CN107118502A - A kind of medical product antibacterial 3D printing material - Google Patents
A kind of medical product antibacterial 3D printing material Download PDFInfo
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- CN107118502A CN107118502A CN201710467131.4A CN201710467131A CN107118502A CN 107118502 A CN107118502 A CN 107118502A CN 201710467131 A CN201710467131 A CN 201710467131A CN 107118502 A CN107118502 A CN 107118502A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
- C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
- C08K2003/3045—Sulfates
- C08K2003/3081—Aluminum sulfate
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- 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
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
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- 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
- C08K3/38—Boron-containing compounds
- C08K2003/387—Borates
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- 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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- 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
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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Abstract
The invention discloses a kind of medical product antibacterial 3D printing material, its raw material includes ABS resin, organic epoxy resin, acrylic resin, Lauxite, poly butyric ester, antimicrobial enhancing agent part, modified zeolite, calcium molybdate, forging white powder, zeolite powder, nitrocotton, trbasic zinc phosphate, bentonite, antimony oxide, zinc oxide, seawood meal, diatomite, antimony trioxide, zirconium oxide, aluminum sulfate, aluminum oxide, natrosol, lauryl acrylate, trimethyl phosphate, acrylonitrile, silane coupler KH 560, sulfonated oil, defoamer and modified additive.The 3D printing material of the present invention has excellent anti-microbial property.
Description
Technical field
The present invention relates to the technical field of 3D printing material, more particularly to a kind of medical product antibacterial 3D printing material.
Background technology
PLA have the advantages that high intensity, good biocompatibility and can biology explain, but its crisp, poor toughness of property etc.
Feature limits its application, and the method for traditional PLA toughness reinforcing is that PLA and oligomer or elastomer are directly blended into system
Standby lactic acid composite material, although the toughness of lactic acid composite material can be improved to a certain extent, but sacrifice biological degradability
And antibiotic property.And the articles for use of medicine big multipair its degradability and its anti-microbial property require very high, so needing design one badly
Plant medical product and solve the problems of the prior art with antibacterial 3D printing material.
The content of the invention
To solve technical problem present in background technology, the present invention proposes a kind of medical product antibacterial 3D printing material
Material, with excellent anti-microbial property.
A kind of medical product proposed by the present invention antibacterial 3D printing material, its raw material includes by weight：ABS resin
80-100 parts, organic epoxy resin 5-15 parts, 4-9 parts of acrylic resin, 3-6 parts of Lauxite, poly butyric ester 2-5
Part, 4-8 parts of antimicrobial enhancing agent, 3-6 parts of modified zeolite, 1-5 parts of calcium molybdate, 2-6 parts of white powder of forging, 2-6 parts of zeolite powder, nitrocotton 1-
4 parts, 3-6 parts of trbasic zinc phosphate, 1-4 parts of bentonite, 2-5 parts of antimony oxide, 3-6 parts of zinc oxide, 1-4 parts of seawood meal, diatomite 2-9
Part, 3-12 parts of antimony trioxide, 1-5 parts of zirconium oxide, 1-6 parts of aluminum sulfate, 2-6 parts of aluminum oxide, 1-5 parts of natrosol, third
1-5 parts of olefin(e) acid lauryl, 1-4 parts of trimethyl phosphate, 2-6 parts of acrylonitrile, KH-5601-4 parts of silane coupler, sulfonated oil 2-5
Part, 5-9 parts of defoamer, 5-15 parts of modified additive.
Preferably, the raw material of antimicrobial enhancing agent includes by weight：5-15 parts of urea, 3-5 parts of polyvinylpyrrolidone, go
6-9 parts of ionized water, 1-4 parts of sodium chloride, 2-5 parts of defoamer, 3-6 parts of aluminum nitrate, 4-8 parts of nano titanium oxide, zirconium sulfate 3-5
Part, 2-6 parts of disodium hydrogen phosphate.
Preferably, antimicrobial enhancing agent is prepared by following technique：Urea, polyvinylpyrrolidone and deionized water are mixed
Close uniform, then add sodium chloride and defoamer stirring 10-30min, then add aluminum nitrate and obtain material a；Use separatory funnel
Nano titanium oxide is added into material a and zirconium sulfate is well mixed, then heating water bath is cooled to after room temperature to 70-90 DEG C
Add disodium hydrogen phosphate to be well mixed, be then aged, filtration washing, dry, be cooled to room temperature after calcining and obtain antimicrobial enhancing agent.
Preferably, modified zeolite is prepared by following technique：Natural zeolite and sodium chloride solution are well mixed, stirred
Then 1-3h, filtering means dehydration, drying is calcined 0.5-1.5h in 450-550 DEG C, is subsequently placed in lanthanum chloride solution, stirs 1-3h,
Filtering means dehydration, drying is subsequently placed in 180-220 DEG C of roasting 0.5-1.5h, is subsequently placed in silver nitrate solution, stirs 2-4h, dry
Modified zeolite is obtained after dry.
Preferably, in the preparation technology of modified zeolite, the mass fraction of sodium chloride solution is 1-3%；Lanthanum chloride solution
Mass fraction is 0.3-0.5%, and pH is 9.0-10.0；The mass fraction of silver nitrate solution is 0.1-0.3%.
