CN112662030A - Antibacterial plastic for manufacturing children guardrail and preparation method and application thereof - Google Patents
Antibacterial plastic for manufacturing children guardrail and preparation method and application thereof Download PDFInfo
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- CN112662030A CN112662030A CN202011360174.0A CN202011360174A CN112662030A CN 112662030 A CN112662030 A CN 112662030A CN 202011360174 A CN202011360174 A CN 202011360174A CN 112662030 A CN112662030 A CN 112662030A
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- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 134
- 229920003023 plastic Polymers 0.000 title claims abstract description 71
- 239000004033 plastic Substances 0.000 title claims abstract description 71
- 238000002360 preparation method Methods 0.000 title claims abstract description 37
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 16
- 239000003242 anti bacterial agent Substances 0.000 claims abstract description 44
- 229920001903 high density polyethylene Polymers 0.000 claims abstract description 41
- 239000004700 high-density polyethylene Substances 0.000 claims abstract description 41
- 239000004594 Masterbatch (MB) Substances 0.000 claims abstract description 39
- 239000011347 resin Substances 0.000 claims abstract description 12
- 229920005989 resin Polymers 0.000 claims abstract description 12
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 20
- 239000004332 silver Substances 0.000 claims description 20
- 229910052709 silver Inorganic materials 0.000 claims description 20
- 239000003963 antioxidant agent Substances 0.000 claims description 18
- 230000003078 antioxidant effect Effects 0.000 claims description 18
- 239000007822 coupling agent Substances 0.000 claims description 16
- 239000004599 antimicrobial Substances 0.000 claims description 11
- 239000002270 dispersing agent Substances 0.000 claims description 11
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 10
- 239000004595 color masterbatch Substances 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 8
- 239000002131 composite material Substances 0.000 claims description 7
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 6
- 238000001125 extrusion Methods 0.000 claims description 6
- 238000005469 granulation Methods 0.000 claims description 5
- 230000003179 granulation Effects 0.000 claims description 5
- 230000004048 modification Effects 0.000 claims description 5
- 238000012986 modification Methods 0.000 claims description 5
- -1 3, 5-di-tert-butyl-4-hydroxyphenyl Chemical group 0.000 claims description 4
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 4
- 229910019142 PO4 Inorganic materials 0.000 claims description 4
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 claims description 4
- 239000010452 phosphate Substances 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 4
- 229910000166 zirconium phosphate Inorganic materials 0.000 claims description 4
- LEHFSLREWWMLPU-UHFFFAOYSA-B zirconium(4+);tetraphosphate Chemical compound [Zr+4].[Zr+4].[Zr+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LEHFSLREWWMLPU-UHFFFAOYSA-B 0.000 claims description 4
- 230000000845 anti-microbial effect Effects 0.000 claims description 3
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 claims description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 2
- 239000001506 calcium phosphate Substances 0.000 claims description 2
- 229910000389 calcium phosphate Inorganic materials 0.000 claims description 2
- 235000011010 calcium phosphates Nutrition 0.000 claims description 2
- 239000002734 clay mineral Substances 0.000 claims description 2
- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 claims description 2
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 2
- JUWGUJSXVOBPHP-UHFFFAOYSA-B titanium(4+);tetraphosphate Chemical compound [Ti+4].[Ti+4].[Ti+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O JUWGUJSXVOBPHP-UHFFFAOYSA-B 0.000 claims description 2
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 claims description 2
- WGKLOLBTFWFKOD-UHFFFAOYSA-N tris(2-nonylphenyl) phosphite Chemical compound CCCCCCCCCC1=CC=CC=C1OP(OC=1C(=CC=CC=1)CCCCCCCCC)OC1=CC=CC=C1CCCCCCCCC WGKLOLBTFWFKOD-UHFFFAOYSA-N 0.000 claims description 2
- 230000004888 barrier function Effects 0.000 claims 1
- 230000000840 anti-viral effect Effects 0.000 abstract description 15
- 239000002861 polymer material Substances 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 8
- 239000000463 material Substances 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000000843 powder Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 241000894006 Bacteria Species 0.000 description 3
- 230000003712 anti-aging effect Effects 0.000 description 3
- 229920001684 low density polyethylene Polymers 0.000 description 3
- 239000004702 low-density polyethylene Substances 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 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 description 1
- NWYGETXZXGDGKD-UHFFFAOYSA-N 4-[4-[4-(4-carboxyphenyl)-n-[4-(4-carboxyphenyl)phenyl]anilino]phenyl]benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C1=CC=C(N(C=2C=CC(=CC=2)C=2C=CC(=CC=2)C(O)=O)C=2C=CC(=CC=2)C=2C=CC(=CC=2)C(O)=O)C=C1 NWYGETXZXGDGKD-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 1
- 235000017491 Bambusa tulda Nutrition 0.000 description 1
- 241001330002 Bambuseae Species 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 241000700605 Viruses Species 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000003863 ammonium salts Chemical group 0.000 description 1
- 239000011425 bamboo Substances 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
