WO2023001076A1 - 一种抗菌塑胶母粒、其制备方法和应用 - Google Patents
一种抗菌塑胶母粒、其制备方法和应用 Download PDFInfo
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- WO2023001076A1 WO2023001076A1 PCT/CN2022/106033 CN2022106033W WO2023001076A1 WO 2023001076 A1 WO2023001076 A1 WO 2023001076A1 CN 2022106033 W CN2022106033 W CN 2022106033W WO 2023001076 A1 WO2023001076 A1 WO 2023001076A1
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- Prior art keywords
- antibacterial
- organic
- inorganic
- composition
- thermoplastic
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- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 89
- 239000004033 plastic Substances 0.000 title claims abstract description 66
- 229920003023 plastic Polymers 0.000 title claims abstract description 66
- 239000004594 Masterbatch (MB) Substances 0.000 title claims abstract description 63
- 239000004568 cement Substances 0.000 title abstract 4
- 238000002360 preparation method Methods 0.000 title abstract 2
- 239000000203 mixture Substances 0.000 claims abstract description 80
- 239000003242 anti bacterial agent Substances 0.000 claims abstract description 60
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 57
- 239000005749 Copper compound Substances 0.000 claims abstract description 40
- 150000001880 copper compounds Chemical class 0.000 claims abstract description 40
- 229920001169 thermoplastic Polymers 0.000 claims abstract description 40
- 239000011787 zinc oxide Substances 0.000 claims abstract description 22
- -1 transition metal salt Chemical class 0.000 claims description 54
- 239000000843 powder Substances 0.000 claims description 48
- 239000004416 thermosoftening plastic Substances 0.000 claims description 34
- 229910052723 transition metal Inorganic materials 0.000 claims description 31
- 239000010949 copper Substances 0.000 claims description 29
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 25
- 229910052802 copper Inorganic materials 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 24
- 239000002245 particle Substances 0.000 claims description 24
- 238000009826 distribution Methods 0.000 claims description 22
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 18
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 18
- 239000004743 Polypropylene Substances 0.000 claims description 18
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 17
- 229920001155 polypropylene Polymers 0.000 claims description 16
- 150000003624 transition metals Chemical class 0.000 claims description 13
- 238000004519 manufacturing process Methods 0.000 claims description 12
- 229910052751 metal Inorganic materials 0.000 claims description 12
- 239000002184 metal Substances 0.000 claims description 12
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims description 11
- WBSRIXCTCFFHEF-UHFFFAOYSA-N (3,5-ditert-butyl-4-hydroxyphenyl)methyl-ethoxyphosphinic acid Chemical compound CCOP(O)(=O)CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 WBSRIXCTCFFHEF-UHFFFAOYSA-N 0.000 claims description 10
- HCILJBJJZALOAL-UHFFFAOYSA-N 3-(3,5-ditert-butyl-4-hydroxyphenyl)-n'-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyl]propanehydrazide Chemical group CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)NNC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 HCILJBJJZALOAL-UHFFFAOYSA-N 0.000 claims description 10
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 10
- GHKOFFNLGXMVNJ-UHFFFAOYSA-N Didodecyl thiobispropanoate Chemical group CCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCC GHKOFFNLGXMVNJ-UHFFFAOYSA-N 0.000 claims description 10
- 239000003508 Dilauryl thiodipropionate Substances 0.000 claims description 10
- 229910052791 calcium Inorganic materials 0.000 claims description 10
- 239000011575 calcium Substances 0.000 claims description 10
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 claims description 10
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 claims description 10
- 229940112669 cuprous oxide Drugs 0.000 claims description 10
- 235000019304 dilauryl thiodipropionate Nutrition 0.000 claims description 10
- 229910021589 Copper(I) bromide Inorganic materials 0.000 claims description 9
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 9
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 9
- 239000004698 Polyethylene Substances 0.000 claims description 9
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 9
- 229910052782 aluminium Inorganic materials 0.000 claims description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 9
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 9
- NKNDPYCGAZPOFS-UHFFFAOYSA-M copper(i) bromide Chemical compound Br[Cu] NKNDPYCGAZPOFS-UHFFFAOYSA-M 0.000 claims description 9
- 229940045803 cuprous chloride Drugs 0.000 claims description 9
- 229910052742 iron Inorganic materials 0.000 claims description 9
- 229910052749 magnesium Inorganic materials 0.000 claims description 9
- 239000011777 magnesium Substances 0.000 claims description 9
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 9
- 229910052759 nickel Inorganic materials 0.000 claims description 9
- 229910052760 oxygen Inorganic materials 0.000 claims description 9
- 239000001301 oxygen Substances 0.000 claims description 9
- 229920000573 polyethylene Polymers 0.000 claims description 9
- 239000010936 titanium Substances 0.000 claims description 9
- 229910052719 titanium Inorganic materials 0.000 claims description 9
- QEDNBHNWMHJNAB-UHFFFAOYSA-N tris(8-methylnonyl) phosphite Chemical group CC(C)CCCCCCCOP(OCCCCCCCC(C)C)OCCCCCCCC(C)C QEDNBHNWMHJNAB-UHFFFAOYSA-N 0.000 claims description 9
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 8
- 150000007970 thio esters Chemical class 0.000 claims description 8
- 229910021595 Copper(I) iodide Inorganic materials 0.000 claims description 7
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 7
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 7
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 claims description 7
- 238000009837 dry grinding Methods 0.000 claims description 7
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 5
- 238000005469 granulation Methods 0.000 claims description 3
- 230000003179 granulation Effects 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- 239000011593 sulfur Substances 0.000 claims description 3
- 229910001428 transition metal ion Inorganic materials 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims 1
- GBRBMTNGQBKBQE-UHFFFAOYSA-L copper;diiodide Chemical compound I[Cu]I GBRBMTNGQBKBQE-UHFFFAOYSA-L 0.000 claims 1
- 150000002823 nitrates Chemical class 0.000 claims 1
- 229910017604 nitric acid Inorganic materials 0.000 claims 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims 1
- 150000003568 thioethers Chemical class 0.000 claims 1
- 230000000694 effects Effects 0.000 description 14
- 239000002131 composite material Substances 0.000 description 12
- 239000003963 antioxidant agent Substances 0.000 description 9
- 238000012545 processing Methods 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 230000003078 antioxidant effect Effects 0.000 description 7
- 239000004750 melt-blown nonwoven Substances 0.000 description 7
- 230000003647 oxidation Effects 0.000 description 7
- 238000007254 oxidation reaction Methods 0.000 description 7
- 239000004744 fabric Substances 0.000 description 6
- 230000002401 inhibitory effect Effects 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 230000008569 process Effects 0.000 description 5
- 241000894006 Bacteria Species 0.000 description 4
- 238000010998 test method Methods 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- 241000228245 Aspergillus niger Species 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 description 1
- JAQXDZTWVWLKGC-UHFFFAOYSA-N [O-2].[Al+3].[Fe+2] Chemical compound [O-2].[Al+3].[Fe+2] JAQXDZTWVWLKGC-UHFFFAOYSA-N 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 239000011667 zinc carbonate Substances 0.000 description 1
- 235000004416 zinc carbonate Nutrition 0.000 description 1
- 229910000010 zinc carbonate Inorganic materials 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
Images
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
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
-
- 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
- C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
- C08K3/015—Biocides
-
- 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
- C08K3/10—Metal compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
Definitions
- the invention relates to an antibacterial plastic masterbatch, which comprises an antibacterial agent and a thermoplastic.
