CN115216036A - Composite material for self-adhesive film and preparation method thereof - Google Patents
Composite material for self-adhesive film and preparation method thereof Download PDFInfo
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- 239000002313 adhesive film Substances 0.000 title claims abstract description 58
- 239000002131 composite material Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 36
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 35
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 35
- -1 polyethylene Polymers 0.000 claims description 19
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical class C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 12
- 239000003999 initiator Substances 0.000 claims description 12
- 150000003254 radicals Chemical class 0.000 claims description 12
- 239000005977 Ethylene Substances 0.000 claims description 10
- 239000004698 Polyethylene Substances 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 8
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 8
- 239000003963 antioxidant agent Substances 0.000 claims description 8
- 230000003078 antioxidant effect Effects 0.000 claims description 8
- 229910052740 iodine Inorganic materials 0.000 claims description 8
- 239000011630 iodine Substances 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 229920000573 polyethylene Polymers 0.000 claims description 8
- 229920005653 propylene-ethylene copolymer Polymers 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- 239000012752 auxiliary agent Substances 0.000 claims description 6
- 238000006116 polymerization reaction Methods 0.000 claims description 5
- 229920001897 terpolymer Polymers 0.000 claims description 5
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims description 4
- 239000000178 monomer Substances 0.000 claims description 4
- 229920006027 ternary co-polymer Polymers 0.000 claims description 4
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 2
- 125000001424 substituent group Chemical group 0.000 claims description 2
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims 1
- 238000010025 steaming Methods 0.000 claims 1
- 239000000835 fiber Substances 0.000 abstract description 10
- 238000007789 sealing Methods 0.000 abstract description 10
- 239000000463 material Substances 0.000 abstract description 6
- 239000005022 packaging material Substances 0.000 abstract description 6
- 229940127554 medical product Drugs 0.000 abstract description 3
- 239000003566 sealing material Substances 0.000 abstract description 2
- 230000003373 anti-fouling effect Effects 0.000 abstract 1
- 238000004806 packaging method and process Methods 0.000 description 8
- 239000000853 adhesive Substances 0.000 description 6
- 230000001954 sterilising effect Effects 0.000 description 6
- 238000004659 sterilization and disinfection Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 230000001070 adhesive effect Effects 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- 230000035699 permeability Effects 0.000 description 5
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 239000002985 plastic film Substances 0.000 description 4
- 230000002035 prolonged effect Effects 0.000 description 4
- 229910000077 silane Inorganic materials 0.000 description 4
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 3
- 229920006255 plastic film Polymers 0.000 description 3
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 241000894006 Bacteria Species 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000012790 adhesive layer Substances 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 230000000844 anti-bacterial effect Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000012793 heat-sealing layer Substances 0.000 description 2
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- CPKVUHPKYQGHMW-UHFFFAOYSA-N 1-ethenylpyrrolidin-2-one;molecular iodine Chemical compound II.C=CN1CCCC1=O CPKVUHPKYQGHMW-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- 229920010126 Linear Low Density Polyethylene (LLDPE) Polymers 0.000 description 1
- 229920000153 Povidone-iodine Polymers 0.000 description 1
- 206010039424 Salivary hypersecretion Diseases 0.000 description 1
- 241000700605 Viruses Species 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 230000000249 desinfective effect Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 208000015181 infectious disease Diseases 0.000 description 1
- 230000002147 killing effect Effects 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000012567 medical material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229960001621 povidone-iodine Drugs 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 208000026451 salivation Diseases 0.000 description 1
- 125000005373 siloxane group Chemical group [SiH2](O*)* 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- 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
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/16—Ethene-propene or ethene-propene-diene copolymers
-
- 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
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/04—Homopolymers or copolymers of ethene
- C08J2423/06—Polyethene
-
- 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
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/04—Homopolymers or copolymers of ethene
- C08J2423/08—Copolymers of ethene
-
- 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
- C08J2439/00—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 single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Derivatives of such polymers
- C08J2439/04—Homopolymers or copolymers of monomers containing heterocyclic rings having nitrogen as ring member
- C08J2439/06—Homopolymers or copolymers of N-vinyl-pyrrolidones
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Laminated Bodies (AREA)
Abstract
The invention provides a composite material for a self-adhesive film and a preparation method thereof. The composite material for the self-adhesive film has high peel strength and composite antifouling capacity, and can automatically fall off from an interface during peeling, so that the completeness of the peeling interface is ensured, and fiber debris is avoided. The self-adhesive film prepared from the material has high strength, including tensile strength, puncture strength, tearing strength, peeling strength and the like. Simultaneously meets the requirement of peeling integrity, and is particularly suitable for sealing and packaging materials of medical products.