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- 238000011161 development Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229920006262 high density polyethylene film Polymers 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
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- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920013716 polyethylene resin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 229910001923 silver oxide Inorganic materials 0.000 description 1
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Landscapes
- Compositions Of Macromolecular Compounds (AREA)
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Abstract
The invention provides an antibacterial plastic for manufacturing a child guardrail and a preparation method and application thereof, wherein the antibacterial plastic comprises the following components in parts by weight: 80-85 parts of high-density polyethylene resin and 4-7 parts of antibacterial master batch; the antibacterial master batch comprises the following components in parts by weight: 80-85 parts of high-density polyethylene resin and 15-20 parts of modified inorganic antibacterial agent; the antibacterial plastic improves the surface energy of the high polymer material and the inorganic antibacterial agent and improves the adhesion of the interface of the high polymer material and the inorganic antibacterial agent by selecting the modified inorganic antibacterial agent; in addition, by optimizing the formula of the modified inorganic antibacterial agent and the HDPE, the prepared antibacterial plastic has excellent antibacterial and antiviral effects and excellent mechanical properties, can be applied to toy products for children, and has high application value.
Description
Technical Field
The invention belongs to the technical field of material preparation, and particularly relates to an antibacterial plastic for manufacturing a child guardrail and a preparation method and application thereof.
Background
High Density Polyethylene (HDPE) has good mechanical properties, and its hardness, tensile strength and creep are superior to those of low density polyethylene; and has excellent wear resistance, electrical insulation, toughness and cold resistance; the chemical stability is good, the corrosion of various acids, alkalis and salts can be resisted, and the paint is insoluble in any organic solvent at room temperature; HDPE films have low water absorption and low permeability to water vapor and air. HDPE is also widely used in the fields of packaging materials, daily necessities, and the like; wherein, in the daily necessities industry, the children that HDPE made crawls guardrail has obtained extensive application, and the baby of just birth relies on the taste to know this world for a long time, so it is very necessary to make the children and crawl guardrail with antibiotic antiviral HDPE material.
CN105801976A discloses an HDPE antibacterial plastic and a preparation method thereof, the antibacterial plastic has excellent mechanical property and processability, good flame retardant property and good antibacterial property, and can be used for various plastic products such as plastic films, pipes, plates and the like. However, the formula of the material uses organic antibacterial agents, which is not beneficial to the health of children, so the material is not suitable for being used as a material of the guardrail of the crawling pad for children.
CN103980598A discloses a preparation method of natural anti-aging and antibacterial composite plastic particles and a double-layer PPR pipe thereof, which is characterized in that 0.1-5 parts of No. 10 white oil, 2-8 parts of polyethylene wax, 0.1-5 parts of a silane coupling agent, 20-40 parts of polyethylene resin, 5-10 parts of 80-100 mesh shell powder and 3-6 parts of 80-200 mesh silver-loaded bamboo charcoal powder are added into a high-speed mixer for mixing, and the mixture is extruded by a double-screw extruder for granulation after being uniformly mixed. The method has the advantages of simple and convenient operation, strong practicability, low cost, environmental protection, good dispersity of the obtained natural anti-aging and antibacterial composite plastic particles, stable property, excellent anti-aging and antibacterial performances of the obtained PPR pipe, high cost performance, and stronger practical application value and market development prospect. CN107540913A discloses an environment-friendly antibacterial plastic, which comprises the following raw materials in parts by weight: 100-120 parts of low-density polyethylene, 60-80 parts of polyurethane, 20-28 parts of acrylate, 10-18 parts of polypropylene grafted maleic anhydride, 4-9 parts of methyl silicone oil, 12-18 parts of polyvinyl alcohol, 10-15 parts of a dispersing agent and 3-8 parts of an antibacterial agent, wherein the antibacterial agent comprises nano-scale silver oxide, silica gel, activated carbon, dodecyl biquaternary ammonium salt and a silane coupling agent; the obtained environment-friendly plastic has good antibacterial performance by adding the antibacterial agent, can kill common bacteria, has full raw material sources due to the matching effect of the raw materials, is environment-friendly and pollution-free in the manufacturing process, and ensures good common performance of the plastic. However, the hardness and tensile strength of the low-density polyethylene are poor, and the prepared antibacterial plastic cannot meet the requirements of the plastic toy products for children on the hardness and strength of the materials, so that the wide-range application of the antibacterial plastic is limited.