- the antibacterial agent is an organic-inorganic composite antibacterial powder with a micron size.
- metals such as nano-silver particles
- plastic masterbatches In the field of antibacterial technology known today, in order to endow plastics with antibacterial properties, metals, such as nano-silver particles, are often added to plastic masterbatches, and then processed into plastics with antibacterial functions through extrusion molding or injection molding. product.
- the added metals are often oxidized and deteriorated due to high-temperature operating conditions, resulting in the final plastic products being prone to roughness, reduced mechanical strength, and discoloration in appearance, and at the same time greatly reducing the quality of the final product. Antibacterial effect.
- the present invention discloses an antibacterial plastic masterbatch and its manufacturing method.
- the composition of the antibacterial plastic masterbatch of the present invention includes micron-sized organic-inorganic composite antibacterial powder, which can effectively make the plastic product obtained after processing the antibacterial plastic masterbatch have the technical effect of inhibiting the growth of bacteria or/and mold .
- antibacterial includes preventing or inhibiting the growth of bacteria, preventing or inhibiting the growth of mold, or simultaneously preventing or inhibiting the growth of bacteria and mold.
- the first purpose of the present invention is to disclose an antibacterial plastic masterbatch.
- the composition of the antibacterial plastic masterbatch includes an antibacterial agent and a thermoplastic, and the weight ratio of the antibacterial agent to the thermoplastic is 1/99 to 10/90.
- the weight addition ratio of plastic is 2/98 ⁇ 5/95.
- the antibacterial agent is an organic-inorganic composite antibacterial powder with a micron size, and its particle size distribution (d50) is 2-10 microns, preferably, its particle size distribution (d50) is 2-3 microns.
- the antibacterial agent is composed of an organic-inorganic mixture, zinc oxide and a copper compound. Based on the total weight of the antibacterial agent, the weight percentage of the organic-inorganic mixture is 30-40 wt%. The percentage by weight is 30-40 wt%, and the percentage by weight of the copper compound is 20-40 wt%.
- the composition of the organic-inorganic hybrid comprises 1-5 wt% of organic components and 95-99 wt% of inorganic components.
- the organic composition is an antioxidant comprising a trialkylphosphite, a dialkylthioester, a bishydrazide, a phosphonate, or any combination thereof; and the inorganic composition comprises at least one transition metal salt.
- the trialkylphosphite is triisodecylphosphite; the dialkylthioester is dilaurylthiodipropionate; the bishydrazide is N,N'-bis[3- (3,5-di-tert-butyl-4-hydroxyphenyl)propionyl]hydrazine; and the phosphonate is calcium bis(3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid monoethyl ester) .
- the transition metal salt has the general formula of MX, wherein M represents a transition metal that is magnesium, aluminum, manganese, titanium, iron or nickel; and X is selected from one or a combination of the following groups: Carbonate (CO 3 2- ), Nitrate (NO3 - ), Sulfate (SO 4 2- ), Sulfide (S 2- ) and Oxygen (O 2- ).
- the copper compound is selected from one or a combination of the following groups: copper metal, cuprous oxide, cuprous chloride, cuprous bromide and cuprous iodide.
- the second object of the present invention is to provide a method for manufacturing antibacterial plastic masterbatch, which includes but not limited to the following steps.
- Step 1 dry-grinding the organic-inorganic hybrid, zinc oxide and copper compound to obtain organic-inorganic hybrid powder, zinc oxide powder and copper compound powder with a particle size distribution (d50) of 2-10 microns, respectively.
- the purpose of the above-mentioned dry grinding is to increase the body surface area of each component, so that the components can contact each other more effectively during the subsequent mixing process, thereby achieving the technical effect of uniform mixing.
- the present invention proves through excessive experiments that when the powder size of each component is controlled at the micron level, it has the best mixing effect. However, when the powder size is nanoscale, because the surface energy is too high, it will cause aggregation during mixing, which is not conducive to the subsequent processing process.
- the above components refer to the organic-inorganic hybrid, the zinc oxide, the copper compound or its powder.
- Step 2 Mixing the organic-inorganic hybrid powder, the zinc oxide powder and the copper compound powder to obtain an antibacterial agent, based on the total weight of the antibacterial agent, the weight percentage of the organic-inorganic hybrid powder is 30-30% 40 wt%, the weight percentage of the zinc oxide powder is 30-40 wt%, and the weight percentage of the copper compound powder is 20-40 wt%.
- the above-mentioned mixing steps will not change the size of the organic-inorganic hybrid powder, the zinc oxide powder and the copper compound powder, and the antibacterial agent obtained after mixing still has a particle size distribution (d50) of 2 to 10 microns of powder.
- Step 3 Mix the antibacterial agent and thermoplastic to obtain an antibacterial plastic composition.
- the thermoplastic comprises polyethylene, polypropylene or a combination thereof. Based on the total weight of the antibacterial plastic composition, the antibacterial agent accounts for The weight percent of the thermoplastic is 1-10wt%, and the weight percent of the thermoplastic is 90-99wt%.
- Step 4 Execute a granulation procedure to make the antibacterial plastic composition into an antibacterial plastic masterbatch.
- the composition of the organic-inorganic mixture includes 1-5 wt% of organic components and 95-99 wt% of inorganic components; in particular, the organic components are antioxidants, which include trialkyl phosphites, di Alkyl thioester, bishydrazide, phosphonate or any combination thereof, and the inorganic composition contains at least one transition metal salt.
- the organic components are antioxidants, which include trialkyl phosphites, di Alkyl thioester, bishydrazide, phosphonate or any combination thereof, and the inorganic composition contains at least one transition metal salt.
- the trialkylphosphite is triisodecylphosphite
- the dialkylthioester is dilaurylthiodipropionate
- the bishydrazide is N,N'-bis[3- (3,5-di-tert-butyl-4-hydroxyphenyl)propionyl]hydrazine
- the phosphonate is calcium bis(3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid monoethyl ester) .
- the transition metal salts have the general formula of MX, wherein M represents a transition metal ion, the transition metal is magnesium, aluminum, manganese, titanium, iron or nickel; and X is selected from one or a combination of the following groups : Carbonate (CO 3 2- ), Nitrate (NO3 - ), Sulfate (SO 4 2- ), Sulfide (S 2- ) and Oxygen (O 2- ).
- the copper compound is selected from one or a combination of the following groups: copper metal, cuprous oxide, cuprous chloride, cuprous bromide and cuprous iodide.
- the third object of the present invention is to provide a method for making thermoplastics antibacterial, which includes but not limited to the following steps.
- Step 1 provide an antibacterial agent, the antibacterial agent is a powder with a particle size distribution (d50) of 2 to 10 microns, and its composition includes organic-inorganic mixtures, zinc oxide and copper compounds, based on the total weight of the antibacterial agent, the The weight percent of the organic-inorganic compound is 30-40wt%, the weight percent of the zinc oxide is 30-40wt%, and the weight percent of the copper compound is 20-40wt%.
- d50 particle size distribution
- Step 2 adding the antibacterial agent to the thermoplastic masterbatch, so that the produced thermoplastic has an antibacterial effect, and the thermoplastic masterbatch includes polyethylene masterbatch, polypropylene masterbatch or a combination thereof.
- the composition of the organic-inorganic hybrid comprises 1-5 wt% of organic components and 95-99 wt% of inorganic components.
- the organic composition is an antioxidant comprising a trialkyl phosphite, a dialkyl thioester, a bishydrazide, a phosphonate, or any combination thereof, and the inorganic composition comprises at least one transition metal salt.
