chlorine short bond is reduced;
3. the sodium citrate is used for adsorbing the semiconductor ultraviolet absorbing material in the solution, so that the dispersity of the semiconductor ultraviolet absorbing material is improved. The sodium citrate is in an anionic electrolyte in the aqueous solution, and the semiconductor ultraviolet absorption material is fixed on the surface of the PVC film by the sodium citrate electrolyte through the positive and negative electric adsorption;
4. in this application, adopt acrylic resin to cover on the modified PVC film, isolated the contact of semiconductor ultraviolet absorbing material and air and vapor, further prevent that semiconductor ultraviolet absorbing material from reacting with air and vapor, forming the free radical, and take place the problem of free radical degradation on the PVC film.
Detailed Description
In the application, the inventor discovers through previous experiments and investigations that bismuth trioxide, aluminum oxide and manganese trioxide as semiconductor materials have good capability of absorbing ultraviolet light; meanwhile, the inventors have found that the mechanical strength of the resin can be adjusted when at least one of calcium carbonate, diatomaceous earth and barium sulfate is used as a filler.
The present application is further illustrated below by reference to preparation examples, examples and comparative examples.
Preparation examples of the heat-resistant modifier preparation example 1 will be described below.
Preparation example 1
The preparation example adopts the following components in parts by weight: 60g of water, 10g of N, N-dimethylformamide and 30g of p-aminophenol.
In this preparation example, the heat-resistant modifier was prepared as follows:
mixing water, N-dimethylformamide and p-aminophenol, and stirring for 30min until the mixture is uniformly mixed to obtain the heat-resistant modifier.
Preparation examples 2 to 3
Preparation examples 2 to 3 differed from preparation example 1 in that: the amounts of the raw material components used are different and are shown in table 1.
TABLE 1
Preparation example of aqueous sodium citrate solution
The following description will be made by taking preparation example 4 as an example.
Preparation example 4
The mass ratio of sodium citrate to water in this preparation example was 3:7.
In this preparation, the aqueous sodium citrate solution was prepared as follows:
adding sodium citrate into water, stirring for 20min, and mixing to obtain sodium citrate water solution.
Preparation example 5
The difference between the preparation example and the preparation example 4 is that: the mass ratio of sodium citrate to water is 2:3.
Preparation example 6
The difference between the preparation example and the preparation example 4 is that: the mass ratio of sodium citrate to water is 1:1.
Examples
The following description will be given by taking example 1 as an example.
Example 1
This example provides components of an ultraviolet resistant PVC film, including a modified PVC film and an acrylic resin film, where the modified PVC film includes 100g of a polyvinyl chloride resin, 50g of bismuth trioxide, 40g of the heat resistant modifier of preparation example 1, 30g of epoxidized soybean oil, and 2g of calcium carbonate.
A preparation method of an anti-ultraviolet PVC film comprises the following steps:
firstly, putting polyvinyl chloride resin, bismuth trioxide, epoxidized soybean oil and calcium carbonate into a kneading machine for mixing and stirring, fully mixing and uniformly dispersing; then heating the mixed material to 100 ℃ by using an internal mixer to convert the mixed material into a viscous flow state, and then extruding PVC into a film by using a calender at the temperature of 60 ℃; after the film is formed, the film passes through a cooling roller to be cooled and shaped; and finally, slitting to obtain the PVC film.
The PVC film was then washed with distilled water 3 times to remove surface impurities, and then immersed in the heat-resistant modifier of preparation example 1. And (3) heating to 55 ℃, keeping the temperature for 6h, taking out the PVC film, cooling to room temperature, washing with distilled water for 4 times, and drying the PVC film at 40 ℃ to obtain the modified PVC film.
Finally, the acrylic resin was melted at 100 ℃. And then transferring the acrylic resin into a mold, cooling the acrylic resin to the normal temperature, and keeping for 0.5h to obtain the acrylic resin film with the surface kept in a dry state. And then taking the acrylic resin film out of the die, covering the acrylic resin film on the surface of the modified PVC film, carrying out bubble removal treatment on the acrylic resin film, then placing the acrylic resin film and the modified PVC film in a roller press for extrusion treatment, and cooling for 24 hours to obtain the ultraviolet-resistant PVC film.