Therefore, it is very important to develop an antibacterial plastic with antibacterial and antiviral functions and excellent mechanical properties for manufacturing children guardrails.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide an antibacterial plastic for manufacturing a child guardrail and a preparation method and application thereof, wherein the antibacterial plastic adopts the combination of antibacterial master batches containing modified inorganic antibacterial agents and high-density polyethylene resin to obtain the antibacterial plastic with antibacterial and antiviral effects and excellent strength and wear resistance, and can simultaneously meet the requirements of a child plastic toy product on antibacterial effect and strength.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides an antibacterial plastic, which comprises the following components in parts by weight: 80-85 parts of high-density polyethylene (HDPE) resin and 4-7 parts of antibacterial master batch;
the antibacterial master batch comprises the following components in parts by weight: 80-85 parts of HDPE and 15-20 parts of modified inorganic antibacterial agent.
The HDPE in the antibacterial plastic and the antibacterial master batch may be, independently, 80.5 parts by weight, 81 parts by weight, 81.5 parts by weight, 82 parts by weight, 82.5 parts by weight, 83 parts by weight, 83.5 parts by weight, 84 parts by weight, 84.5 parts by weight, or the like.
The antibacterial master batch in the antibacterial plastic can be 4.2 parts by weight, 4.4 parts by weight, 4.6 parts by weight, 4.8 parts by weight, 55 parts by weight, 5.2 parts by weight, 5.4 parts by weight, 5.6 parts by weight, 5.8 parts by weight, 6 parts by weight, 6.2 parts by weight, 6.4 parts by weight, 6.6 parts by weight or 6.8 parts by weight and the like.
The modified inorganic antibacterial agent in the antibacterial master batch can be 16.5 parts by weight, 17 parts by weight, 17.5 parts by weight, 18 parts by weight, 18.5 parts by weight, 19 parts by weight or 19.5 parts by weight and the like.
The antibacterial plastic provided by the invention comprises a combination of antibacterial master batches and HDPE, wherein the antibacterial master batches comprise a combination of a modified inorganic antibacterial agent and HDPE; on one hand, the interface performance between HDPE and the inorganic antibacterial agent is improved, and the adhesion of the interface is improved; on the other hand, the antibacterial master batch comprises 80-85 parts by weight of HDPE and 15-20 parts by weight of modified inorganic antibacterial agent, and the prepared antibacterial plastic has excellent antibacterial and antiviral effects and excellent mechanical properties at the same time, and can meet the requirements for manufacturing children flower basket products; if the concentration of the antibacterial agent is too low, the antibacterial performance is lowered; if the solubility of the antibacterial agent is too high, the dispersion uniformity of the antibacterial agent in HDPE is poor, so that the antibacterial property of the prepared large-area antibacterial plastic is not uniform, and the antibacterial property of the prepared child guardrail is not uniform, so that the using effect of the child guardrail is influenced; therefore, the antibacterial plastic prepared by matching within the reasonable range provided by the invention has excellent mechanical and antibacterial properties, can be used in children toy products, and has very high application value.
Preferably, the antibacterial plastic further comprises a color master batch.
Preferably, the amount of the color masterbatch in the antibacterial plastic is 0.5 to 1.5 parts by weight, such as 0.6 part by weight, 0.7 part by weight, 0.8 part by weight, 0.9 part by weight, 1 part by weight, 1.1 part by weight, 1.2 parts by weight, 1.3 parts by weight or 1.4 parts by weight, and specific values therebetween are limited by space and for brevity, and the invention is not exhaustive of the specific values included in the range.