- the trialkylphosphite is triisodecylphosphite
- the dialkylthioester is dilaurylthiodipropionate
- the bishydrazide is N,N'-bis[3- (3,5-di-tert-butyl-4-hydroxyphenyl)propionyl]hydrazine
- the phosphonate is calcium bis(3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid monoethyl ester) .
- the transition metal salt has the general formula of MX, wherein M represents a transition metal that is magnesium, aluminum, manganese, titanium, iron or nickel; and X is selected from one or a combination of the following groups: Carbonate (CO 3 2- ), Nitrate (NO3 - ), Sulfate (SO 4 2- ), Sulfide (S 2- ) and Oxygen (O 2- ).
- the copper compound is selected from one or a combination of the following groups: copper metal, cuprous oxide, cuprous chloride, cuprous bromide and cuprous iodide.
- the present invention has at least the following technical features and effects.
- the present invention discloses an antibacterial plastic masterbatch, which consists of micron-sized organic-inorganic composite antibacterial powder.
- the micron-sized organic-inorganic composite antibacterial powder has a large body surface area and is easily dispersed in the plastic masterbatch advantages in.
- the micron-sized organic-inorganic composite antibacterial powder has the effect of inhibiting copper oxidation, and can prevent the technical effect of reducing the antibacterial activity of the copper-containing plastic masterbatch due to copper oxidation and deterioration during processing.
- the thermoplastic plastic product made by applying the antibacterial plastic masterbatch of the present invention has good antibacterial activity, and can effectively inhibit and prevent the growth of bacteria or mold.
- Fig. 1 is the particle size distribution diagram of zinc oxide after dry grinding according to the present invention.
- Fig. 2 is a particle size distribution diagram of the antibacterial agent of the present invention.
- Fig. 3 is the Cu2p XPS spectrum of the meltblown nonwoven fabric that antibacterial polypropylene masterbatch of the present invention is made.
- the present invention provides a novel antibacterial plastic masterbatch.
- the antibacterial plastic masterbatch contains a micron-sized organic-inorganic composite antibacterial powder and thermoplastic plastics.
- the micron-sized organic-inorganic composite antibacterial powder has a large body surface area, is easy to disperse and prevents copper oxidation. Effect.
- the composition of the antibacterial plastic masterbatch includes an antibacterial agent and a thermoplastic, and the weight ratio of the antibacterial agent to the thermoplastic is 1/99 to 10/90.
- the antibacterial agent is The weight ratio of the thermoplastic plastic is 2/98 ⁇ 5/95.
- the antibacterial agent is an organic-inorganic composite antibacterial powder with a micron-scale size, and its particle size distribution (d50) is 2 to 10 microns. Preferably, its particle size distribution (d50) is 2 to 3 microns. Micron.
- the antibacterial agent is composed of organic-inorganic mixture, zinc oxide and copper compound, based on the total weight of the antibacterial agent, the weight percentage of the organic-inorganic mixture is 30-40wt%, the The weight percent of zinc oxide is 30-40wt%, and the weight percent of the copper compound is 20-40wt%.
- the weight percentage of the organic-inorganic mixture is 35-40 wt%
- the weight percentage of the zinc oxide is 35-40 wt%
- the copper The weight percent of the compound is 30-40wt%.
- the composition of the organic-inorganic hybrid comprises 1-5wt% organic composition and 95-99wt% inorganic composition.
- the organic composition is an antioxidant comprising a trialkyl phosphite, a dialkyl thioester, a bishydrazide, a phosphonate, or any combination thereof, and the inorganic composition comprises at least one transition metal salt.
- the trialkylphosphite is triisodecylphosphite; the dialkylthioester is dilaurylthiodipropionate; the bishydrazide is N,N'-bis[ 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl]hydrazine; and the phosphonate is bis(3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid monoethyl ester )calcium.
- the transition metal salt has the general formula MX, wherein M represents a transition metal, the transition metal is magnesium, aluminum, manganese, titanium, iron or nickel; and X is selected from one of the following groups or Its combination: carbonate (CO 3 2- ), nitrate (NO3 - ), sulfate (SO 4 2- ), sulfur ion (S 2- ) and oxygen ion (O 2- ).
- the copper compound is selected from one or a combination of the following groups: copper metal, cuprous oxide, cuprous chloride, cuprous bromide and cuprous iodide.
- the second embodiment of the present invention provides a method for manufacturing antibacterial plastic masterbatch, which includes but not limited to the following steps.
- Step 1 dry-grinding the organic-inorganic hybrid, zinc oxide and copper compound to obtain organic-inorganic hybrid powder, zinc oxide powder and copper compound powder with a particle size distribution (d50) of 2-10 microns, respectively.
- step 1 is to obtain organic-inorganic hybrid powder, zinc oxide powder and copper compound powder with a particle size distribution (d50) of 2-3 microns.
- the above-mentioned components refer to organic-inorganic hybrids, zinc oxide, copper compounds or powders thereof.
- Step 2 Mixing the organic-inorganic hybrid powder, the zinc oxide powder and the copper compound powder to obtain an antibacterial agent, based on the total weight of the antibacterial agent, the weight percentage of the organic-inorganic hybrid powder is 30-30% 40 wt%, the weight percentage of the zinc oxide powder is 30-40 wt%, and the weight percentage of the copper compound powder is 20-40 wt%.
- the above-mentioned mixing step will not change the size of the organic-inorganic hybrid powder, the zinc oxide powder and the copper compound powder, and the antibacterial agent obtained after mixing has a particle size distribution (d50) of 2 to 10 microns powder.
- the weight percentage of the organic-inorganic mixture is 35-40 wt%
- the weight percentage of the zinc oxide is 35-40 wt%
- the copper The weight percent of the compound is 30-40wt%.
- Step 3 Mix the antibacterial agent and thermoplastic to obtain an antibacterial plastic composition.
- the thermoplastic comprises polyethylene, polypropylene or a combination thereof. Based on the total weight of the antibacterial plastic composition, the antibacterial agent accounts for The weight percent of the thermoplastic is 1-10wt%, and the weight percent of the thermoplastic is 90-99wt%.
- Step 4 Execute a granulation procedure to make the antibacterial plastic composition into an antibacterial plastic masterbatch.
- the composition of the organic-inorganic mixture comprises 1-5wt% organic composition and 95-99wt% inorganic composition; in particular, the organic composition is antioxidant, including trialkyl phosphite , dialkylthioester, bishydrazide, phosphonate or any combination thereof, and the inorganic composition contains at least one transition metal salt.
- the trialkylphosphite is triisodecylphosphite
- the dialkylthioester is dilaurylthiodipropionate
- the bishydrazide is N,N'-bis[ 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl]hydrazine
- the phosphonate is bis(3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid monoethyl ester) calcium.
- the transition metal salt has the general formula of MX, wherein M represents a transition metal ion, the transition metal is magnesium, aluminum, manganese, titanium, iron or nickel; and X is selected from one of the following groups Or a combination thereof: carbonate (CO 3 2- ), nitrate (NO3 - ), sulfate (SO 4 2- ), sulfide (S 2- ) and oxygen ion (O 2- ).
- the copper compound is selected from one or a combination of the following groups: copper metal, cuprous oxide, cuprous chloride, cuprous bromide and cuprous iodide.
- thermoplastics antibacterial which includes but not limited to the following steps.
- Step 1 provide an antibacterial agent, the antibacterial agent is a powder with a particle size distribution (d50) of 2 to 10 microns, and its composition includes organic-inorganic mixtures, zinc oxide and copper compounds, based on the total weight of the antibacterial agent, the The weight percent of the organic-inorganic compound is 30-40wt%, the weight percent of the zinc oxide is 30-40wt%, and the weight percent of the copper compound is 20-40wt%.
- d50 particle size distribution
- the weight percentage of the organic-inorganic mixture is 35-40 wt%
- the weight percentage of the zinc oxide is 35-40 wt%
- the copper The weight percent of the compound is 30-40wt%.
- Step 2 adding the antibacterial agent to the thermoplastic masterbatch, so that the produced thermoplastic has an antibacterial effect, and the thermoplastic masterbatch includes polyethylene masterbatch, polypropylene masterbatch or a combination thereof.
- the composition of the organic-inorganic hybrid comprises 1-5wt% organic composition and 95-99wt% inorganic composition.
- the organic composition is an antioxidant comprising a trialkyl phosphite, a dialkyl thioester, a bishydrazide, a phosphonate, or any combination thereof, and the inorganic composition comprises at least one transition metal salt.
- the trialkylphosphite is triisodecylphosphite
- the dialkylthioester is dilaurylthiodipropionate
- the bishydrazide is N,N'-bis[ 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl]hydrazine
- the phosphonate is bis(3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid monoethyl ester )calcium.
- the transition metal salt has the general formula MX, wherein M represents a transition metal, the transition metal is magnesium, aluminum, manganese, titanium, iron or nickel; and X is selected from one of the following groups or Its combination: carbonate (CO 3 2- ), nitrate (NO3 - ), sulfate (SO 4 2- ), sulfur ion (S 2- ) and oxygen ion (O 2- ).
- the copper compound is selected from one or a combination of the following groups: copper metal, cuprous oxide, cuprous chloride, cuprous bromide and cuprous iodide.
- the manufacturing method of the organic-inorganic hybrid of the present invention is as follows. First, dry grinding and mixing of inorganic components and organic antioxidants, sampling during the grinding process and monitoring the particle size distribution with a particle size analyzer, when the particle size distribution (d50) is about 3 microns, the organic-inorganic mixture of the present invention is obtained .
- the inorganic composition contains 5wt% zinc carbonate, 20wt% magnesium carbonate and 75wt% titanium dioxide; the composition of the inorganic composition can also be zinc nitrate, zinc sulfate, magnesium nitrate, magnesium sulfate, aluminum oxide, aluminum oxide Iron or any combination thereof; the organic antioxidant is bis(3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid monoethyl ester) calcium, N,N'-bis[3-(3,5- Di-tert-butyl-4-hydroxyphenyl)propionyl]hydrazine or any combination thereof, and the weight ratio of the inorganic composition to the organic antioxidant is 98:2 .
- the antibacterial agent of the above representative experimental example was added into polyethylene masterbatch or polypropylene masterbatch, and then granulated to make antibacterial plastic masterbatch.
- the weight ratio of the antibacterial agent to the polyethylene masterbatch or polypropylene masterbatch is 1/99 ⁇ 10/90.
- the particle size distribution (d50) of the dry-milled zinc oxide of the present invention is 2.25 microns.
- the particle size distribution (d50) of the antibacterial agent of the present invention is 2.81 microns.
- FIG. 3 is an XPS analysis spectrum of a melt-blown nonwoven fabric made of PP plastic masterbatch added with 7wt% of the antibacterial agent of the present invention.
- the XPS spectrum shows that the binding energy of the melt-blown nonwoven in Cu 2p is located at 932.1 electron volts (eV), which is very close to copper metal or cuprous ((Cu (0) ) or Cu (I) (Cu 2 O)) in The position of 932.8 electron volts (eV), which means that the copper contained in the meltblown nonwoven fabric has not oxidized.
- the antibacterial agent of the present invention also has the technical effect of inhibiting the oxidation of copper compounds, which can ensure that the copper-containing antibacterial plastic masterbatch of the present invention will not be lost or lost due to copper oxidation caused by high temperature or harsh processing environment during processing. Reduce the antibacterial effect of the final plastic product.
- a PP melt-blown non-woven fabric was made from a polypropylene masterbatch added with 7wt% of the antibacterial agent of the present invention and tested for antibacterial efficacy.
- the test method is based on ASTM E2149-13a, and the test results are shown in Table 1.
- the anti-mold performance test was carried out on the injection-molded polypropylene plastic with the polypropylene masterbatch added with 10 wt% of the antibacterial agent of the present invention.
- the test method is based on ASTM G21-15, and the test results are shown in Table 2.
- the antibacterial performance test was carried out on polypropylene plastic injection molded by adding 5 wt% of the antibacterial agent of the present invention to the polypropylene masterbatch.
- the test method is based on JIS Z2801, and the test results are shown in Table 3.
- the antibacterial efficacy test was carried out on the spun-bonded non-woven fabric made of polypropylene masterbatch added with 7wt% antibacterial agent of the present invention.
- the test method is based on JIS L 1902:2015, and the test results are shown in Table 4.
- the results showed that no growth of Aspergillus niger (ATCC 6275) was observed after 28 days, and the width of the inhibition zone was 0.46mm.
- the antibacterial activity was measured according to the AATCC TM30-2017e (III) method, and the results are shown in Table 5.
- the present invention provides an innovative antibacterial plastic masterbatch, which has the following technical features and effects.
- the composition of the antibacterial plastic masterbatch of the present invention comprises the organic-inorganic composite antibacterial powder of micron-scale size, and the organic-inorganic composite antibacterial powder of this micron-scale size has the advantages of large body surface area and is easily dispersed in the plastic masterbatch.
- the micron-sized organic-inorganic composite antibacterial powder has the effect of preventing copper oxidation, and can prevent the technical effect of reducing the antibacterial activity of the copper-containing plastic masterbatch due to copper oxidation and deterioration during processing.
- the plastic product made by applying the antibacterial plastic masterbatch of the present invention has good antibacterial activity, and is especially suitable for application in the industrial fields related to the manufacture of antibacterial plastic products.