Examples 2 to 5
Examples 2-5 differ from example 1 in that: the amounts of the raw material components used were varied and are shown in Table 2.
TABLE 2
Example 6
Example 6 differs from example 2 in that: the heat-resistant modifier was the heat-resistant modifier of preparation example 2.
Example 7
Example 7 differs from example 2 in that: the heat-resistant modifier was the heat-resistant modifier of preparation example 3.
Example 8
Example 8 differs from example 2 in that: replacing the bismuth trioxide with a mixture of equal amounts of bismuth trioxide, aluminum oxide and manganese trioxide, the weight ratio of bismuth trioxide, aluminum oxide and manganese trioxide being 1.
Example 9
Example 9 differs from example 2 in that: replacing calcium carbonate with a mixture of equal amounts of calcium carbonate, diatomaceous earth and barium sulfate, the weight ratio of calcium carbonate, diatomaceous earth and barium sulfate being 1.
Example 10
Example 10 differs from example 2 in that: when the heat-resistant modifier of preparation example 1 was added, the temperature was raised to 50 ℃.
Example 11
Example 11 differs from example 2 in that: when the heat-resistant modifier of preparation example 1 was added, the temperature was raised to 60 ℃.
Example 12
This example provides components of an ultraviolet resistant PVC film comprising a modified PVC film and an acrylic resin film, wherein the modified PVC film comprises 100g of a polyvinyl chloride resin, 50g of a semiconductor ultraviolet absorber, 40g of the heat resistant modifier of preparation example 1, 30g of epoxidized soybean oil, and 2g of calcium carbonate; wherein 50g of the semiconductor ultraviolet absorbent is a mixture of bismuth trioxide and the sodium citrate aqueous solution of preparation example 4, and the weight ratio of the bismuth trioxide to the sodium citrate aqueous solution of preparation example 4 is 1:1.
A preparation method of an ultraviolet-resistant PVC film comprises the following steps:
firstly, putting polyvinyl chloride resin, epoxidized soybean oil and calcium carbonate into a kneading machine for mixing and stirring, fully mixing and uniformly dispersing; then heating the mixed material to 100 ℃ by using an internal mixer to convert the mixed material into a viscous flow state, and then extruding the mixed material into a film by using a calender at the temperature of 60 ℃; after the film is formed, the film passes through a cooling roller to be cooled and shaped; and finally, slitting to obtain the PVC film. The PVC film was washed with distilled water 3 times to remove surface impurities, and then the PVC film was immersed in the heat-resistant modifier of preparation example 1. And (3) heating to 55 ℃, keeping the temperature for 6h, taking out the PVC film, cooling to room temperature, washing with distilled water for 4 times, and drying the PVC film at 40 ℃ to obtain the heat-resistant PVC film.
Bismuth trioxide and the sodium citrate aqueous solution of preparation example 4 were mixed, stirred for 30min to be uniform, and the pH of the mixed solution was adjusted to 4 to obtain a reaction solution. And then soaking the heat-resistant PVC film into the reaction solution, taking out the PVC film after 5 hours, washing away free ions on the surface of the PVC film by using distilled water, putting the PVC film into an oven to be dried for 3 hours at the temperature of 60 ℃, and cooling the PVC film to room temperature to obtain the modified PVC film.
Finally, the acrylic resin was melted at 100 ℃. And then transferring the acrylic resin into a mold, cooling the acrylic resin to the normal temperature, and keeping for 0.5h to obtain the acrylic resin film with the surface kept in a dry state. And then taking the acrylic resin film out of the die, covering the acrylic resin film on the surface of the modified PVC film, carrying out bubble removal treatment on the acrylic resin film, then placing the acrylic resin film and the modified PVC film in a roller press for extrusion treatment, and cooling for 24 hours to obtain the ultraviolet-resistant PVC film.
Example 13
Example 13 differs from example 12 in that: the sodium citrate solution used in preparation example 5 was selected.
Example 14
Example 14 differs from example 12 in that: the sodium citrate solution used in preparation example 6 was selected.
Example 15
Example 15 differs from example 12 in that: the pH of the reaction solution was 3.