Preferably, in the preparation technology of modified zeolite, natural zeolite, sodium chloride solution, lanthanum chloride solution and silver nitrate are molten
The weight ratio of liquid is 1-3：2-5：3-6：1-4.
Preferably, the raw material of modified additive includes by weight：5-15 parts of glass fibre, 3-6 parts of montmorillonite, silica flour 2-
6 parts, 1-4 parts of ceramic, 3-5 parts of clay, 4-8 parts of zinc stearate, 2-5 parts of Firebrake ZB, 1-4 parts of nano silicon, mica
2-3 parts, 1-4 parts of wollastonite in powder, 2-5 parts of kaolin, 3-6 parts of talcum powder, 2-5 parts of hydroxyethyl cellulose, 1-3 parts of dolomite dust,
2-5 parts of aluminium dihydrogen phosphate, 1-4 parts of magnesium aluminate, 2-5 parts of magnesia, 3-6 parts of tetraethyl orthosilicate, VTES 3-6
Part, 4-9 parts of ammoniacal liquor, 3-6 parts of acetylbutyrylcellulose.
Preferably, modified additive is prepared by following technique：By glass fibre, montmorillonite, silica flour, ceramic,
It is clay, zinc stearate, Firebrake ZB, nano silicon, mica, wollastonite in powder, kaolin, talcum powder, hydroxyethyl cellulose, white
Marble dust, aluminium dihydrogen phosphate, magnesium aluminate, magnesia and absolute ethyl alcohol are well mixed, and 1-3h, Ran Housheng are stirred under nitrogen protection
Temperature adds tetraethyl orthosilicate, VTES and ammoniacal liquor and is well mixed, stir 5-7h, vacuum mistake to 30-70 DEG C
Filter, is washed 2-4 times with absolute ethyl alcohol, is then added after acetylbutyrylcellulose mixing, and stirring 20-40min obtains modified additive.
A kind of medical product antibacterial 3D printing material of the present invention, its raw material includes ABS resin, Organic fluoride asphalt mixtures modified by epoxy resin
Fat, acrylic resin, Lauxite, poly butyric ester, antimicrobial enhancing agent part, modified zeolite, calcium molybdate, forging white powder, zeolite
Powder, nitrocotton, trbasic zinc phosphate, bentonite, antimony oxide, zinc oxide, seawood meal, diatomite, antimony trioxide, zirconium oxide, sulfuric acid
Aluminium, aluminum oxide, natrosol, lauryl acrylate, trimethyl phosphate, acrylonitrile, silane coupler KH-560, sulfonation
Oil, defoamer and modified additive.The 3D printing material of the present invention has excellent anti-microbial property.Wherein, antimicrobial enhancing agent passes through
Urea, polyvinylpyrrolidone and deionized water are well mixed, sodium chloride and defoamer stirring is then added, then adds nitre
Sour aluminium obtains material a；Nano titanium oxide being added into material a with separatory funnel and zirconium sulfate being well mixed, then water-bath adds
Heat, is cooled to addition disodium hydrogen phosphate after room temperature and is well mixed, be then aged, filtration washing, dry, room temperature is cooled to after calcining
Antimicrobial enhancing agent is obtained, is applied in 3D printing material of the present invention, the anti-microbial property of 3D printing material of the present invention is effectively increased.
Modified zeolite is stirred, filtering means dehydration by the way that natural zeolite and sodium chloride solution are well mixed, and then drying is calcined, then puts
In lanthanum chloride solution, then stirring, filtering means dehydration, drying is put roasting, is subsequently placed in silver nitrate solution, stirs, after drying
Modified zeolite is obtained, modified zeolite surface is reduced with the presence of substantial amounts of ball thing, and composite zeolite surface apertures compared with modified zeolite,
This is probably due to adsorbing the AgNO on zeolite granular surface3Do not elute completely, the Ag being decomposed to form in drying course2O group
Gather on its surface, cause zeolite portion aperture to be blocked, thus it is a number of silver-colored with ion shape except having in silver type antibacterial zeolite particles
Formula is present in outside the cation exchange position of antibacterial sorbing material and duct, also part Ag2O is present in the surface of material, from
And ensure that silver and Escherichia coli has enough contacts area.In modified recombination process, most of sodium ion and silver ion pass through
Ion exchange enters inside zeolite, and composite zeolite denitrogenation is by cation and NH4 such as the sodium ions in zeolite structured+Generation ion
Exchange, dephosphorization is the Electrostatic Absorption of the hydrous zirconia gel by zeolite surface, antibacterial is the antibacterial Ag ions because bactericidal property
It is loaded into.Wherein, modified additive by by glass fibre, montmorillonite, silica flour, ceramic, clay, zinc stearate, Firebrake ZB,
Nano silicon, mica, wollastonite in powder, kaolin, talcum powder, hydroxyethyl cellulose, dolomite dust, aluminium dihydrogen phosphate, aluminium
Sour magnesium, magnesia and absolute ethyl alcohol are well mixed, stir, then heat up under nitrogen protection, add tetraethyl orthosilicate, vinyl
Triethoxysilane and ammoniacal liquor are well mixed, and stirring, vacuum filter is washed with absolute ethyl alcohol, then add acetate butyrate fiber
Element mixing after, stirring obtain modified additive, apply to the present invention 3D printing material in, with the present invention antimicrobial enhancing agent and change
Property zeolite coordinate, impart the excellent anti-microbial property of 3D printing material of the present invention and mechanical property.