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Abstract
本发明揭示一种抗菌塑胶母粒、其制备方法和应用。特别地，该抗菌塑胶母粒的组成包含抗菌剂和热可塑性塑胶，该抗菌剂包含30～40wt％的有机无机混成物、30～40wt％的氧化锌和20～40wt％的铜化合物。
Description
本发明是关于一种抗菌塑胶母粒，其组成包含抗菌剂和热可塑性塑胶。特别地，该抗菌剂是一种微米级尺寸的有机无机复合型抗菌粉末。
在现今习知的抗菌技术领域，为了赋予塑胶具有抗菌的性能，常常是加入金属，如纳米银粒子，到塑胶母粒中，然后通过押出成型或射出成型等加工程序制成具有抗菌功能的塑胶产品。但在上述抗菌塑胶的加工工艺中常因高温的作业条件使加入的金属氧化变质，导致最后制成的塑胶产品容易出现粗糙、机械强度降低和外观变色的品质瑕疵，同时更大幅降低了最后产品的抗菌效果。
综上所述，在现今塑胶产业，对于开发在加工工艺中能防止抗菌效果失活的塑胶母粒，并且能应用在制造抗菌塑胶产品实为一亟待解决和研发的重要课题。
发明内容
鉴于先前的技术背景，为了符合未来产业的需求，本发明揭示一种抗菌塑胶母粒和其制造方法。特别地，本发明的抗菌塑胶母粒的组成包含微米级的有机无机复合型抗菌粉末，能有效地使该抗菌塑胶母粒在加工后得到的塑胶产品具有抑制细菌或/和霉菌生长的技术功效。
本发明揭示的「抗菌」用语，其涵义范围包括防止或抑制细菌生长、防止或抑制霉菌生长或同时防止或抑制细菌和霉菌生长。
本发明第一目的在于揭示一种抗菌塑胶母粒。具体地，该抗菌塑胶母粒的组成包含抗菌剂和热可塑性塑胶，该抗菌剂对该热可塑性塑胶的重量添加比例是1/99～10/90，较佳的，该抗菌剂对该热可塑性塑胶的重量添加比例是2/98～5/95。
特别地，该抗菌剂是一微米级尺寸的有机无机复合型抗菌粉末，其粒径分布(d50)是2～10微米，较佳的，其粒径分布(d50)是2～3微米。
具体地，该抗菌剂是由有机无机混成物、氧化锌和铜化合物所组成，以该抗菌剂的总重量计，该有机无机混成物所占的重量百分比是30～40wt％，该氧化锌所占的重量百分比是30～40wt％，和该铜化合物所占的重量百分比是20～40wt％。
具体地，该有机无机混成物的组成包含1～5wt％的有机组成物和95～99wt％的无机组成物。特别地，该有机组成物是抗氧化剂，其包含三烷基亚磷酸酯、二烷基硫酯、双酰肼、膦酸酯或其任一组合；和该无机组成物包含至少一种过渡金属盐类。
更具体地，该三烷基亚磷酸酯是三异癸基亚磷酸酯；该二烷基硫酯是硫代二丙酸二月桂酯；该双酰肼是N,N'-双[3-(3,5-二叔丁基-4-羟基苯基)丙酰]肼；和该膦酸酯是双(3,5-二叔丁基-4-羟基苄基膦酸单乙酯)钙。
具体地，该过渡金属盐类具有MX的通式，其中M表示过渡金属，该过渡金属是镁、铝、锰、钛、铁或镍；和X是选自下列群组之一或其组合：碳酸根(CO
3
2-)、硝酸根(NO3
-)、硫酸根(SO
4
2-)、硫离子(S
2-)和氧离子(O
2-)。
具体地，该铜化合物是选自下列群组之一或其组合：铜金属、氧化亚铜、氯化亚铜、溴化亚铜和碘化亚铜。
本发明第二目的在于提供一种抗菌塑胶母粒的制造方法，其包含但不限于下述步骤。
步骤一：干式研磨有机无机混成物、氧化锌和铜化合物，借此分别得到粒径分布(d50)是2～10微米的有机无机混成物粉末、氧化锌粉末和铜化合物粉末。
上述的干式研磨的目的是增加了各组成份的体表面积，以利于在后续混合加工时使各组成份之间能更有效地互相接触，借此达到混合均匀的技术效果。本发明经由过度实验证明当各组成份的粉末尺寸控制在微米级时具有最佳的混合效果。但是当粉末尺寸是纳米级时，因表面能太高，在混合时反而造成聚集的现象，不利于后续的加工流程。
上述各组成份是指该有机无机混成物、该氧化锌、该铜化合物或其粉末。
步骤二：混合该有机无机混成物粉末、该氧化锌粉末和该铜化合物粉末，借此得到抗菌剂，以该抗菌剂的总重量计，该有机无机混成物粉末所占的重量百分比是30～40wt％，该氧化锌粉末所占的重量百分比是 30～40wt％，和该铜化合物粉末所占的重量百分比是20～40wt％。
具体地，上述的混合步骤不会改变该有机无机混成物粉末、该氧化锌粉末和该铜化合物粉末的尺寸大小，在混合后得到的抗菌剂仍是粒径分布(d50)在2～10微米的粉末。
步骤三：混合该抗菌剂和热可塑性塑胶，借此得到抗菌塑胶组合物，该热可塑性塑胶包含聚乙烯、聚丙烯或其组合，以该抗菌塑胶组合物的总重量计，该抗菌剂所占的重量百分比是1～10wt％，和该热可塑性塑胶所占的重量百分比是90～99wt％。
步骤四：执行造粒程序，使该抗菌塑胶组合物制成为抗菌塑胶母粒。
具体地，该有机无机混成物的组成包含1～5wt％的有机组成物和95～99wt％的无机组成物；特别地，该有机组成物是抗氧化剂，其包含三烷基亚磷酸酯、二烷基硫酯、双酰肼、膦酸酯或其任一组合，和该无机组成物包含至少一种过渡金属盐类。
更具体地，该三烷基亚磷酸酯是三异癸基亚磷酸酯，该二烷基硫酯是硫代二丙酸二月桂酯，该双酰肼是N,N'-双[3-(3,5-二叔丁基-4-羟基苯基)丙酰]肼，和该膦酸酯是双(3,5-二叔丁基-4-羟基苄基膦酸单乙酯)钙。
具体地，该过渡金属盐类具有MX的通式，其中M表示过渡金属离子，该过渡金属是镁、铝、锰、钛、铁或镍；和X是选自下列群组之一或其组合：碳酸根(CO
3
2-)、硝酸根(NO3
-)、硫酸根(SO
4
2-)、硫离子(S
2-)和氧离子(O
2-)。
具体地，该铜化合物是选自下列群组之一或其组合：铜金属、氧化亚铜、氯化亚铜、溴化亚铜和碘化亚铜。
本发明第三目的在于提供一种使热可塑性塑胶抗菌的方法，其包含但不限于下述步骤。
步骤一：提供抗菌剂，该抗菌剂是粒径分布(d50)是2～10微米的粉末，和其组成包含有机无机混成物、氧化锌和铜化合物，以该抗菌剂的总重量计，该有机无机混成物所占的重量百分比是30～40wt％，该氧化锌所占的重量百分比是30～40wt％，和该铜化合物所占的重量百分比是20～40wt％。
步骤二：在热可塑性塑胶母粒加入该抗菌剂，借此使所制成的热可塑性塑胶具有抗菌的效果，该热可塑性塑胶母粒包含聚乙烯母粒、聚丙烯母粒或其组合。
具体地，该有机无机混成物的组成包含1～5wt％的有机组成物和 95～99wt％的无机组成物。特别地，该有机组成物是抗氧化剂，其包含三烷基亚磷酸酯、二烷基硫酯、双酰肼、膦酸酯或其任一组合，和该无机组成物包含至少一种过渡金属盐类。
更具体地，该三烷基亚磷酸酯是三异癸基亚磷酸酯，该二烷基硫酯是硫代二丙酸二月桂酯，该双酰肼是N,N'-双[3-(3,5-二叔丁基-4-羟基苯基)丙酰]肼，和该膦酸酯是双(3,5-二叔丁基-4-羟基苄基膦酸单乙酯)钙。
具体地，该过渡金属盐类具有MX的通式，其中M表示过渡金属，该过渡金属是镁、铝、锰、钛、铁或镍；和X是选自下列群组之一或其组合：碳酸根(CO
3
2-)、硝酸根(NO3
-)、硫酸根(SO
4
2-)、硫离子(S
2-)和氧离子(O
2-)。
具体地，该铜化合物是选自下列群组之一或其组合：铜金属、氧化亚铜、氯化亚铜、溴化亚铜和碘化亚铜。
综上所述，本发明至少具有如下所述的技术特征和功效。(1)本发明揭示了一种抗菌塑胶母粒，其组成包含微米级尺寸的有机无机复合型抗菌粉末，该微米级尺寸的有机无机复合型抗菌粉末具有体表面积大，容易分散在塑胶母粒中的优点。(2)该微米级尺寸的有机无机复合型抗菌粉末具有抑制铜氧化的效果，能够防止含铜塑胶母粒在加工过程中因铜氧化变质导致降低抗菌活性的技术功效。(3)应用本发明的抗菌塑胶母粒所制成的热可塑性塑胶产品具有良好的抗菌活性，能够有效地抑制和防止细菌或霉菌的生长。
附图的简要说明
图1是本发明经干式研磨后的氧化锌的粒径分布图。
图2是本发明的抗菌剂的粒径分布图。
图3是本发明抗菌聚丙烯母粒制成的熔喷不织布的的Cu2p XPS图谱。
实现发明的最佳方式
根据本发明第一实施例，本发明提供一种新颖的抗菌塑胶母粒。具体地，该抗菌塑胶母粒包含一种微米级尺寸的有机无机复合型抗菌粉末和热可塑性塑胶，该微米级尺寸的有机无机复合型抗菌粉末具有体表面积大，容易分散和防止铜氧化的技术效果。
在一具体实施例，该抗菌塑胶母粒的组成包含抗菌剂和热可塑性塑胶， 该抗菌剂对该热可塑性塑胶的重量添加比例是1/99～10/90，较佳的，该抗菌剂对该热可塑性塑胶的重量添加比例是2/98～5/95。
在一具体实施例，该抗菌剂是一微米级尺寸的有机无机复合型抗菌粉末，其粒径分布(d50)是2～10微米，较佳的，其粒径分布(d50)是2～3微米。
在一具体实施例，该抗菌剂是由有机无机混成物、氧化锌和铜化合物所组成，以该抗菌剂的总重量计，该有机无机混成物所占的重量百分比是30～40wt％，该氧化锌所占的重量百分比是30～40wt％，和该铜化合物所占的重量百分比是20～40wt％。
在一较佳具体实施例，以该抗菌剂的总重量计，该有机无机混成物所占的重量百分比是35～40wt％，该氧化锌所占的重量百分比是35～40wt％，和该铜化合物所占的重量百分比是30～40wt％。
在一具体实施例，该有机无机混成物的组成包含1～5wt％的有机组成物和95～99wt％的无机组成物。特别地，该有机组成物是抗氧化剂，其包含三烷基亚磷酸酯、二烷基硫酯、双酰肼、膦酸酯或其任一组合，和该无机组成物包含至少一种过渡金属盐类。
在一代表实施例，该三烷基亚磷酸酯是三异癸基亚磷酸酯；该二烷基硫酯是硫代二丙酸二月桂酯；该双酰肼是N,N'-双[3-(3,5-二叔丁基-4-羟基苯基)丙酰]肼；和该膦酸酯是双(3,5-二叔丁基-4-羟基苄基膦酸单乙酯)钙。
在一具体实施例，该过渡金属盐类具有MX的通式，其中M表示过渡金属，该过渡金属是镁、铝、锰、钛、铁或镍；和X是选自下列群组之一或其组合：碳酸根(CO
3
2-)、硝酸根(NO3
-)、硫酸根(SO
4
2-)、硫离子(S
2-)和氧离子(O
2-)。
在一具体实施例，该铜化合物是选自下列群组之一或其组合：铜金属、氧化亚铜、氯化亚铜、溴化亚铜和碘化亚铜。
本发明第二实施例在于提供一种抗菌塑胶母粒的制造方法，其包含但不限于下述步骤。
步骤一：干式研磨有机无机混成物、氧化锌和铜化合物，借此分别得到粒径分布(d50)是2～10微米的有机无机混成物粉末、氧化锌粉末和铜化合物粉末。
在一具体实施例，上述的干式研磨是为了增加各组成份的体表面积，以利于在后续混合加工时使各组成份之间能更有效的互相接触，借此达到 混合均匀的技术效果。本发明经由过度实验证明当各组成份的粉末控制在微米级时具有最佳的混合效果。较佳的，经步骤一是得到粒径分布(d50)2～3微米的有机无机混成物粉末、氧化锌粉末和铜化合物粉末。
上述各组成份是指有机无机混成物、氧化锌、铜化合物或其粉末。
步骤二：混合该有机无机混成物粉末、该氧化锌粉末和该铜化合物粉末，借此得到抗菌剂，以该抗菌剂的总重量计，该有机无机混成物粉末所占的重量百分比是30～40wt％，该氧化锌粉末所占的重量百分比是30～40wt％，和该铜化合物粉末所占的重量百分比是20～40wt％。
具体地，上述的混合步骤不会改变该有机无机混成物粉末、该氧化锌粉末和该铜化合物粉末的尺寸大小，在混合后得到的抗菌剂是粒径分布(d50)在2～10微米的粉末。
在一较佳具体实施例，以该抗菌剂的总重量计，该有机无机混成物所占的重量百分比是35～40wt％，该氧化锌所占的重量百分比是35～40wt％，和该铜化合物所占的重量百分比是30～40wt％。
步骤三：混合该抗菌剂和热可塑性塑胶，借此得到抗菌塑胶组合物，该热可塑性塑胶包含聚乙烯、聚丙烯或其组合，以该抗菌塑胶组合物的总重量计，该抗菌剂所占的重量百分比是1～10wt％，和该热可塑性塑胶所占的重量百分比是90～99wt％。
步骤四：执行造粒程序，使该抗菌塑胶组合物制成为抗菌塑胶母粒。
在一具体实施例，该有机无机混成物的组成包含1～5wt％的有机组成物和95～99wt％的无机组成物；特别地，该有机组成物是抗氧化剂，包含三烷基亚磷酸酯、二烷基硫酯、双酰肼、膦酸酯或其任一组合，和该无机组成物包含至少一种过渡金属盐类。
在一代表实施例，该三烷基亚磷酸酯是三异癸基亚磷酸酯，该二烷基硫酯是硫代二丙酸二月桂酯，该双酰肼是N,N'-双[3-(3,5-二叔丁基-4-羟基苯基)丙酰]肼，该膦酸酯是双(3,5-二叔丁基-4-羟基苄基膦酸单乙酯)钙。
在一具体实施例，该过渡金属盐类具有MX的通式，其中M表示过渡金属离子，该过渡金属是镁、铝、锰、钛、铁或镍；和X是选自下列群组之一或其组合：碳酸根(CO
3
2-)、硝酸根(NO3
-)、硫酸根(SO
4
2-)、硫离子(S
2-)和氧离子(O
2-)。
在一具体实施例，该铜化合物是选自下列群组之一或其组合：铜金属、 氧化亚铜、氯化亚铜、溴化亚铜和碘化亚铜。
本发明第三实施例在于提供一种使热可塑性塑胶抗菌的方法，其包含但不限于下述步骤。
步骤一：提供抗菌剂，该抗菌剂是粒径分布(d50)是2～10微米的粉末，和其组成包含有机无机混成物、氧化锌和铜化合物，以该抗菌剂的总重量计，该有机无机混成物所占的重量百分比是30～40wt％，该氧化锌所占的重量百分比是30～40wt％，和该铜化合物所占的重量百分比是20～40wt％。
在一较佳具体实施例，以该抗菌剂的总重量计，该有机无机混成物所占的重量百分比是35～40wt％，该氧化锌所占的重量百分比是35～40wt％，和该铜化合物所占的重量百分比是30～40wt％。
步骤二：在热可塑性塑胶母粒加入该抗菌剂，借此使所制成的热可塑性塑胶具有抗菌的效果，该热可塑性塑胶母粒包含聚乙烯母粒、聚丙烯母粒或其组合。
在一具体实施例，该有机无机混成物的组成包含1～5wt％的有机组成物和95～99wt％的无机组成物。特别地，该有机组成物是抗氧化剂，其包含三烷基亚磷酸酯、二烷基硫酯、双酰肼、膦酸酯或其任一组合，和该无机组成物包含至少一种过渡金属盐类。
在一代表实施例，该三烷基亚磷酸酯是三异癸基亚磷酸酯，该二烷基硫酯是硫代二丙酸二月桂酯，该双酰肼是N,N'-双[3-(3,5-二叔丁基-4-羟基苯基)丙酰]肼，和该膦酸酯是双(3,5-二叔丁基-4-羟基苄基膦酸单乙酯)钙。
在一具体实施例，该过渡金属盐类具有MX的通式，其中M表示过渡金属，该过渡金属是镁、铝、锰、钛、铁或镍；和X是选自下列群组之一或其组合：碳酸根(CO
3
2-)、硝酸根(NO3
-)、硫酸根(SO
4
2-)、硫离子(S
2-)和氧离子(O
2-)。
在一具体实施例，该铜化合物是选自下列群组之一或其组合：铜金属、氧化亚铜、氯化亚铜、溴化亚铜和碘化亚铜。
以下以具体实验例阐述本发明的技术特征和效果。
在一实验例，本发明的有机无机混成物的制造方法如下所述。首先，干式研磨混合无机组成物和有机抗氧化剂，研磨过程采样以粒径分析仪监控其粒径分布，当粒径分布(d50)是约3微米时，即得到本发明的有机无机混成物。其中该无机组成物含有5wt％碳酸锌，20wt％碳酸镁和75wt％的二氧 化钛；该无机组成物的组成也可以是硝酸锌、硫酸锌、硝酸镁、硫酸镁、三氧化二铝、三氧化二铁或其任一组合；该有机抗氧化剂是双(3,5-二叔丁基-4-羟基苄基膦酸单乙酯)钙、N,N'-双[3-(3,5-二叔丁基-4-羟基苯基)丙酰]肼或其任组合，和该无机组成物对该有机抗氧化剂的重量比例是98：2
。
在另一代表实验例，混合上述的粒径分布(d50)是约3微米的有机无机混成物粉末34克、经干式研磨后得到粒径分布(d50)是约3微米的氧化锌粉末34克和粒径分布(d50)是约3微米的氧化亚铜粉末32克，经充分混合后得到本发明所述的抗菌剂。
上述代表实验例的抗菌剂加入聚乙烯母粒或聚丙烯母粒后，再经过造粒程序制成抗菌塑胶母粒。其中该抗菌剂对该聚乙烯母粒或聚丙烯母粒的添加重量比例是1/99～10/90。
在一代表实验例，请参照图1所示，本发明经过干式研磨的氧化锌的粒径分布(d50)是2.25微米。在另一代表实验例，请参照图2所示，本发明的抗菌剂的粒径分布(d50)是2.81微米。
在又一代表实验例，请参照图3，其是加入7wt％本发明抗菌剂的PP塑胶母粒制成的熔喷不织布的XPS分析图谱。该XPS图谱显示该熔喷不织布在Cu 2p的束缚能是位于932.1电子伏特(eV)，其非常接近铜金属或亚铜((Cu
(0))或Cu
(I)(Cu
2O))在932.8电子伏特(eV)的位置，这表示该熔喷不织布所含有的铜没有发生氧化现象。同时该熔喷不织布在940-948电子伏特之间也没有观察到振动激发峰群(shake-up excitation)，更加证实了该熔喷不织布所含有的铜没有氧化。据此，本发明的抗菌剂还具有抑制铜化合物氧化的技术功效，能确保本发明的含铜抗菌塑胶母粒在加工的过程中不会因高温或严苛的加工环境造成铜氧化而丧失或降低最终塑胶产品的抗菌效果。
抗菌效能测试
在一代表实验例，以加入7wt％的本发明抗菌剂的聚丙烯母粒制成PP熔喷不织布进行抗菌效能测试。测试方法是依据ASTM E2149-13a，测试结果如表一所示。
表一
在一代表实验例，以加入10wt％的本发明抗菌剂的聚丙烯母粒，经射出成型后的聚丙烯塑胶进行防霉效能测试。测试方法是依据ASTM G21-15，测试结果如表二所示。
表二
在一代表实验例，以加入5wt％的本发明抗菌剂的聚丙烯母粒，经射出成型后的聚丙烯塑胶进行抗菌效能测试。测试方法是依据JIS Z2801，测试结果如表三所示。
表三
在一代表实验例，以加入7wt％的本发明抗菌剂的聚丙烯母粒所制成的纺粘不织布进行抗菌效能测试。测试方法是依据JIS L 1902:2015，测试结果如表四所示。结果显示在28天后没有观察到Aspergillus niger(ATCC 6275)的生长，且抑菌区域宽度是0.46mm。另依据AATCC TM30-2017e(Ⅲ)方法测量其抗菌活性，结果如表五所示。
表四
表五
综上所述，本发明提供一种创新的抗菌塑胶母粒，其具有如下的技术特征和功效。(1)本发明抗菌塑胶母粒的组成包含微米级尺寸的有机无机复合型抗菌粉末，该微米级尺寸的有机无机复合型抗菌粉末具有体表面积大，容易分散在塑胶母粒中的优点。(2)该微米级尺寸的有机无机复合型抗菌粉末具有防止铜氧化的效果，能够防止含铜塑胶母粒在加工过程中因铜氧化变质导致降低抗菌活性的技术功效。(3)应用本发明的抗菌塑胶母粒制成的塑胶产品具有良好的抗菌活性，特别适合应用在制造抗菌塑胶产品相关产业领域。
以上虽以特定实验例说明本发明，但并不因此限定本发明的范围，只要不脱离本发明的要旨，熟悉本技艺者了解在不脱离本发明的意图及范围下可进行各种变形或变更。此外，摘要部分和标题仅是用来辅助专利文件搜寻之用，并非用来限制本发明的权利范围。
Claims (19)
- 一种抗菌塑胶母粒，其特征在于，其组成包含抗菌剂和热可塑性塑胶，该抗菌剂对该热可塑性塑胶的重量添加比例是1/99～10/90；和该抗菌剂是由有机无机混成物、氧化锌和铜化合物所组成，以该抗菌剂的总重量计，该有机无机混成物所占的重量百分比是30～40wt％，该氧化锌所占的重量百分比是30～40wt％，和该铜化合物所占的重量百分比是20～40wt％。
- 根据权利要求1所述的抗菌塑胶母粒，其特征在于，该有机无机混成物的组成包含1～5wt％的有机组成物和95～99wt％的无机组成物，该有机组成物包含三烷基亚磷酸酯、二烷基硫酯、双酰肼、膦酸酯或其任一组合，和该无机组成物包含至少一种过渡金属盐类。
- 根据权利要求2所述的抗菌塑胶母粒，其特征在于，该三烷基亚磷酸酯是三异癸基亚磷酸酯，该二烷基硫酯是硫代二丙酸二月桂酯，该双酰肼是N,N'-双[3-(3,5-二叔丁基-4-羟基苯基)丙酰]肼，和该膦酸酯是双(3,5-二叔丁基-4-羟基苄基膦酸单乙酯)钙。
- 根据权利要求2所述的抗菌塑胶母粒，其特征在于，该过渡金属盐类具有MX的通式，其中M表示过渡金属，X是选自下列群组之一或其组合：碳酸根、硝酸根、硫酸根、硫离子和氧离子。
- 根据权利要求4所述的抗菌塑胶母粒，其特征在于，该过渡金属是镁、铝、锰、钛、铁或镍。
- 根据权利要求1所述的抗菌塑胶母粒，其特征在于，该铜化合物是选自下列群组之一或其组合：铜金属、氧化亚铜、氯化亚铜、溴化亚铜和碘化亚铜。
- 根据权利要求1所述的抗菌塑胶母粒，其特征在于，该热可塑性塑胶包含聚乙烯、聚丙烯或其组合。
- 一种抗菌塑胶母粒的制造方法，其特征在于，其步骤包含：干式研磨有机无机混成物、氧化锌和铜化合物，借此分别得到粒径分布(d50)是2～10微米的有机无机混成物粉末、氧化锌粉末和铜化合物粉末；混合该有机无机混成物粉末、该氧化锌粉末和该铜化合物粉末，借此得到抗菌剂，以该抗菌剂的总重量计，该有机无机混成物粉末所占的重量百分比是30～40wt％，该氧化锌粉末所占的重量百分比是30～40wt％，和该铜化合物粉末所占的重量百分比是20～40wt％；混合该抗菌剂和热可塑性塑胶，借此得到抗菌塑胶组合物，该热可塑性塑胶包含聚乙烯、聚丙烯或其组合，以该抗菌塑胶组合物的总重量计，该抗菌剂所占的重量百分比是1～10wt％，和该热可塑性塑胶所占的重量百分比是90～99wt％；和执行造粒程序，使该抗菌塑胶组合物制成为抗菌塑胶母粒。