Example 16
Example 16 differs from example 12 in that: the reaction solution had a pH of 5.
Example 17
Example 17 differs from example 12 in that: when the heat-resistant modifier of preparation example 1 was added, the temperature was raised to 50 ℃.
Example 18
Example 18 differs from example 12 in that: when the heat-resistant modifier of preparation example 1 was added, the temperature was raised to 60 ℃.
Comparative example
Comparative example 1
Comparative example 1 differs from example 2 in that: comparative example 1 contained no bismuth trioxide, heat resistance modifier and stabilizing film.
Comparative example 2
Comparative example 2 differs from example 2 in that: comparative example 2 contained no bismuth trioxide.
Comparative example 3
Comparative example 3 differs from example 2 in that: the bismuth trioxide was replaced by an equal amount of silica.
Comparative example 4
Comparative example 4 differs from example 2 in that: in comparative example 4, no heat resistance modifier was added.
Comparative example 5
Comparative example 5 differs from example 2 in that: the heat resistant modifier was replaced with an equivalent amount of sodium azide.
Comparative example 6
Comparative example 6 differs from example 2 in that: comparative example 6 did not contain an acrylic resin film.
Comparative example 7
Comparative example 7 differs from example 2 in that: the acrylic film is replaced with an epoxy film.
Performance detection
The following tests were performed on the uv resistant PVC films provided in examples 1 to 18 of the present application and comparative examples 1 to 7, and specific test data are shown in table 3,
ultraviolet light aging test: refer to GB/T16422.3-1997 plastics laboratory light exposure method-third part: fluorescent ultraviolet lamp "the ultraviolet ray irradiation tests were performed on the ultraviolet ray resistant PVC films provided in examples 1 to 18 and comparative examples 1 to 7, and the ultraviolet ray irradiation time and intensity were the same for each group.
And (3) testing the bending strength: the bending strength of the ultraviolet-resistant PVC films provided in examples 1-18 and comparative examples 1-7 before and after ultraviolet irradiation was tested by referring to GB/T9341-88 Plastic bending Performance test method.
The bending aging rate calculation method comprises the following steps: the bending aging rate is calculated by the following formula:
and (3) testing tensile property: the tensile properties of the ultraviolet-resistant PVC films provided in examples 1-18 and comparative examples 1-7 before and after ultraviolet irradiation were tested by referring to GB/T1040-92 Plastic tensile Property test method.
The method for calculating the stretching aging rate comprises the following steps: the tensile aging rate is calculated by the following formula:
and (3) hardness testing: the UV-resistant PVC films provided in examples 1 to 18 and comparative examples 1 to 7 were tested for surface hardness after UV irradiation, with reference to GB/T6739-1986 paint hardness test method.
Yellowing test: the yellowness index of the UV-resistant PVC films provided in examples 1 to 18 and comparative examples 1 to 7 before and after UV irradiation was measured with reference to ASTM D-1925.
The method for calculating the stretching aging rate comprises the following steps: the yellowing rate is calculated by the following formula:
TABLE 3
Compared with example 2, the bending aging rate, the tensile aging rate and the yellowing rate of the comparative example 1 are far higher than those of example 2, and the hardness is lower than that of example 2, which shows that the PVC film is beneficial to improving the anti-ultraviolet performance and reducing the aging and the yellowing after a semiconductor ultraviolet absorbent and a heat-resistant modifier are added.
Compared to example 2, comparative example 2, which did not contain a semiconductor ultraviolet absorber, had higher bending aging rate, tensile aging rate and yellowing rate than example 2; the hardness of the PVC film after being irradiated by ultraviolet rays is also poorer than that of the PVC film in example 2, which shows that the semiconductor ultraviolet ray absorbent plays an effective role in preventing ultraviolet rays in the PVC film and solves the problems of aging, mechanical property reduction and yellowing of the PVC film caused by the absorption of ultraviolet rays.
The bending aging rate, the tensile aging rate and the yellowing rate of comparative example 3 to which silica was added were also higher than those of example 2 and lower than those of the ultraviolet-resistant PVC film of example 2, which indicates that the semiconductor ultraviolet absorber of the present application has better ultraviolet resistance.