Preferably, the modified inorganic antimicrobial agent comprises a coupling agent modified inorganic antimicrobial agent.
Preferably, the coupling agent comprises a silane coupling agent and/or a titanate coupling agent.
The silane coupling agent can be any one of or a combination of at least two of a silane coupling agent KH-550, a silane coupling agent KH-570 or a silane coupling agent KH-792.
The titanate coupling agent may be any one of or a combination of at least two of titanate coupling agent 201, titanate coupling agent 311, or titanate coupling agent 102.
Preferably, the inorganic antimicrobial agent comprises a silver-loaded phosphate-based antimicrobial agent and/or a silver-loaded silicate-based antimicrobial agent.
Preferably, the silver-loaded phosphate-based antimicrobial agent comprises any one of or a combination of at least two of silver-loaded zirconium phosphate, silver-loaded calcium phosphate or silver-loaded titanium phosphate.
Preferably, the silver-loaded silicate comprises silver-loaded clay mineral.
Preferably, the modified inorganic antibacterial agent is prepared by a method comprising: and mixing the inorganic antibacterial agent and the coupling agent to obtain the modified inorganic antibacterial agent.
Preferably, the mass ratio of the inorganic antibacterial agent to the coupling agent is 1 (0.01-0.03), for example, 1:0.01, 1:0.012, 1:0.014, 1:0.016, 1:0.018, 1:0.02, 1:0.022, 1:0.024, 1:0.026, 1:0.028, and the like.
Preferably, the mixing modification time is 1 to 2 hours, such as 1.1h, 1.2h, 1.3h, 1.4h, 1.5h, 1.6h, 1.7h, 1.8h or 1.9h, and the specific values therebetween are limited by space and for the sake of brevity, and the invention is not exhaustive of the specific values included in the range.
Preferably, the temperature of the mixing modification is 50-60 ℃, for example, 51 ℃, 52 ℃, 53 ℃, 54 ℃, 55 ℃, 56 ℃, 57 ℃, 58 ℃ or 59 ℃, and the specific values therebetween are limited by space and for the sake of brevity, and the invention is not exhaustive of the specific values included in the range.
Preferably, the antibacterial master batch further comprises a composite antioxidant and/or a dispersing agent.
Preferably, the content of the composite antioxidant in the antibacterial mother particle is 1 to 1.5 parts by weight, such as 1.05 parts by weight, 1.1 parts by weight, 1.15 parts by weight, 1.2 parts by weight, 1.25 parts by weight, 1.3 parts by weight, 1.35 parts by weight, 1.4 parts by weight or 1.45 parts by weight, and specific values therebetween are limited by space and for the sake of brevity, and the invention is not exhaustive.
Preferably, the complex antioxidant comprises a primary antioxidant and/or a secondary antioxidant.
Preferably, the primary antioxidant comprises pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] and/or 2, 2' -methylenebis (4-methyl-6-tert-butylphenol).
Preferably, the secondary antioxidant comprises tris [2, 4-di-tert-butylphenyl ] phosphite and/or tris (nonylphenyl) phosphite.
Preferably, the content of the dispersing agent in the antibacterial mother particle is 1.5 to 2 parts by weight, such as 1.55 parts by weight, 1.6 parts by weight, 1.65 parts by weight, 1.7 parts by weight, 1.75 parts by weight, 1.8 parts by weight, 1.85 parts by weight, 1.9 parts by weight or 1.95 parts by weight, and specific values therebetween are limited by space and for brevity, and the invention is not exhaustive.
Preferably, the dispersant comprises white oil and/or N, N' -ethylene bis stearamide. In a second aspect, the present invention provides a method for preparing the antibacterial plastic according to the first aspect, the method comprising: and co-extruding the high-density polyethylene resin, the antibacterial master batch and the optional color master batch to obtain the antibacterial plastic.
Preferably, the temperature of the extrusion is 150-190 ℃, such as 155 ℃, 160 ℃, 165 ℃, 170 ℃, 175 ℃, 180 ℃, 185 ℃, and the specific values therebetween are limited by space and for the sake of brevity, the invention is not exhaustive of the specific values included in the ranges.
Preferably, the preparation method of the antibacterial masterbatch comprises the following steps: and extruding and granulating the high-density polyethylene resin, the modified inorganic antibacterial agent, the optional antioxidant and the optional dispersing agent to obtain the antibacterial master batch.