Embodiment
The present invention is described in detail with reference to specific embodiment, it should be appreciated that embodiment is served only for illustrating this hair
It is bright, rather than for limiting the invention, any modification made on the basis of the present invention, equivalent substitution etc. are in this hair
In bright protection domain.
In embodiment, the parts by weight of ABS resin can for 80 parts, 81 parts, 82 parts, 83 parts, 84 parts, 85 parts, 86
Part, 87 parts, 88 parts, 89 parts, 90 parts, 91 parts, 92 parts, 93 parts, 94 parts, 95 parts, 96 parts, 97 parts, 98 parts, 99 parts, 100 parts；Have
The parts by weight of machine epoxy resin can be 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, 11 parts, 12 parts, 13 parts, 14 parts, 15 parts；
The parts by weight of acrylic resin can for 4 parts, 4.5 parts, 5 parts, 5.5 parts, 6 parts, 6.5 parts, 7 parts, 7.5 parts, 8 parts, 8.5 parts, 9
Part；The parts by weight of Lauxite can be 3 parts, 3.5 parts, 4 parts, 4.5 parts, 5 parts, 5.5 parts, 6 parts；The weight of poly butyric ester
Part can be 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts, 4.5 parts, 5 parts；The parts by weight of antimicrobial enhancing agent can for 4 parts, 5 parts, 6
Part, 7 parts, 8 parts；The parts by weight of modified zeolite can be 3 parts, 3.5 parts, 4 parts, 4.5 parts, 5 parts, 5.5 parts, 6 parts；The weight of calcium molybdate
It can be 1 part, 2 parts, 3 parts, 4 parts, 5 parts to measure part；The parts by weight for forging white powder can be 2 parts, 3 parts, 4 parts, 5 parts, 6 parts；Zeolite powder
Parts by weight can be 2 parts, 3 parts, 4 parts, 5 parts, 6 parts；The parts by weight of nitrocotton can for 1 part, 1.5 parts, 2 parts, 2.5 parts, 3
Part, 3.5 parts, 4 parts；The parts by weight of trbasic zinc phosphate can be 3 parts, 3.5 parts, 4 parts, 4.5 parts, 5 parts, 5.5 parts, 6 parts；It is bentonitic heavy
It can be 1 part, 1.5 parts, 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts to measure part；The parts by weight of antimony oxide can for 2 parts, 2.5
Part, 3 parts, 3.5 parts, 4 parts, 4.5 parts, 5 parts；The parts by weight of zinc oxide can for 3 parts, 3.5 parts, 4 parts, 4.5 parts, 5 parts, 5.5 parts,
6 parts；The parts by weight of seawood meal can be 1 part, 1.5 parts, 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts；Diatomaceous parts by weight can be with
For 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts, 4.5 parts, 5 parts, 5.5 parts, 6 parts, 6.5 parts, 7 parts, 7.5 parts, 8 parts, 8.5 parts, 9 parts；
The parts by weight of antimony trioxide can be 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, 11 parts, 12 parts；The weight of zirconium oxide
Part can be 1 part, 2 parts, 3 parts, 4 parts, 5 parts；The parts by weight of aluminum sulfate can for 1 part, 1.5 parts, 2 parts, 2.5 parts, 3 parts, 3.5
Part, 4 parts, 4.5 parts, 5 parts, 5.5 parts, 6 parts；The parts by weight of aluminum oxide can be 2 parts, 3 parts, 4 parts, 5 parts, 6 parts；Cellulose hydroxyl second
The parts by weight of base ether can be 1 part, 2 parts, 3 parts, 4 parts, 5 parts；The parts by weight of lauryl acrylate can for 1 part, 2 parts, 3 parts, 4
Part, 5 parts；The parts by weight of trimethyl phosphate can be 1 part, 1.5 parts, 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts；The weight of acrylonitrile
Part can be 2 parts, 3 parts, 4 parts, 5 parts, 6 parts；Silane coupler KH-560 parts by weight can for 1 part, 1.5 parts, 2 parts, 2.5
Part, 3 parts, 3.5 parts, 4 parts；The parts by weight of sulfonated oil can be 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts, 4.5 parts, 5 parts；Defoamer
Parts by weight can be 5 parts, 5.5 parts, 6 parts, 6.5 parts, 7 parts, 7.5 parts, 8 parts, 8.5 parts, 9 parts；The parts by weight of modified additive can
Think 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, 11 parts, 12 parts, 13 parts, 14 parts, 15 parts.