Compared with the example 2, the heat-resistant modifier is not added in the comparative example 4, the heat-resistant modifier is replaced by the sodium azide in the comparative example 5, and the test data shows that the bending aging rate, the tensile aging rate and the yellowing rate of the comparative examples 4 and 5 are higher than those of the example 2, and the hardness is lower than that of the ultraviolet-resistant PVC film of the example 2, which shows that the heat-resistant modifier adopted in the application can effectively improve the heat-resistant stability of the PVC film, and when the PVC film absorbs certain heat, the structural change of the PVC film due to unstable bonds is avoided.
Compared with example 2, when the acrylic resin film is not present in comparative example 6, the test data shows that the bending aging rate, the tensile aging rate and the yellowing rate of comparative example 6 are all higher than those of example 2, and the hardness of comparative example 6 is lower than that of example 2, which shows that the acrylic resin used in the application can effectively prevent the ultraviolet-resistant PVC film from contacting with air and water vapor, and prevent the semiconductor material from generating redox reaction with the air and the water vapor to form active free radicals, thereby effectively improving the ultraviolet resistance of the PVC film.
When the kind of the stabilizing film was changed to the epoxy resin film, the bending aging rate, the stretching aging rate and the yellowing rate of comparative example 7 were slightly higher than those of example 2, and the hardness of comparative example 7 was slightly lower than that of example 2. The data results of comparative examples 3, 5 and 7 in combination with example 2 show that the synergistic effect among the uv absorber, the heat-resistant modifier and the stabilizing film in the present application can further improve the uv protection capability of the PVC film.
From the bending aging rate, the stretching aging rate, the yellowing rate and the hardness of the examples 1 to 5, it can be known that the ultraviolet-resistant PVC films prepared by the raw material ratios and the process conditions of the examples 1 to 5 have excellent ultraviolet-resistant capability, wherein the example 2 is a preferred example.
Compared with the example 2, the examples 6 and 7 also have good bending aging rate, tensile aging rate and yellowing rate, and the hardness is similar to the example 2, which shows that the heat-resistant modifier can improve the anti-ultraviolet capability of the ultraviolet-resistant PVC film within the range of the mixture ratio provided by the application, thereby improving the defect that the PVC is easy to absorb ultraviolet aging.
The bending aging rate, the stretching aging rate and the yellowing rate of the PVC film are better than those of the PVC film in example 2, and the hardness of the PVC film in example 8 is similar to that of the PVC film in example 2, which shows that the bismuth oxide, the aluminum oxide and the manganese oxide can effectively absorb ultraviolet rays as semiconductor ultraviolet ray materials, so that the ultraviolet ray resistance of the PVC film is improved.
The bending aging rate, the stretching aging rate and the yellowing rate of the example 9 are similar to those of the example 2, and the hardness of the example 9 is higher than that of the example 2, which shows that when a mixture of calcium sulfate, diatomite and barium sulfate is added into the ultraviolet-resistant PVC film as a filler, the mechanical strength of the ultraviolet-resistant PVC film can be improved, so that the hardness of the ultraviolet-resistant PVC film is improved, and meanwhile, the PVC film in the example also has a better ultraviolet-resistant function.
The bending aging rate, the tensile aging rate, the yellowing rate and the hardness of examples 10 to 11 were similar to those of example 2, and it was demonstrated that the ultraviolet-resistant PVC film having good ultraviolet resistance can be prepared by adjusting the temperature within the temperature range of the present application during the preparation process.
Compared with example 2, the hardness of example 12 is similar to that of example 2, and example 12 has better bending aging rate, tensile aging rate and yellowing rate, because in example 12, the sodium citrate solution is added into the semiconductor ultraviolet absorbent, and the dispersibility of the bismuth trioxide is further promoted; meanwhile, the sodium citrate solution can also improve the connectivity of the PVC film modified by the heat-resistant modifier and the bismuth trioxide, and effectively improves the ultraviolet resistance of the ultraviolet-resistant PVC film.
Examples 13-14 also have good bend aging, tensile aging, yellowing and hardness compared to example 12, which demonstrates that sodium citrate solutions in the ranges provided herein can improve the uv resistance of PVC films.