Preferably, the temperature of the extrusion granulation is 160-190 ℃, such as 162 ℃, 164 ℃, 166 ℃, 168 ℃, 170 ℃, 172 ℃, 174 ℃, 176 ℃, 178 ℃, 180 ℃, 182 ℃, 184 ℃, 186 ℃ or 188 ℃, and the specific values therebetween are limited by space and for the sake of brevity, and the invention is not exhaustive of the specific values included in the range.
Preferably, the rotation speed of the screw during the extrusion granulation is 200-300 r/min, such as 210r/min, 220r/min, 230r/min, 240r/min, 250r/min, 260r/min, 270r/min, 280r/min or 290r/min, and the specific values therebetween are limited by space and for the sake of brevity, and the invention is not exhaustive.
As a preferred technical scheme, the preparation method comprises the following steps: and co-extruding the HDPE, the antibacterial master batch and the optional color master batch at 150-190 ℃ to obtain the antibacterial plastic.
The preparation method of the antibacterial master batch comprises the following steps: and (3) extruding and granulating the HDPE, the coupling agent modified inorganic antibacterial agent, the optional antioxidant and the optional dispersing agent at the rotating speed of a screw of 200-300 r/min and at 160-190 ℃ to obtain the antibacterial master batch.
In a third aspect, the present invention provides the use of an antimicrobial plastic according to the first aspect in a toy article.
Compared with the prior art, the invention has the following beneficial effects:
the antibacterial plastic for manufacturing the children guardrail comprises a combination of antibacterial master batches and HDPE, wherein the antibacterial master batches comprise a combination of a modified inorganic antibacterial agent and HDPE; on one hand, the interface performance between the high polymer material HDPE and the inorganic antibacterial agent is improved, and the adhesion of the interface is improved; on the other hand, the antibacterial plastic prepared by optimizing the formula of the modified inorganic antibacterial agent and the HDPE has excellent antibacterial and antiviral effects and excellent mechanical properties; experiments show that the antibacterial plastic provided by the invention has an antiviral activity rate of 99.23-99.9% and an antibacterial rate of 99.02-99.9%; compared with the antibacterial plastic provided by the prior art, the antiviral activity rate is improved by 26-28%, and the antibacterial rate is improved by 28-30%; can be applied to children toy products and has high application value.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Preparation examples 1 to 5
The antibacterial master batch comprises the following specific components in parts by weight as shown in Table 1.
TABLE 1
| Preparation example 1 | Preparation example 2 | Preparation example 3 | Preparation example 4 | Preparation example 5 | |
| HDPE | 82 | 80 | 85 | 80 | 85 |
| Modified inorganic antibacterial agent | 18 | 15 | 20 | 20 | 15 |
| Antioxidant 1010 | 0.75 | 0.75 | 1 | 0.75 | 0.75 |
| Antioxidant 168 | 0.5 | 0.25 | 0.5 | 0.5 | 0.5 |
| White oil | 1.75 | 1.5 | 2 | 1.75 | 1.75 |
The preparation method comprises the following steps:
(1) dissolving silver-loaded zirconium phosphate powder (an antibacterial agent of Beijing Aisler science and technology Limited, SR-T-104) in ethanol, ultrasonically dispersing for 40min, adding a silane coupling agent KH-792 at 55 ℃, mixing for 1.5h, standing for layering, taking lower layer powder after complete layering, drying and grinding to obtain a surface-modified inorganic silver-loaded antibacterial agent, wherein the mass ratio of the silver-loaded zirconium phosphate to the silane coupling agent KH-792 is 1:0.02, and obtaining the modified inorganic antibacterial agent;
(2) and (2) extruding and granulating the HDPE, the modified inorganic antibacterial agent obtained in the step (1), the antioxidant 1010, the antioxidant 168 and the white oil at 180 ℃ and at the screw rotation speed of 250r/min to obtain the antibacterial master batch.
Comparative example preparation example 1
An antibacterial masterbatch is different from preparation example 1 only in that HDPE is used in an amount of 75 parts by weight, a modified inorganic antibacterial agent is used in an amount of 25 parts by weight, and other components, amounts and preparation methods of the antibacterial masterbatch are the same as those of preparation example 1, to obtain the antibacterial masterbatch.