- 根据权利要求8所述的抗菌塑胶母粒的制造方法，其特征在于，该有机无机混成物的组成包含1～5wt％的有机组成物和95～99wt％的无机组成物，该有机组成物包含三烷基亚磷酸酯、二烷基硫酯、双酰肼、膦酸酯或其任一组合，和该无机组成物包含至少一种过渡金属盐类。
- 根据权利要求9所述的抗菌塑胶母粒的制造方法，其特征在于，该三烷基亚磷酸酯是三异癸基亚磷酸酯，该二烷基硫酯是硫代二丙酸二月桂酯，该双酰肼是N,N'-双[3-(3,5-二叔丁基-4-羟基苯基)丙酰]肼，和该膦酸酯是双(3,5-二叔丁基-4-羟基苄基膦酸单乙酯)钙。
- 根据权利要求9所述的抗菌塑胶母粒的制造方法，其特征在于，该过渡金属盐类具有MX的通式，其中M表示过渡金属离子，X是选自下列群组之一或其组合：碳酸根、硝酸根、硫酸根、硫离子和氧离子。
- 根据权利要求10所述的抗菌塑胶母粒的制造方法，其特征在于，该过渡金属是镁、铝、锰、钛、铁或镍。
- 根据权利要求8所述的抗菌塑胶母粒的制造方法，其特征在于，该铜化合物是选自下列群组之一或其组合：铜金属、氧化亚铜、氯化亚铜、溴化亚铜和碘化亚铜。
- 一种使热可塑性塑胶抗菌的方法，其特征在于，其步骤包含：提供抗菌剂，该抗菌剂是粒径分布(d50)是2～10微米的粉末，和该抗菌剂的组成包含有机无机混成物、氧化锌和铜化合物，以该抗菌剂的总重量计，该有机无机混成物所占的重量百分比是30～40wt％，该氧化锌所占的重量百分比是30～40wt％，和该铜化合物所占的重量百分比是20～40wt％；和在热可塑性塑胶母粒加入该抗菌剂，借此使所制成的热可塑性塑胶具有抗菌的效果，该热可塑性塑胶母粒包含聚乙烯母粒、聚丙烯母粒或其组合。
- 根据权利要求14所述的使热可塑性塑胶抗菌的方法，其特征在于，该有机无机混成物的组成包含1～5wt％的有机组成物和95～99wt％的无机组成物，该有机组成物包含三烷基亚磷酸酯、二烷基硫酯、双酰肼、膦酸酯或其任一组合，和该无机组成物包含至少一种过渡金属盐类。
- 根据权利要求15所述的使热可塑性塑胶抗菌的方法，其特征在于，该三烷基亚磷酸酯是三异癸基亚磷酸酯，该二烷基硫酯是硫代二丙酸二月桂酯，该双酰肼是N,N'-双[3-(3,5-二叔丁基-4-羟基苯基)丙酰]肼，和该膦酸酯是双(3,5-二叔丁基-4-羟基苄基膦酸单乙酯)钙。
- 根据权利要求15所述的使热可塑性塑胶抗菌的方法，其特征在于，该过渡金属盐类具有MX的通式，其中M表示过渡金属，X是选自下列群组之一或其组合：碳酸根、硝酸根、硫酸根、硫离子和氧离子。
- 根据权利要求17所述的使热可塑性塑胶抗菌的方法，其特征在于，该过渡金属是镁、铝、锰、钛、铁或镍。
- 根据权利要求14所述的使热可塑性塑胶抗菌的方法，该铜化合物是选自下列群组之一或其组合：铜金属、氧化亚铜、氯化亚铜、溴化亚铜和碘化亚铜。
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| JPH10168265A (ja) * | 1996-12-05 | 1998-06-23 | Toagosei Co Ltd | 抗菌性塩化ビニル樹脂組成物 |
| KR100384929B1 (en) * | 2001-11-28 | 2003-05-22 | Dong Won Plastic Inc | Resin composition for antibacterial and antifungal pipes of waterwork and sewerage, and antibacterial and antifungal pipes of waterwork and sewerage produced by using the same |
| WO2010136792A2 (en) * | 2009-05-26 | 2010-12-02 | Intrinsiq Materials Limited | Antibacterial composition |
| CN104592629A (zh) * | 2015-01-05 | 2015-05-06 | 上海纳旭实业有限公司 | 一种Cu/ZnO 复合抗菌PP母粒的制备方法 |
| CN106280423A (zh) * | 2016-08-30 | 2017-01-04 | 宁波伊德尔新材料有限公司 | 一种抗菌尼龙复合材料及其制备方法 |
| TWI647082B (zh) * | 2017-12-19 | 2019-01-11 | 康豪奈米應用材料有限公司 | 銅抗菌母粒製造方法 |
| TW202100621A (zh) * | 2020-09-04 | 2021-01-01 | 戴壟科技股份有限公司 | 一種抗菌方法 |
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- 2022-07-15 WO PCT/CN2022/106033 patent/WO2023001076A1/zh active Application Filing
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|---|---|---|---|---|
| JPH10168265A (ja) * | 1996-12-05 | 1998-06-23 | Toagosei Co Ltd | 抗菌性塩化ビニル樹脂組成物 |
| KR100384929B1 (en) * | 2001-11-28 | 2003-05-22 | Dong Won Plastic Inc | Resin composition for antibacterial and antifungal pipes of waterwork and sewerage, and antibacterial and antifungal pipes of waterwork and sewerage produced by using the same |
| WO2010136792A2 (en) * | 2009-05-26 | 2010-12-02 | Intrinsiq Materials Limited | Antibacterial composition |
| CN104592629A (zh) * | 2015-01-05 | 2015-05-06 | 上海纳旭实业有限公司 | 一种Cu/ZnO 复合抗菌PP母粒的制备方法 |
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| TW202100621A (zh) * | 2020-09-04 | 2021-01-01 | 戴壟科技股份有限公司 | 一種抗菌方法 |
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