Examples 15-16 also have good bending aging, tensile aging, yellowing and hardness compared to example 12, which shows that the UV resistant PVC films have better UV protection capability in the pH range provided in this application, thereby improving the resistance of the UV resistant PVC films to aging.
Examples 17-18 also have good bend aging, tensile aging, yellowing and hardness compared to example 12, which shows that UV resistant PVC films can be well prepared within the temperature range of the process provided herein, resulting in PVC films with excellent UV resistance.
The present embodiment is only for explaining the present application, and it is not limited to the present application, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present application.
Claims (10)
1. An ultraviolet-resistant PVC film is characterized in that: the PVC film comprises a modified PVC film and a stable film, wherein the stable film is covered on the surface of the modified PVC film, and the modified PVC film is prepared from the following raw materials in parts by weight: the flame-retardant polyvinyl chloride wire and cable material comprises 100-140 parts of polyvinyl chloride resin, 50-70 parts of semiconductor ultraviolet absorbent, 40-60 parts of heat-resistant modifier, 30-50 parts of plasticizer and 2-15 parts of filler, wherein the semiconductor ultraviolet absorbent comprises at least one of bismuth trioxide, aluminum oxide and manganese trioxide.
2. The ultraviolet resistant PVC film of claim 1, wherein: the modified PVC film comprises, by weight, 120-130 parts of a polyvinyl chloride resin, 45-65 parts of a semiconductor ultraviolet absorber, 45-55 parts of a heat-resistant modifier, 35-45 parts of a plasticizer and 5-10 parts of a filler.
3. The ultraviolet resistant PVC film of claim 1, wherein: the heat-resistant modifier is prepared from the following raw materials in parts by weight: 60-80 parts of water, 10-20 parts of N, N dimethylformamide and 30-40 parts of p-aminophenol.
4. The UV-resistant PVC film according to claim 3, wherein: the semiconductor ultraviolet absorbent also comprises a sodium citrate aqueous solution.
5. An ultraviolet resistant PVC film according to claim 1, characterised in that: the stable film is an acrylic resin film.
6. An ultraviolet resistant PVC film according to claim 1, characterised in that: the plasticizer is epoxidized soybean oil.
7. The ultraviolet resistant PVC film of claim 1, wherein: the filler is at least one of calcium carbonate, diatomite and barium sulfate.
8. The preparation method of the ultraviolet-resistant PVC film is characterized by comprising the following steps:
s1, mixing, banburying, plasticizing, calendering, cooling and slitting polyvinyl chloride resin, a semiconductor ultraviolet absorbent, a plasticizer and a filler to prepare a semiconductor PVC film; cleaning a semiconductor PVC film, immersing the semiconductor PVC film in a heat-resistant modifier, heating to 50-60 ℃, preserving heat for 6 hours, cooling to room temperature, cleaning and drying to obtain a modified PVC film;
and S2, after the acrylic resin is melted, transferring the acrylic resin into a mold, cooling to the normal temperature, keeping for 0.5h to obtain an acrylic resin film with a surface dry state, covering the surface of the modified PVC film with the acrylic resin film, and performing air bubble removal, extrusion and cooling to obtain the ultraviolet-resistant PVC film.
9. The preparation method of the ultraviolet-resistant PVC film is characterized by comprising the following steps:
p1, mixing, banburying, plasticizing, calendering, cooling and slitting the polyvinyl chloride resin, the plasticizer and the filler to prepare a PVC film; cleaning a PVC film, immersing the cleaned PVC film in a heat-resistant modifier, heating to 50-60 ℃, preserving heat for 6 hours, cooling to room temperature, cleaning and drying to obtain a heat-resistant PVC film;
p2, uniformly mixing the semiconductor material and the sodium citrate aqueous solution to obtain a reaction solution;
p3, putting the heat-resistant PVC film into the reaction solution, then taking out, cleaning, drying and cooling to room temperature to obtain a modified PVC film;
and P4, melting the acrylic resin, transferring the acrylic resin into a mold, cooling to normal temperature, keeping for 0.5h to obtain an acrylic resin film in a surface dry state, covering the surface of the modified PVC film with the acrylic resin film, and performing air bubble removal, extrusion and cooling to obtain the ultraviolet-resistant PVC film.