Comparative example preparation example 2
An antibacterial masterbatch is different from preparation example 1 only in that the amount of HDPE is 90 parts by weight, the amount of modified inorganic antibacterial agent is 10 parts by weight, and other components, amounts and preparation methods of the antibacterial masterbatch are the same as those of preparation example 1, so that the antibacterial masterbatch is obtained.
Examples 1 to 5
An antibacterial plastic for manufacturing a child guardrail comprises the following specific components shown in Table 2, wherein the dosage unit of each component is 'part by weight', and the antibacterial plastic comprises the antibacterial master batches obtained in preparation examples 1-5;
TABLE 2
| Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | |
| HDPE | 82 | 80 | 85 | 82 | 82 |
| Antibacterial masterbatch | 6 | 4 | 7 | 6 | 6 |
| Color master batch | 1 | 0.5 | 1.5 | 1 | 11 |
The preparation method comprises the following steps: HDPE, antibacterial master batch and color master batch (E51970 yellow of Jiangsu pleck red plum color master batch Co., Ltd.) are extruded together at 140 ℃ to obtain the antibacterial plastic.
Comparative examples 1 and 2
An antibacterial plastic for manufacturing a child guardrail only differs from example 1 in that the antibacterial master batch obtained in preparation example 1 is replaced by the antibacterial master batch obtained in comparative preparation examples 1 and 2, and other components, using amounts and preparation methods are the same as those of example 1, so that the antibacterial plastic is obtained.
Comparative example 3
An antibacterial plastic for manufacturing a child guardrail is different from the antibacterial plastic in example 1 in that HDPE is used in an amount of 85 parts by weight, antibacterial master batch is used in an amount of 3 parts by weight, and other components, use amounts and preparation methods are the same as those of example 1, so that the antibacterial plastic is obtained.
Application examples 1 to 5
A child guardrail comprises 60 x 40 x 3.5cm specification of the antibacterial plastic for manufacturing the child guardrail obtained in the embodiment 1-5;
the preparation method comprises the following steps: pouring the antibacterial plastic for manufacturing the child guardrail obtained in the embodiment 1-5 into a hopper, and continuously extruding the antibacterial plastic by heating and a core rod to form a colloidal hollow cylindrical embryonic form; when a hollow cylindrical prototype is extruded to 3cm beyond the edges of the die cavities, the dies on the left side and the right side are closed, the top end of the prototype is cut into single pieces by the blades, air is injected into the prototype through the air charging rod, and the prototype is tightly attached to the inner wall of the die to be cooled and solidified to form a desired shape; after cooling is finished, the left and right molds are opened, and the part is demoulded; and trimming the parts by using a repair tool to obtain the child guardrail.
And (3) performance testing:
(1) the antibacterial rate is as follows: testing the antibacterial rate according to GB/T31402-2015 test method for the antibacterial performance of the plastic surface;
(2) antiviral activity rate (H1N1, H3N 2): the antiviral performance test was performed according to the test method disclosed in ISO 21702-2019 (determination of antiviral activity on plastics and other non-porous surfaces), using H1N1 and H3N2 as test viruses;
(3) uniformity: the antibacterial rate is tested according to GB/T31402-2015 method for testing the antibacterial performance of the plastic surface, the number of bacteria at different positions of the sample is tested, and if the number meets the following formula, the sample is considered to be uniform:
(Lmax-Lmin)/(Lmean)≤0.2
wherein L ismaxA log representing the maximum viable count on the sample; l isminA log representing the minimum number of viable bacteria on the sample; l ismeanRepresents the log of the geometric mean viable count on the sample.
The antibacterial plastics obtained in examples 1 to 5 and comparative examples 1 to 3 were tested according to the above test method, and the test results are shown in table 3:
TABLE 3
As can be seen from the data in table 3:
the antibacterial plastic provided by the invention has excellent antibacterial and antiviral effects through the matching of the modified inorganic antibacterial agent and HDPE. Specifically, the antibacterial plastic provided in examples 1 to 5 has an antiviral activity rate of 99.23 to 99.9% and an antibacterial rate of 99.02 to 99.9%; compared with the antibacterial plastic provided by the comparative examples 1 and 3, the antiviral activity rate is improved by 26-28%, and the antibacterial rate is improved by 28-30%; in addition, comparative example 2 provides the antibacterial plastic which has high antiviral activity and antibacterial activity, but it was found through the test that the antibacterial effect is not uniform due to the uneven distribution of the antibacterial agent in the antibacterial mother particle or the antibacterial mother particle in the antibacterial plastic.
The applicant states that the invention is illustrated by the above examples to provide an antibacterial plastic and a preparation method and an application method thereof, but the invention is not limited to the above examples, i.e. it does not mean that the invention must be implemented by the above examples. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (10)
1. The antibacterial plastic for manufacturing the children guardrail is characterized by comprising the following components in parts by weight: 80-85 parts of high-density polyethylene resin and 4-7 parts of antibacterial master batch;
the antibacterial master batch comprises the following components in parts by weight: 80-85 parts of high-density polyethylene resin and 15-20 parts of modified inorganic antibacterial agent.
2. The antimicrobial plastic of claim 1, further comprising a color masterbatch;
preferably, the content of the color master batch in the antibacterial plastic is 0.5-1.5 parts by weight.
3. The antibacterial plastic according to claim 1 or 2, wherein the modified inorganic antibacterial agent is an inorganic antibacterial agent modified with a coupling agent;
preferably, the coupling agent comprises a silane coupling agent and/or a titanate coupling agent;
preferably, the inorganic antimicrobial agent comprises a silver-loaded phosphate-based antimicrobial agent and/or a silver-loaded silicate-based antimicrobial agent;
preferably, the silver-loaded phosphate-based antibacterial agent comprises any one or a combination of at least two of silver-loaded zirconium phosphate, silver-loaded calcium phosphate or silver-loaded titanium phosphate;
preferably, the silver-loaded silicate comprises silver-loaded clay mineral.
4. The antimicrobial plastic of claim 3, wherein the modified inorganic antimicrobial agent is prepared by a process comprising: mixing and modifying an inorganic antibacterial agent and a coupling agent to obtain a modified inorganic antibacterial agent;
preferably, the mass ratio of the inorganic antibacterial agent to the coupling agent is 1 (0.01-0.03);
preferably, the mixing modification time is 1-2 h;
preferably, the temperature of the mixing modification is 50-60 ℃.
5. The antibacterial plastic according to any one of claims 1 to 4, wherein the antibacterial master batch further comprises a composite antioxidant and/or a dispersant;
preferably, the content of the composite antioxidant in the antibacterial master batch is 1-1.5 parts by weight;
preferably, the composite antioxidant comprises a primary antioxidant and/or a secondary antioxidant;
preferably, the primary antioxidant comprises pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] and/or 2, 2' -methylenebis (4-methyl-6-tert-butylphenol);
preferably, the secondary antioxidant comprises tris [2, 4-di-tert-butylphenyl ] phosphite and/or tris (nonylphenyl) phosphite;
preferably, the content of the dispersing agent in the antibacterial master batch is 1.5-2 parts by weight;
preferably, the dispersant comprises white oil and/or N, N' -ethylene bis stearamide.
6. A method for preparing the antibacterial plastic as claimed in any one of claims 1 to 5, characterized in that the method comprises the following steps: and co-extruding the high-density polyethylene resin, the antibacterial master batch and the optional color master batch to obtain the antibacterial plastic.
7. The method of claim 6, wherein the temperature of the co-extrusion is 150 to 190 ℃.
8. The preparation method of claim 6 or 7, wherein the preparation method of the antibacterial masterbatch comprises the following steps: extruding and granulating high-density polyethylene resin, a modified inorganic antibacterial agent, an optional antioxidant and an optional dispersing agent to obtain the antibacterial master batch;
preferably, the temperature of the extrusion granulation is 160-190 ℃;
preferably, the rotating speed of the screw during the extrusion granulation is 200-300 r/min.
9. The production method according to any one of claims 6 to 8, characterized by comprising: co-extruding the high-density polyethylene resin, the antibacterial master batch and the optional color master batch at 150-190 ℃ to obtain the antibacterial plastic;
the preparation method of the antibacterial master batch comprises the following steps: and extruding and granulating the high-density polyethylene resin, the inorganic antibacterial agent modified by the coupling agent, the optional antioxidant and the optional dispersing agent at the rotating speed of a screw of 200-300 r/min and the temperature of 160-190 ℃ to obtain the antibacterial master batch.
10. Use of the antibacterial plastic according to any one of claims 1 to 5 in a child barrier.
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Application publication date: 20210416 |