Embodiment 1
A kind of medical product proposed by the present invention antibacterial 3D printing material, its raw material includes by weight：ABS resin 90
Part, 10 parts of organic epoxy resin, 6.5 parts of acrylic resin, 4.5 parts of Lauxite, 3.5 parts of poly butyric ester, antibacterial increase
Strong 6 parts of agent, 4.5 parts of modified zeolite, 3 parts of calcium molybdate, 4 parts of white powder of forging, 4 parts of zeolite powder, 2.5 parts of nitrocotton, 4.5 parts of trbasic zinc phosphate,
2.5 parts of bentonite, 3.5 parts of antimony oxide, 4.5 parts of zinc oxide, 2.5 parts of seawood meal, 5.5 parts of diatomite, antimony trioxide 7.5
Part, 3 parts of zirconium oxide, 3.5 parts of aluminum sulfate, 4 parts of aluminum oxide, 3 parts of natrosol, 3 parts of lauryl acrylate, tripotassium phosphate
2.5 parts of ester, 4 parts of acrylonitrile, 2.5 parts of silane coupler KH-560,3.5 parts of sulfonated oil, 7 parts of defoamer, 10 parts of modified additive.
Antimicrobial enhancing agent is prepared by following technique：By weight by 10 parts of urea, 4 parts of polyvinylpyrrolidones and
7.5 parts of deionized waters are well mixed, and are then added 2.5 parts of sodium chloride and 3.5 parts of defoamer stirring 20min, are then added 4.5 parts
Aluminum nitrate obtains material a；6 parts of nano titanium oxides are added into material a with separatory funnel and 4 parts of zirconium sulfates are well mixed, so
Heating water bath is cooled to 4 parts of disodium hydrogen phosphates of addition after room temperature and is well mixed, be then aged, filtration washing, do to 80 DEG C afterwards
It is dry, room temperature is cooled to after calcining and obtains antimicrobial enhancing agent.
Modified zeolite is prepared by following technique：It is 2% by weight by 2 parts of natural zeolites and 3.5 parts of mass fractions
Sodium chloride solution is well mixed, and stirs 2h, and then filtering means dehydration, drying is calcined 1h in 500 DEG C, is subsequently placed in 4.5 parts of quality point
During number is the lanthanum chloride solution that 0.4%, pH is 9.5,2h is stirred, filtering means dehydration, drying is subsequently placed in 200 DEG C of roasting 1h, then
2.5 parts of mass fractions are placed in 0.2% silver nitrate solution, to stir 3h, modified zeolite is obtained after drying.
Modified additive is prepared by following technique：By weight by 10 parts of glass fibres, 4.5 parts of montmorillonites, 4 parts of quartz
Powder, 2.5 parts of ceramics, 4 parts of clays, 6 parts of zinc stearates, 3.5 parts of Firebrake ZBs, 2.5 parts of nano silicons, 2.5 parts of micas,
2.5 parts of wollastonites in powder, 3.5 parts of kaolin, 4.5 parts of talcum powder, 3.5 parts of hydroxyethyl celluloses, 2 parts of dolomite dusts, 3.5 parts of phosphoric acid
Aluminum dihydrogen, 2.5 parts of magnesium aluminates, 3.5 parts of magnesia and absolute ethyl alcohol are well mixed, and 2h is stirred under nitrogen protection, is then heated up
To 50 DEG C, add 4.5 parts of tetraethyl orthosilicates, 4.5 parts of VTESs and 6.5 parts of ammoniacal liquor and be well mixed, stir 6h,
Vacuum filter, is washed 3 times with absolute ethyl alcohol, is then added after 4.5 parts of acetylbutyrylcellulose mixing, stirring 30min is changed
Property auxiliary agent.
Embodiment 2
A kind of medical product proposed by the present invention antibacterial 3D printing material, its raw material includes by weight：ABS resin 80
Part, 15 parts of organic epoxy resin, 4 parts of acrylic resin, 6 parts of Lauxite, 2 parts of poly butyric ester, antimicrobial enhancing agent 8
Part, 3 parts of modified zeolite, 5 parts of calcium molybdate, 2 parts of white powder of forging, 6 parts of zeolite powder, 1 part of nitrocotton, 6 parts of trbasic zinc phosphate, 1 part of bentonite, three
Aoxidize 5 parts of two antimony, 3 parts of zinc oxide, 4 parts of seawood meal, 2 parts of diatomite, 12 parts of antimony trioxide, 1 part of zirconium oxide, 6 parts of aluminum sulfate, oxygen
Change 2 parts of aluminium, 5 parts of natrosol, 1 part of lauryl acrylate, 4 parts of trimethyl phosphate, 2 parts of acrylonitrile, silane coupler
4 parts of KH-560,2 parts of sulfonated oil, 9 parts of defoamer, 5 parts of modified additive.
Antimicrobial enhancing agent is prepared by following technique：By weight by 5 parts of urea, 5 parts of polyvinylpyrrolidones and 6 parts
Deionized water is well mixed, and is then added 4 parts of sodium chloride and 2 parts of defoamer stirring 30min, is then added 3 parts of aluminum nitrates and obtain
Material a；8 parts of nano titanium oxides are added into material a with separatory funnel and 3 parts of zirconium sulfates are well mixed, then heating water bath
To 90 DEG C, it is cooled to 2 parts of disodium hydrogen phosphates of addition after room temperature and is well mixed, be then aged, filtration washing, dry, it is cold after calcining
But antimicrobial enhancing agent is obtained to room temperature.
Modified zeolite is prepared by following technique：It is 1% chlorine by weight by 1 part of natural zeolite and 5 parts of mass fractions
Change sodium solution to be well mixed, stir 3h, then filtering means dehydration, drying is calcined 1.5h in 450 DEG C, is subsequently placed in 3 parts of mass fractions
In the lanthanum chloride solution for being 9.0 for 0.5%, pH, 3h is stirred, filtering means dehydration, drying is subsequently placed in 180 DEG C of roasting 1.5h, then
1 part of mass fraction is placed in 0.3% silver nitrate solution, to stir 2h, modified zeolite is obtained after drying.
Modified additive is prepared by following technique：By weight by 5 parts of glass fibres, 6 parts of montmorillonites, 2 parts of silica flour,
4 parts of ceramics, 3 parts of clays, 8 parts of zinc stearates, 2 parts of Firebrake ZBs, 4 parts of nano silicons, 2 parts of micas, 4 parts of wollastonites
Powder, 2 parts of kaolin, 6 parts of talcum powder, 2 parts of hydroxyethyl celluloses, 3 parts of dolomite dusts, 2 parts of aluminium dihydrogen phosphates, 4 parts of magnesium aluminates, 2
Part magnesia and absolute ethyl alcohol are well mixed, and 3h is stirred under nitrogen protection, then heat to 30 DEG C, add 6 parts of positive silicic acid second
Ester, 3 parts of VTESs and 9 parts of ammoniacal liquor are well mixed, and stir 5h, vacuum filter is washed 4 times with absolute ethyl alcohol,
Then add after 3 parts of acetylbutyrylcellulose mixing, stirring 40min obtains modified additive.
Embodiment 3
A kind of medical product proposed by the present invention antibacterial 3D printing material, its raw material includes by weight：ABS resin
100 parts, 5 parts of organic epoxy resin, 9 parts of acrylic resin, 3 parts of Lauxite, 5 parts of poly butyric ester, antimicrobial enhancing agent 4
Part, 6 parts of modified zeolite, 1 part of calcium molybdate, 6 parts of white powder of forging, 2 parts of zeolite powder, 4 parts of nitrocotton, 3 parts of trbasic zinc phosphate, 4 parts of bentonite, three
Aoxidize 2 parts of two antimony, 6 parts of zinc oxide, 1 part of seawood meal, 9 parts of diatomite, 3 parts of antimony trioxide, 5 parts of zirconium oxide, 1 part of aluminum sulfate, oxygen
Change 6 parts of aluminium, 1 part of natrosol, 5 parts of lauryl acrylate, 1 part of trimethyl phosphate, 6 parts of acrylonitrile, silane coupler
1 part of KH-560,5 parts of sulfonated oil, 5 parts of defoamer, 15 parts of modified additive.
Antimicrobial enhancing agent is prepared by following technique：By weight by 15 parts of urea, 3 parts of polyvinylpyrrolidones and 9
Part deionized water is well mixed, and is then added 1 part of sodium chloride and 5 parts of defoamers stirring 10min, is then added 6 parts of aluminum nitrates and obtain
To material a；4 parts of nano titanium oxides being added into material a with separatory funnel and 5 parts of zirconium sulfates being well mixed, then water-bath adds
Heat is cooled to 6 parts of disodium hydrogen phosphates of addition after room temperature and is well mixed, be then aged, filtration washing, dry, after calcining to 70 DEG C
It is cooled to room temperature and obtains antimicrobial enhancing agent.
Modified zeolite is prepared by following technique：It is 3% chlorine by weight by 3 parts of natural zeolites and 2 parts of mass fractions
Change sodium solution to be well mixed, stir 1h, then filtering means dehydration, drying is calcined 0.5h in 550 DEG C, is subsequently placed in 6 parts of mass fractions
In the lanthanum chloride solution for being 10.0 for 0.3%, pH, 1h is stirred, filtering means dehydration, drying is subsequently placed in 220 DEG C of roasting 0.5h, so
After 4 parts of mass fractions are placed in 0.1% silver nitrate solution, to stir 4h, modified zeolite is obtained after drying.
Modified additive is prepared by following technique：By weight by 15 parts of glass fibres, 3 parts of montmorillonites, 6 parts of quartz
Powder, 1 part of ceramic, 5 parts of clays, 4 parts of zinc stearates, 5 parts of Firebrake ZBs, 1 part of nano silicon, 3 parts of micas, 1 part of silicon ash
Stone flour, 5 parts of kaolin, 3 parts of talcum powder, 5 parts of hydroxyethyl celluloses, 1 part of dolomite dust, 5 parts of aluminium dihydrogen phosphates, 1 part of magnesium aluminate,
5 parts of magnesia and absolute ethyl alcohol are well mixed, and 1h is stirred under nitrogen protection, then heat to 70 DEG C, add 3 parts of positive silicic acid second
Ester, 6 parts of VTESs and 4 parts of ammoniacal liquor are well mixed, and stir 7h, vacuum filter is washed 2 times with absolute ethyl alcohol,
Then add after 6 parts of acetylbutyrylcellulose mixing, stirring 20min obtains modified additive.