10. The method of preparing an ultraviolet resistant PVC film according to claim 9, wherein in the P2 step, the pH of the reaction solution is adjusted to 3-5.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211115130.0A CN115401968B (en) | 2022-09-14 | 2022-09-14 | Ultraviolet-resistant PVC film and preparation process thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211115130.0A CN115401968B (en) | 2022-09-14 | 2022-09-14 | Ultraviolet-resistant PVC film and preparation process thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115401968A true CN115401968A (en) | 2022-11-29 |
| CN115401968B CN115401968B (en) | 2024-05-24 |
Family
ID=84166408
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211115130.0A Active CN115401968B (en) | 2022-09-14 | 2022-09-14 | Ultraviolet-resistant PVC film and preparation process thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115401968B (en) |
Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09316115A (en) * | 1996-05-31 | 1997-12-09 | Nippon Kayaku Co Ltd | Heat-ray-shielding resin composition and coating film |
| JPH10219058A (en) * | 1997-02-05 | 1998-08-18 | Mitsubishi Chem Mkv Co | Vinyl chloride resin composition |
| CN103059466A (en) * | 2012-12-25 | 2013-04-24 | 东莞市祺龙电业有限公司 | Ultraviolet-proof environmental-friendly polyvinyl chloride (PVC) modified material and preparation method thereof |
| CN103289250A (en) * | 2013-06-24 | 2013-09-11 | 苏州新区佳合塑胶有限公司 | Safe non-toxic PVC film and preparation method thereof |
| CN106633526A (en) * | 2016-12-26 | 2017-05-10 | 南京工业大学 | Flame-retardant transparent plasticized PVC functional film and preparation method thereof |
| CN109337248A (en) * | 2018-10-18 | 2019-02-15 | 合肥万之景门窗有限公司 | A kind of heat-resisting anti-aging Corvic |
| CN110698787A (en) * | 2019-10-28 | 2020-01-17 | 江苏大海塑料股份有限公司 | Outdoor ultraviolet-resistant non-flow-line PVC film |
| CN110760141A (en) * | 2019-10-28 | 2020-02-07 | 江苏大海塑料股份有限公司 | High cold-resistant PVC film for vehicle |
| CN111298759A (en) * | 2020-04-07 | 2020-06-19 | 新昌县同生生物技术股份有限公司 | Pn-type semiconductor-magnetic porous carbon photocatalysis composite adsorbing material and its preparing method |
| CN112063069A (en) * | 2020-08-05 | 2020-12-11 | 百通达科技（东台）有限公司 | Ultraviolet-resistant polyvinyl chloride gloves and preparation process thereof |
| CN112980111A (en) * | 2021-03-25 | 2021-06-18 | 浙江清钰科技有限公司 | Ultraviolet-resistant PVC film and preparation method thereof |
| CN114231198A (en) * | 2021-11-09 | 2022-03-25 | 胡中兰 | High-molecular self-adhesive waterproof coiled material and preparation method thereof |
| CN114605754A (en) * | 2022-03-24 | 2022-06-10 | 江苏创念数字科技有限公司 | Preparation method of high-light-transmittance ultraviolet aging resistant polyvinyl chloride film |
-
2022
- 2022-09-14 CN CN202211115130.0A patent/CN115401968B/en active Active
Patent Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09316115A (en) * | 1996-05-31 | 1997-12-09 | Nippon Kayaku Co Ltd | Heat-ray-shielding resin composition and coating film |
| JPH10219058A (en) * | 1997-02-05 | 1998-08-18 | Mitsubishi Chem Mkv Co | Vinyl chloride resin composition |
| CN103059466A (en) * | 2012-12-25 | 2013-04-24 | 东莞市祺龙电业有限公司 | Ultraviolet-proof environmental-friendly polyvinyl chloride (PVC) modified material and preparation method thereof |
| CN103289250A (en) * | 2013-06-24 | 2013-09-11 | 苏州新区佳合塑胶有限公司 | Safe non-toxic PVC film and preparation method thereof |
| CN106633526A (en) * | 2016-12-26 | 2017-05-10 | 南京工业大学 | Flame-retardant transparent plasticized PVC functional film and preparation method thereof |
| CN109337248A (en) * | 2018-10-18 | 2019-02-15 | 合肥万之景门窗有限公司 | A kind of heat-resisting anti-aging Corvic |
| CN110698787A (en) * | 2019-10-28 | 2020-01-17 | 江苏大海塑料股份有限公司 | Outdoor ultraviolet-resistant non-flow-line PVC film |