Description
Technical Field
The invention relates to the field of medical instrument packaging materials, in particular to a composite material for a self-adhesive film and a preparation method thereof.
Background
The self-adhesive film is a soft film with high transparency and elasticity. It has high tensile strength, tear strength and excellent puncture resistance. The novel packaging material is prepared by taking Linear Low Density Polyethylene (LLDPE) as a main raw material, adding a small amount of auxiliary materials, uniformly mixing, melting and plasticizing by an extrusion system, and then performing single-layer, double-layer or multi-layer coextrusion salivation on a machine head and a forming die. Self-adhesive films are another type of product in protective films. Has the advantages of more environmental protection, cleaner, more stability, convenient lamination, difficult falling and the like. Self-adhesion means that the surface is self-adhesive, not gummed, and has no adhesive residue after being torn off from the surface of the product.
Different from common packages, a plurality of medical instruments need to be stored under an aseptic condition all the time before use, medical infection accidents caused by medical material instruments are avoided, and therefore the requirements on the bacteria resistance performance of the medical packaging bags are strict. In particular, for a medical packaging bag requiring sterilization, ethylene oxide is used for sterilization, and the packaging bag needs to have certain air permeability to allow the ethylene oxide to enter the packaging bag, so that the contents in the packaging bag can be sterilized. The self-adhesive film does not have air permeability or has poor air permeability, so that the self-adhesive film used as the raw material of the medical packaging bag needs to be combined with other materials with air permeability to meet the requirement of allowing the ethylene oxide to be used for sterilization.
Patent CN202122537046.5 discloses a self-adhesive film for sterilization packaging of medical instruments, which can be heat-sealed with medical dialyzing paper base paper or coated dialyzing paper for preparing sterilization packaging bags of medical instruments; the structure of it is: the base film is a composite plastic film consisting of polyethylene and other plastics and is divided into a front surface and a back surface, and the front surface is a printable surface; the reverse surface is the PE layer outer surface of the basal membrane, and the heat sealing layer is arranged on the outer surface of the PE layer. After the self-adhesive film is heat-sealed with the medical dialyzing paper base paper or the coated dialyzing paper, the heat-sealing stripping force is within the range of 1.3N/15mm-8.0N/15 mm.
The heat seal peel strength is generally opposite to the peel integrity, with high heat seal peel strength and low peel integrity, and the peel face is prone to fiber chipping. The heat seal layer of the medical packaging material not only needs higher heat seal peel strength to avoid package breakage during sterilization operation, but also needs higher peel integrity requirement to prevent fiber scraps from being generated on the peel surface during peeling.
Disclosure of Invention
The invention aims to provide a composite material for a self-adhesive film with higher peel strength and higher peel integrity and a preparation method thereof.
The technical scheme of the invention is as follows:
the composite material for the self-adhesive film comprises 5-15 parts by weight of a polyvinylpyrrolidone-iodine-polymethacryloyloxypropyltrimethoxysilane ternary complex, 45-75 parts by weight of a propylene-ethylene copolymer, 8-35 parts by weight of an ethylene derivative-acrylic acid-maleic anhydride ternary copolymer, 1-4 parts by weight of polyethylene wax, 0.1-0.5 part by weight of an antioxidant and 0.2-1.5 parts by weight of a PPA auxiliary agent, wherein the polyvinylpyrrolidone-iodine-polymethacryloyloxypropyltrimethoxysilane ternary complex has a chemical formula of [ (PVP) m-I 2 -(PMMPSi)n]。
The polyvinyl pyrrolidone, PVP for short, is a nontoxic water-soluble high molecular compound, has good film-forming property, and the PVP number average molecular weight for medicine is 10000-40000. PVP can be dissolved in water and can also be dissolved in a plurality of organic solvents such as alcohol, carboxylic acid, amine, halogenated hydrocarbon and the like. The povidone iodine is a loose complex formed by combining elemental iodine and PVP. Wherein the polyvinylpyrrolidone plays a role of a carrier and a dissolving assisting role. The ternary compound of polyvinylpyrrolidone-iodine-polymethacryloyloxypropyltrimethoxysilane contains iodine, and can release free iodine continuously to exert antibacterial effect, denature and kill protein, and has strong killing and disinfecting effects on bacteria, spores, fungi and viruses.
Besides the bactericidal effect of iodine element, the free iodine is combined with the hydrophilic PVP component, so that the polarity of the composite material can be improved, the direct bonding force with the base paper can be improved, and the peeling strength of the self-adhesive film can be improved. And the free iodine and the hydrophilic PVP component are combined to inhibit the adhesion of fiber debris, so that when the compound is packaged and opened, the self-adhesive film is cleanly separated from the surface of the base paper material, the integrity of a stripping surface is ensured, and the generation of the fiber debris is avoided.
The polyvinyl pyrrolidone-iodine-polymethacryloyloxypropyl trimethoxysilane ternary compound contains polymethacryloyloxypropyl trimethoxysilane, siloxane groups can be chemically bonded with hydroxyl on base paper fibers, the peeling strength of the self-adhesive film is improved, good film forming property and durability can be provided for polymers, and the service life of the self-adhesive film is prolonged.
The composite material for the self-adhesive film meets the requirements of self-adhesion and heat seal between the self-adhesive film and base paper, and has sufficient strength, tensile strength, piercing strength, tearing strength, peeling strength and the like. Also has higher peeling integrity, and is particularly suitable for the heat sealing layer of the sealing packaging material of medical products.
Wherein, the molar ratio of m to n in [ (PVP) m-I2- (PMMPSi) n ] is 80-97.
Through multiple experiments, the inventor finds that when the molar ratio of the polyvinylpyrrolidone to the polymethacryloyloxypropyltrimethoxysilane in the polyvinylpyrrolidone-iodine-polymethacryloyloxypropyltrimethoxysilane ternary complex is within a range from 80 to 97 and 2.5 to 19.5, the aging time of the self-adhesive film can be greatly prolonged, and the service life of the self-adhesive film is prolonged by 30 to 50 percent.
A preparation method of a composite material for a self-adhesive film comprises the following steps:
step 1): preparation of acetone solution of polyvinylpyrrolidone-iodine-polymethacryloyloxypropyltrimethoxysilane ternary complex [ (PVP) m-I2- (PMMPSi) n ] prepared as following formula (1):
mixing vinyl pyrrolidone and methacryloylMixing oxypropyltrialkoxysilane and free radical initiator to obtain mixture, adding 5-25 weight portions of the mixture into 100 weight portions of acetone, polymerizing at 50-90 deg.c in nitrogen atmosphere for 5-15 hr, adding simple iodine, and stirring at 50 deg.c for 20-60 min to obtain (PVP) m-I 2 - (PMMPSi) n acetone solution, the radical initiator being AIBME;
step 2): preparation of the composite material for the self-adhesive film:
mixing (PVP) m-I prepared in the step 1) 2 - (PMMPSi) n acetone solution containing (PVP) m-I 2 5-15 parts of dry matter- (PMMPSi) n, 45-75 parts of propylene-ethylene copolymer, 8-35 parts of ethylene derivative-acrylic acid-maleic anhydride terpolymer, 1-4 parts of polyethylene wax, 0.1-0.5 part of antioxidant and 0.2-1.5 parts of PPA auxiliary agent by weight are mixed, and the mixture is heated and distilled at the stirring speed of 100-1000r/min to remove acetone, so as to obtain the self-adhesive film composite material.
The propylene-ethylene copolymer regulates and controls air permeability, the ethylene derivative-acrylic acid-maleic anhydride terpolymer regulates and controls autohension, the ethylene wax and PAA additive regulate and controls processability, the antioxidant prevents materials from aging and degrading, and the service life of the autohension film is prolonged.
Wherein, the molar ratio of the free radical initiator AIBME to m + n in the step 1) is 0.5-3.
The addition amount of the free radical initiator AIBME ensures the stability of self-adhesion of the obtained material and ensures that the self-adhesive film has higher peel strength.
AIBME (Dimethyl 2,2' -azobis (2-methylproprionate), the Chinese name is azodiisobutyrate methyl ester, and the molecular formula is C 10 H 14 N 2 O 4 . The relative molecular mass was 226.23. Azodiisobutyronitrile methyl ester is one of the most commonly used azo-type initiators. It features stable decomposition reaction, only 1 kind of free radicals and no poison of decomposed product.
The addition amount of the elementary iodine in the step 1) is (PVP) m-I 2 (PMMPSi) n in an amount of 0.01-3% by weight of dry matter.
Preparing a ternary compound of (PVP) m-I2- (PMMPSi) n in the step 1), wherein a substituent R in the monomer MMPSi is methyl or ethyl; during polymerization, the MMPSi monomer added can be one of or a mixture of the trimethoxysilane and the triethoxysilane in any ratio.
The ethylene derivative-acrylic acid-maleic anhydride terpolymer used in the step 2) has an ethylene derivative structural unit which is an ethylene, propylene or 1-butene polymerization unit.
The composite material for the self-adhesive film reduces the cost, and the [ (PVP) m-I 2 -(PMMPSi)n]I in ternary complexes 2 The self-adhesive film has high peel strength and self-cleaning capability, can be completely and cleanly separated from the interface when being peeled off, thereby ensuring that the peeling interface is clean and flat without fiber scraps, and is particularly suitable for sealing and packaging materials of medical products.
The self-adhesive film prepared from the composite material has the advantages of good attaching effect with the surface of an adherend, strong adhesive force, no adhesive residue, easy peeling, difficult adhesion of the surface layer and the self-adhesive layer during peeling, better mechanical property, higher tensile strength and higher nominal strain rate of fracture.
Detailed Description
Example 1
Step 1) mixing Vinyl Pyrrolidone (VP), methacryloxypropyl trialkyloxy silane (MMPSi) and a free radical initiator AIBME to obtain a mixture, wherein the molar ratio m: n of the vinyl pyrrolidone to the methacryloxypropyl trialkyloxy silane is 90 2 (PMMPSi) n 3% by weight of dry matter, stirring at 50 ℃ for a further 20 minutes to obtain (PVP) m-I 2 - (PMMPSi) n acetone solution, yield 100%.
Step 2) preparation of composite material for self-adhesive film
The (PVP) m-I prepared in the step 1) is 2 - (PMMPSi) n acetone solution of (PVP) m-I 2 (PMMPSi) n ternary complex dry matter weight of 5 weight parts, propylene-ethylene copolymer of 45 weight parts, 8 weight partsAdding 1 part by weight of polyethylene wax, 0.1 part by weight of antioxidant and 0.2 part by weight of PPA (poly (phenylene-co-phenylene-maleic anhydride)) additive into a mixer, stirring at the speed of 1000r/min, and evaporating to recover acetone as a solvent to obtain the composite material for the self-adhesive film.
Example 2
Step 1) mixing Vinylpyrrolidone (VP), methacryloxypropyl trialkyloxy silane (MMPSi) and a free radical initiator AIBME to obtain a mixture, wherein the molar ratio m: n of the vinylpyrrolidone to the methacryloxypropyl trialkyloxy silane is 97 2 (PMMPSi) n 2% by weight of dry matter, stirring at 50 ℃ for a further 60 minutes to obtain (PVP) m-I 2 - (PMMPSi) n acetone solution, yield 100%.
Step 2) preparation of composite material for self-adhesive film
The (PVP) m-I prepared in the step 1) is 2 - (PMMPSi) n acetone solution of (PVP) m-I 2 15 parts by weight of dry matter of the (PMMPSi) n ternary complex, 75 parts by weight of propylene-ethylene copolymer, 35 parts by weight of ethylene derivative-acrylic acid-maleic anhydride ternary copolymer, 4 parts by weight of polyethylene wax, 0.5 part by weight of antioxidant and 1.5 parts by weight of PPA auxiliary agent are added into a mixer, stirred at a speed of 100r/min and the solvent acetone is recovered by evaporation to obtain the composite material for the self-adhesive film.
Example 3
Step 1) mixing Vinylpyrrolidone (VP) with methacryloxypropyl trialkyloxysilane (MMPSi) and a free radical initiator AIBME to obtain a mixture, wherein the molar ratio m: n of the vinylpyrrolidone to the methacryloxypropyl trialkyloxysilane is 80, the molar ratio m: n of the free radical initiator AIBME to m + n is 0.5 2 -(PMMPSi) n 0.01% by weight of dry matter, stirring was continued at 50 ℃ for 40 minutes to obtain (PVP) m-I 2 - (PMMPSi) n acetone solution, yield 100%.
Step 2) preparation of composite material for self-adhesive film
The (PVP) m-I prepared in the step 1) is 2 - (PMMPSi) n acetone solution of (PVP) m-I 2 10 parts by weight of dry matter of the- (PMMPSi) n ternary complex, 60 parts by weight of propylene-ethylene copolymer, 20 parts by weight of ethylene derivative-acrylic acid-maleic anhydride ternary copolymer, 3 parts by weight of polyethylene wax, 0.3 part by weight of antioxidant and 1 part by weight of PPA auxiliary agent are added into a mixer, stirred at the speed of 500r/min, and the solvent acetone is evaporated and recovered to obtain the composite material for the self-adhesive film.
Experimental example 1: the self-adhesive film was prepared using the composite material for self-adhesive films prepared in example 1.
Experimental example 2: the self-adhesive film was prepared using the composite material for self-adhesive films prepared in example 2.
Experimental example 3: the self-adhesive film was prepared using the composite material for self-adhesive films prepared in example 3.
Experimental example 4: the self-adhesive film and base paper composite prepared by the composite material for the self-adhesive film prepared in the example 1 are adopted to prepare a composite film, and the heat sealing temperature is as follows: 200 ℃, heat-seal pressure: 0.5MPa, heat-seal time: for 2 seconds.
Experimental example 5: the composite material for the self-adhesive film prepared in the embodiment 2 is used for preparing a composite film by compounding the self-adhesive film and base paper, and the heat sealing temperature is as follows: 200 ℃, heat-seal pressure: 0.5MPa, heat-seal time: for 2 seconds.
Experimental example 6: the self-adhesive film and base paper composite prepared by the composite material for the self-adhesive film prepared in the example 1 are adopted to prepare a composite film, and the heat sealing temperature is as follows: 200 ℃, heat sealing pressure: 0.5Mpa, heat-sealing time: for 2 seconds.
Tensile strength, nominal strain rate at break test
According to section 3 of determination of tensile Properties of plastics: the tensile strength and elongation at break were measured according to the test conditions for thin plastics and sheets GB/T1040.3-2016, and the results are shown in Table 1;
measuring the friction coefficient according to GB10006-88 standard of Plastic film and sheet friction coefficient determination method; the results are shown in Table 1.
The right-angle tearing force is measured according to the standard of 'Plastic tearing Strength test method' QB/T1130-91, and the test result is shown in Table 2;
measuring the heat-seal peeling force according to GB8808, the test results are shown in Table 2;
measured according to the method for testing the pendulum impact resistance of the plastic film GB8809, and the test results are shown in Table 2.
Results of the experiment
TABLE 1 tensile Strength, nominal strain at Break and coefficient of Friction
TABLE 2 Right Angle tear force, heat seal peel force and pendulum impact resistance
| Right angle tear force | Heat sealing peeling force (N/10 mm) | Pendulum impact resistance | Peeling interface | |
| Experimental example 4 | 6.12 | 6.53 | 2.237 | Smooth and clean without fiber scraps |
| Experimental example 5 | 6.23 | 6.64 | 2.515 | Smooth and clean without fiber scraps |
| Experimental example 6 | 5.98 | 6.52 | 2.945 | Smooth and clean without fiber scraps |
Experimental examples show that the self-adhesive film prepared from the self-adhesive film composite material has high tensile strength and nominal strain rate of fracture, low coefficient of dynamic friction and high coefficient of static friction. After the composite material is compounded with base paper, the right-angle tearing force and the heat-seal peeling force are higher, and the pendulum impact resistance is good. The adhesive force is strong, the stability is good, no adhesive residue, the stripping is easy, the surface layer and the self-adhesive layer are not easy to adhere during stripping, the uncoiling is easy, and the use is convenient.
Claims (7)
1. A composite material for a self-adhesive film, characterized in that: comprises 5 to 15 weight portions of polyvinylpyrrolidone-iodine-polymethacryloyloxypropyltrimethoxysilane ternary complex, 45 to 75 weight portions of propylene-ethylene copolymer, 8 to 35 weight portions of ethylene derivative-acrylic acid-maleic anhydride ternary copolymer, 1 to 4 weight portions of polyethylene wax, 0.1 to 0.5 weight portion of antioxidant and 0.2 to 1.5 weight portions of PPA auxiliary agent, wherein the polyvinylpyrrolidone-iodine-polymethacryloyloxypropyltrimethoxysilane ternary complex has a chemical formula of [ (PVP) m -I 2 -(PMMPSi) n ]。
2. The composite material for self-adhesive films according to claim 1, characterized in that:[(PVP) m -I 2 -(PMMPSi) n ]wherein the mol ratio of m to n is 80-97.
3. A method for preparing the composite material for self-adhesive films according to claim 2, characterized in that: the method comprises the following steps:
step 1): preparation of polyvinylpyrrolidone-iodine-polymethacryloyloxypropyltrimethoxysilane ternary complex [ (PVP) m-I 2 -(PMMPSi)n]Prepared as follows (1):
mixing vinyl pyrrolidone, methacryloxypropyl trialkoxysilane and a free radical initiator to obtain a mixture, adding 5-25 parts by weight of the mixture into 100 parts by weight of acetone, carrying out polymerization reaction at 50-90 ℃ for 5-15 hours under nitrogen atmosphere, adding an iodine simple substance, and continuously stirring at 50 ℃ for 20-60 minutes to obtain (PVP) m-I 2 - (PMMPSi) n acetone solution, the radical initiator being AIBME;
step 2): preparation of the composite material for the self-adhesive film:
mixing the (PVP) m-I prepared in the step 1) 2 - (PMMPSi) n acetone solution containing (PVP) m-I 2 5-15 parts of dry matter- (PMMPSi) n, 45-75 parts of propylene-ethylene copolymer, 8-35 parts of ethylene derivative-acrylic acid-maleic anhydride terpolymer, 1-4 parts of polyethylene wax, 0.1-0.5 part of antioxidant and 0.2-1.5 parts of PPA auxiliary agent by weight, and heating and steaming at a stirring speed of 100-1000r/min to remove acetone to obtain the self-adhesive film composite material.
4. The process for the preparation of the composite material for self-adhesive films according to claim 3, characterized in that: the molar ratio of the free radical initiator AIBME to m + n in the step 1) is 0.5-3.
5. Preparation of the composite material for self-adhesive films according to claim 4The preparation method is characterized by comprising the following steps: the addition amount of the elemental iodine in the step 1) is (PVP) m -I 2 -(PMMPSi) n 0.01-3% of the dry matter mass.
6. The process for the preparation of the composite material for self-adhesive films according to claim 5, characterized in that: step 1) (PVP) m -I 2 -(PMMPSi) n Preparing a ternary complex, wherein a substituent R in the monomer MMPSi is methyl or ethyl; during polymerization, the MMPSi monomer added can be one of or a mixture of the trimethoxysilane and the triethoxysilane in any ratio.
7. The method for preparing a composite material for self-adhesive films according to claim 6, characterized in that: the ethylene derivative-acrylic acid-maleic anhydride terpolymer used in the step 2) has an ethylene derivative structural unit which is an ethylene, propylene or 1-butene polymerization unit.
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| CN202210895712.9A CN115216036B (en) | 2022-07-27 | 2022-07-27 | Composite material for self-adhesive film and preparation method thereof |
| PCT/CN2023/093446 WO2024021765A1 (en) | 2022-07-27 | 2023-05-11 | Composite material for self-adhesive film and preparation method therefor |
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|---|---|---|---|---|
| WO2024021765A1 (en) * | 2022-07-27 | 2024-02-01 | 威海恒瑞新型包装材料有限公司 | Composite material for self-adhesive film and preparation method therefor |
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| US3006900A (en) * | 1953-08-22 | 1961-10-31 | Basf Ag | Production of water-soluble copolymers of methacrylamide and n-vinylpyrrolidone |
| JP2004035591A (en) * | 2002-06-28 | 2004-02-05 | Konishi Co Ltd | Curable resin composition, method for producing the same and method for bonding using the same |
| CN102002132A (en) * | 2009-09-02 | 2011-04-06 | 陈煜� | Improvement on method for preparing complex of polyvinylpyrrolidone grafted with natural polymer or water-soluble derivate thereof and iodine derivate |
| CN105017826A (en) * | 2015-07-12 | 2015-11-04 | 陈翠莲 | Functional paint with added gama-methacryloxypropyltrimethoxysilane |
| CN111333778A (en) * | 2020-03-20 | 2020-06-26 | 博爱新开源医疗科技集团股份有限公司 | Waterproof polymer bactericide and preparation method and application thereof |
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| JP2003064191A (en) * | 2001-08-24 | 2003-03-05 | Japan Polyolefins Co Ltd | Tearable sealant film |
| WO2003031512A1 (en) * | 2001-09-26 | 2003-04-17 | Japan Polyolefins Co., Ltd. | Polyolefin resin material, layered product comprising the same, process for producing the same, and molded object obtained therefrom |
| JP2013094302A (en) * | 2011-10-28 | 2013-05-20 | Nippon Shokubai Co Ltd | Packaging for medical adhesive sheet |
| CN113043695B (en) * | 2021-03-22 | 2022-11-18 | 四川汇利实业有限公司 | Modified PE film and preparation method thereof |
| CN115216036B (en) * | 2022-07-27 | 2023-04-28 | 威海恒瑞新型包装材料有限公司 | Composite material for self-adhesive film and preparation method thereof |
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| US3006900A (en) * | 1953-08-22 | 1961-10-31 | Basf Ag | Production of water-soluble copolymers of methacrylamide and n-vinylpyrrolidone |
| JP2004035591A (en) * | 2002-06-28 | 2004-02-05 | Konishi Co Ltd | Curable resin composition, method for producing the same and method for bonding using the same |
| CN102002132A (en) * | 2009-09-02 | 2011-04-06 | 陈煜� | Improvement on method for preparing complex of polyvinylpyrrolidone grafted with natural polymer or water-soluble derivate thereof and iodine derivate |
| CN105017826A (en) * | 2015-07-12 | 2015-11-04 | 陈翠莲 | Functional paint with added gama-methacryloxypropyltrimethoxysilane |
| CN111333778A (en) * | 2020-03-20 | 2020-06-26 | 博爱新开源医疗科技集团股份有限公司 | Waterproof polymer bactericide and preparation method and application thereof |
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| WO2024021765A1 (en) * | 2022-07-27 | 2024-02-01 | 威海恒瑞新型包装材料有限公司 | Composite material for self-adhesive film and preparation method therefor |
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| CN115216036B (en) | 2023-04-28 |
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Denomination of invention: A composite material for self mucosal use and its preparation method Granted publication date: 20230428 Pledgee: Weihai Commercial Bank Co.,Ltd. Chucun Branch Pledgor: WEIHAI HENGRUI MEDICAL PACKAGING Co.,Ltd. Registration number: Y2024980003131 |