Embodiment 4
A kind of medical product proposed by the present invention antibacterial 3D printing material, its raw material includes by weight：ABS resin 85
Part, 12 parts of organic epoxy resin, 5 parts of acrylic resin, 5 parts of Lauxite, 3 parts of poly butyric ester, antimicrobial enhancing agent 7
Part, 4 parts of modified zeolite, 4 parts of calcium molybdate, 3 parts of white powder of forging, 5 parts of zeolite powder, 2 parts of nitrocotton, 5 parts of trbasic zinc phosphate, 2 parts of bentonite, three
Aoxidize 4 parts of two antimony, 4 parts of zinc oxide, 3 parts of seawood meal, 3 parts of diatomite, 11 parts of antimony trioxide, 2 parts of zirconium oxide, 5 parts of aluminum sulfate, oxygen
Change 3 parts of aluminium, 4 parts of natrosol, 2 parts of lauryl acrylate, 3 parts of trimethyl phosphate, 3 parts of acrylonitrile, silane coupler
3 parts of KH-560,3 parts of sulfonated oil, 8 parts of defoamer, 8 parts of modified additive.
Antimicrobial enhancing agent is prepared by following technique：By weight by 8 parts of urea, 4.5 parts of polyvinylpyrrolidones and 7
Part deionized water is well mixed, and is then added 3 parts of sodium chloride and 3 parts of defoamers stirring 15-25min, is then added 5 parts of aluminum nitrates
Obtain material a；5 parts of nano titanium oxides are added into material a and 4.5 parts of zirconium sulfates are well mixed, Ran Houshui with separatory funnel
Bath is heated to 75 DEG C, is cooled to 5 parts of disodium hydrogen phosphates of addition after room temperature and is well mixed, is then aged, filtration washing, dries, forge
Room temperature is cooled to after burning and obtains antimicrobial enhancing agent.
Modified zeolite is prepared by following technique：It is by 1.5 parts of natural zeolites and 4 parts of mass fractions by weight
1.5% sodium chloride solution is well mixed, and stirs 2.5h, and then filtering means dehydration, drying is calcined 1.2h in 480 DEG C, is subsequently placed in 4
During part mass fraction is the lanthanum chloride solution that 0.45%, pH is 9.2,2.5h is stirred, filtering means dehydration, drying is subsequently placed in 185 DEG C
1.2h is calcined, is subsequently placed in 2 parts of mass fractions in 0.25% silver nitrate solution, to stir 2.5h, modified zeolite is obtained after drying.
Modified additive is prepared by following technique：By weight by 8 parts of glass fibres, 5 parts of montmorillonites, 3 parts of silica flour,
3 parts of ceramics, 3.5 parts of clays, 7 parts of zinc stearates, 3 parts of Firebrake ZBs, 3 parts of nano silicons, 2.2 parts of micas, 3 parts of silicon ashes
Stone flour, 3 parts of kaolin, 5 parts of talcum powder, 3 parts of hydroxyethyl celluloses, 2.5 parts of dolomite dusts, 3 parts of aluminium dihydrogen phosphates, 3 parts of aluminic acids
Magnesium, 3 parts of magnesia and absolute ethyl alcohol are well mixed, and 2.5h is stirred under nitrogen protection, then heat to 35 DEG C, are adding 5 parts just
Silester, 4 parts of VTESs and 8 parts of ammoniacal liquor are well mixed, and stir 5.5h, vacuum filter uses absolute ethyl alcohol
Washing 4 times, is then added after 4 parts of acetylbutyrylcellulose mixing, stirring 35min obtains modified additive.
Embodiment 5
A kind of medical product proposed by the present invention antibacterial 3D printing material, its raw material includes by weight：ABS resin 95
Part, 8 parts of organic epoxy resin, 8 parts of acrylic resin, 4 parts of Lauxite, 4 parts of poly butyric ester, 5 parts of antimicrobial enhancing agent,
5 parts of modified zeolite, 2 parts of calcium molybdate, 5 parts of white powder of forging, 3 parts of zeolite powder, 3 parts of nitrocotton, 4 parts of trbasic zinc phosphate, 3 parts of bentonite, three oxygen
Change 3 parts of two antimony, 5 parts of zinc oxide, 2 parts of seawood meal, 8 parts of diatomite, 4 parts of antimony trioxide, 4 parts of zirconium oxide, 2 parts of aluminum sulfate, oxidation
5 parts of aluminium, 2 parts of natrosol, 4 parts of lauryl acrylate, 2 parts of trimethyl phosphate, 5 parts of acrylonitrile, silane coupler KH-
560 2 parts, 4 parts of sulfonated oil, 6 parts of defoamer, 12 parts of modified additive.
Antimicrobial enhancing agent is prepared by following technique：By weight by 12 parts of urea, 3.5 parts of polyvinylpyrrolidones and
8 parts of deionized waters are well mixed, and are then added 2 parts of sodium chloride and 4 parts of defoamer stirring 15min, are then added 5 parts of aluminum nitrates and obtain
To material a；5 parts of nano titanium oxides are added into material a and 4.5 parts of zirconium sulfates are well mixed, then water-bath with separatory funnel
75 DEG C are heated to, 5 parts of disodium hydrogen phosphates of addition after room temperature is cooled to and is well mixed, be then aged, filtration washing, dry, calcining
After be cooled to room temperature and obtain antimicrobial enhancing agent.
Modified zeolite is prepared by following technique：It is by 2.5 parts of natural zeolites and 3 parts of mass fractions by weight
2.5% sodium chloride solution is well mixed, and stirs 1.5h, and then filtering means dehydration, drying is calcined 0.8h in 520 DEG C, is subsequently placed in 5
During part mass fraction is the lanthanum chloride solution that 0.35%, pH is 9.8,1.5h is stirred, filtering means dehydration, drying is subsequently placed in 215 DEG C
0.8h is calcined, is subsequently placed in 3 parts of mass fractions in 0.15% silver nitrate solution, to stir 3.5h, modified zeolite is obtained after drying.
Modified additive is prepared by following technique：By weight by 12 parts of glass fibres, 4 parts of montmorillonites, 5 parts of quartz
Powder, 2 parts of ceramics, 4.5 parts of clays, 5 parts of zinc stearates, 4 parts of Firebrake ZBs, 2 parts of nano silicons, 2.8 parts of micas, 2 parts
Wollastonite in powder, 4 parts of kaolin, 4 parts of talcum powder, 4 parts of hydroxyethyl celluloses, 1.5 parts of dolomite dusts, 4 parts of aluminium dihydrogen phosphates, 2 parts
Magnesium aluminate, 4 parts of magnesia and absolute ethyl alcohol are well mixed, and 1.5h is stirred under nitrogen protection, then heat to 65 DEG C, add 4
Part tetraethyl orthosilicate, 5 parts of VTESs and 5 parts of ammoniacal liquor are well mixed, and stir 6.5h, vacuum filter, with anhydrous
Ethanol is washed 2 times, is then added after 5 parts of acetylbutyrylcellulose mixing, stirring 25min obtains modified additive.
The foregoing is only a preferred embodiment of the present invention, but protection scope of the present invention be not limited thereto,
Any one skilled in the art the invention discloses technical scope in, technique according to the invention scheme and its
Inventive concept is subject to equivalent substitution or change, should all be included within the scope of the present invention.
Claims (8)
1. a kind of medical product antibacterial 3D printing material, it is characterised in that its raw material includes by weight：ABS resin 80-
100 parts, organic epoxy resin 5-15 parts, it is 4-9 parts of acrylic resin, 3-6 parts of Lauxite, 2-5 parts of poly butyric ester, anti-
4-8 parts of bacterium reinforcing agent, 3-6 parts of modified zeolite, 1-5 parts of calcium molybdate, forging 2-6 parts of white powder, 2-6 parts of zeolite powder, 1-4 parts of nitrocotton,
3-6 parts of trbasic zinc phosphate, 1-4 parts of bentonite, 2-5 parts of antimony oxide, 3-6 parts of zinc oxide, 1-4 parts of seawood meal, 2-9 parts of diatomite,
3-12 parts of antimony trioxide, 1-5 parts of zirconium oxide, 1-6 parts of aluminum sulfate, 2-6 parts of aluminum oxide, 1-5 parts of natrosol, acrylic acid
1-5 parts of lauryl, 1-4 parts of trimethyl phosphate, 2-6 parts of acrylonitrile, KH-5601-4 parts of silane coupler, 2-5 parts of sulfonated oil, disappear
5-9 parts of infusion, 5-15 parts of modified additive.
2. medical product according to claim 1 antibacterial 3D printing material, it is characterised in that the raw material of antimicrobial enhancing agent
Include by weight：5-15 parts of urea, 3-5 parts of polyvinylpyrrolidone, 6-9 parts of deionized water, 1-4 parts of sodium chloride, defoamer
2-5 parts, 3-6 parts of aluminum nitrate, 4-8 parts of nano titanium oxide, 3-5 parts of zirconium sulfate, 2-6 parts of disodium hydrogen phosphate.
3. medical product according to claim 1 or 2 antibacterial 3D printing material, it is characterised in that antimicrobial enhancing agent is pressed
It is prepared by following technique：Urea, polyvinylpyrrolidone and deionized water are well mixed, sodium chloride and froth breaking is then added
10-30min is stirred in agent, is then added aluminum nitrate and is obtained material a；Added with separatory funnel into material a nano titanium oxide and
Zirconium sulfate is well mixed, and then heating water bath is cooled to addition disodium hydrogen phosphate after room temperature and be well mixed, then to 70-90 DEG C
Ageing, filtration washing is dried, is cooled to room temperature after calcining and obtains antimicrobial enhancing agent.
4. the medical product antibacterial 3D printing material according to claim any one of 1-3, it is characterised in that modified zeolite
Prepared by following technique：Natural zeolite and sodium chloride solution are well mixed, 1-3h is stirred, filtering means dehydration is dried, then
0.5-1.5h is calcined in 450-550 DEG C, is subsequently placed in lanthanum chloride solution, 1-3h is stirred, filtering means dehydration, drying is subsequently placed in
180-220 DEG C of roasting 0.5-1.5h, is subsequently placed in silver nitrate solution, stirs 2-4h, modified zeolite is obtained after drying.
5. the medical product antibacterial 3D printing material according to claim any one of 1-4, it is characterised in that modified zeolite
Preparation technology in, the mass fraction of sodium chloride solution is 1-3%；The mass fraction of lanthanum chloride solution is 0.3-0.5%, and pH is
9.0-10.0；The mass fraction of silver nitrate solution is 0.1-0.3%.
6. the medical product antibacterial 3D printing material according to claim any one of 1-5, it is characterised in that modified zeolite
Preparation technology in, natural zeolite, sodium chloride solution, the weight ratio of lanthanum chloride solution and silver nitrate solution are 1-3：2-5：3-6：
1-4。
7. the medical product antibacterial 3D printing material according to claim any one of 1-6, it is characterised in that modified additive
Raw material include by weight：5-15 parts of glass fibre, 3-6 parts of montmorillonite, 2-6 parts of silica flour, 1-4 parts of ceramic, clay
3-5 parts, it is 4-8 parts of zinc stearate, 2-5 parts of Firebrake ZB, 1-4 parts of nano silicon, 2-3 parts of mica, 1-4 parts of wollastonite in powder, high
2-5 parts of ridge soil, 3-6 parts of talcum powder, 2-5 parts of hydroxyethyl cellulose, 1-3 parts of dolomite dust, 2-5 parts of aluminium dihydrogen phosphate, magnesium aluminate
1-4 parts, 2-5 parts of magnesia, 3-6 parts of tetraethyl orthosilicate, 3-6 parts of VTES, 4-9 parts of ammoniacal liquor, acetate butyrate
3-6 parts of cellulose.
8. the medical product antibacterial 3D printing material according to claim any one of 1-7, it is characterised in that modified additive
Prepared by following technique：By glass fibre, montmorillonite, silica flour, ceramic, clay, zinc stearate, Firebrake ZB, receive
Rice silica, mica, wollastonite in powder, kaolin, talcum powder, hydroxyethyl cellulose, dolomite dust, aluminium dihydrogen phosphate, aluminic acid
Magnesium, magnesia and absolute ethyl alcohol are well mixed, and 1-3h is stirred under nitrogen protection, then heat to 30-70 DEG C, add positive silicic acid
Ethyl ester, VTES and ammoniacal liquor are well mixed, stir 5-7h, and vacuum filter is washed 2-4 times with absolute ethyl alcohol,
Then add after acetylbutyrylcellulose mixing, stirring 20-40min obtains modified additive.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107603175A (en) * | 2017-09-14 | 2018-01-19 | 芜湖林电子科技有限公司 | A kind of Medical Devices antibacterial oil resistant 3D printing material |
| CN107916564A (en) * | 2017-11-25 | 2018-04-17 | 长沙秋点兵信息科技有限公司 | Embroidery thread for three-dimensional embroidery and preparation method thereof |
| CN108485149A (en) * | 2018-03-22 | 2018-09-04 | 长沙小新新能源科技有限公司 | A kind of high hydroscopic resin and preparation method thereof |
| CN108532354A (en) * | 2018-03-22 | 2018-09-14 | 长沙小新新能源科技有限公司 | A kind of toilet paper and preparation method thereof |
| CN108522540A (en) * | 2018-03-19 | 2018-09-14 | 长沙秋点兵信息科技有限公司 | Copper humate-containing antibacterial yield-increasing composition and preparation method thereof |
| CN109172410A (en) * | 2018-11-17 | 2019-01-11 | 长沙浩然医疗科技有限公司 | A kind of foundation emulsion and preparation method thereof that antibiotic property is good |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107603175A (en) * | 2017-09-14 | 2018-01-19 | 芜湖林电子科技有限公司 | A kind of Medical Devices antibacterial oil resistant 3D printing material |
| CN107916564A (en) * | 2017-11-25 | 2018-04-17 | 长沙秋点兵信息科技有限公司 | Embroidery thread for three-dimensional embroidery and preparation method thereof |
| CN108522540A (en) * | 2018-03-19 | 2018-09-14 | 长沙秋点兵信息科技有限公司 | Copper humate-containing antibacterial yield-increasing composition and preparation method thereof |
| CN108485149A (en) * | 2018-03-22 | 2018-09-04 | 长沙小新新能源科技有限公司 | A kind of high hydroscopic resin and preparation method thereof |
| CN108532354A (en) * | 2018-03-22 | 2018-09-14 | 长沙小新新能源科技有限公司 | A kind of toilet paper and preparation method thereof |
| CN109172410A (en) * | 2018-11-17 | 2019-01-11 | 长沙浩然医疗科技有限公司 | A kind of foundation emulsion and preparation method thereof that antibiotic property is good |
| CN110169730A (en) * | 2019-05-24 | 2019-08-27 | 江苏三乔智能科技有限公司 | A kind of portable toilet |
| CN111084928A (en) * | 2019-12-13 | 2020-05-01 | 刘敏 | Prostate treatment device based on temperature partition |
| CN116143409A (en) * | 2023-02-06 | 2023-05-23 | 福建省德化县紫嘉工艺有限公司 | Formula and preparation method of sand glaze for ceramic appliance surface |
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