| CN110760141A (en) * | 2019-10-28 | 2020-02-07 | 江苏大海塑料股份有限公司 | High cold-resistant PVC film for vehicle |
| CN111298759A (en) * | 2020-04-07 | 2020-06-19 | 新昌县同生生物技术股份有限公司 | Pn-type semiconductor-magnetic porous carbon photocatalysis composite adsorbing material and its preparing method |
| CN112063069A (en) * | 2020-08-05 | 2020-12-11 | 百通达科技（东台）有限公司 | Ultraviolet-resistant polyvinyl chloride gloves and preparation process thereof |
| CN112980111A (en) * | 2021-03-25 | 2021-06-18 | 浙江清钰科技有限公司 | Ultraviolet-resistant PVC film and preparation method thereof |
| CN114231198A (en) * | 2021-11-09 | 2022-03-25 | 胡中兰 | High-molecular self-adhesive waterproof coiled material and preparation method thereof |
| CN114605754A (en) * | 2022-03-24 | 2022-06-10 | 江苏创念数字科技有限公司 | Preparation method of high-light-transmittance ultraviolet aging resistant polyvinyl chloride film |
Non-Patent Citations (1)
| Title |
|---|
| 丹东市轻化工研究所: "《制革化工材料手册》", 中国轻工业出版社, pages: 408 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115401968B (en) | 2024-05-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP0612794B1 (en) | Thermostable copper-containing polyamide mouldings | |
| CN102417668A (en) | Cable sheath material for wind power generation and production method thereof | |
| CN109593290B (en) | Silane crosslinked flame-retardant polyvinyl chloride cable material and preparation method thereof | |
| CN114426766A (en) | High-shading double-color TPU (thermoplastic polyurethane) film and production process thereof | |
| CN111205565B (en) | Dynamic vulcanized halogen-free flame-retardant insulator sheath, umbrella skirt composite material and preparation method | |
| CN114957975A (en) | Environment-friendly waterproof outdoor cloth and preparation method thereof | |
| CN115401968A (en) | Ultraviolet-resistant PVC (polyvinyl chloride) film and preparation process thereof | |
| CN110128634B (en) | Preparation method of graphene modified polyester chip | |
| CN113717438A (en) | Calcium-zinc stabilizer with ultraviolet light shielding effect and preparation method thereof | |
| CN104004386A (en) | Preparation method of modified nano SiO2 and polyvinyl chloride (PVC) composition | |
| CN112708181A (en) | Nano modified weather-resistant TPO waterproof coiled material | |
| CN115287903B (en) | Seamless curtain with adhesive decorative connecting piece and preparation process | |
| CN115386200B (en) | PET composition and preparation method and application thereof | |
| CN105924905A (en) | Polyester film | |
| CN114044937B (en) | Nano-silver antibacterial agent, preparation method and application thereof | |
| CN115011088A (en) | Color master batch for carbon black coloring polyethylene glycol terephthalate and preparation method thereof | |
| CN113861584A (en) | PVC (polyvinyl chloride) plate and manufacturing method thereof | |
| CN101173121B (en) | Anti-ultraviolet organic-inorganic nano composite transparent coating and method for producing the same | |
| CN114805935A (en) | Preparation method of composite ultraviolet absorbent | |
| CN110684332B (en) | Lampshade of motorcycle headlamp and preparation method thereof | |
| KR100470765B1 (en) | The manufactural method of compounds for sealing rubber door gasket for drum type washing machine | |
| CN105670133A (en) | UV-yellowing-resistant TPV (thermoplastic vulcanizate) material and preparation method thereof | |
| CN118165397B (en) | Polyethylene composite material for plastic barrels and preparation method thereof | |
| CN114864195B (en) | Novel halogen-free low-smoke flame-retardant photovoltaic cable manufacturing method | |
| CN117510922B (en) | High-light-transmittance polyester film and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |