CN109135260A - A kind of circuit board antibacterial corrosion resistant composite material and preparation method - Google Patents

A kind of circuit board antibacterial corrosion resistant composite material and preparation method Download PDF

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CN109135260A
CN109135260A CN201811003166.3A CN201811003166A CN109135260A CN 109135260 A CN109135260 A CN 109135260A CN 201811003166 A CN201811003166 A CN 201811003166A CN 109135260 A CN109135260 A CN 109135260A
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circuit board
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CN109135260B (en
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不公告发明人
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Shenzhen Jinglai New Material Technology Co ltd
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Shenzhen Nan Shuo Ming Tai Technology Co Ltd
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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
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • 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
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C08K2003/0806—Silver
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C08K2003/265—Calcium, strontium or barium carbonate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
    • C08K2003/3045—Sulfates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives
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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
    • C08K2201/013—Additives applied to the surface of polymers or polymer particles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets
    • 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

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Abstract

The invention discloses a kind of circuit board antibacterial corrosion resistant composite materials, are prepared by the primary raw material of following parts by weight: 80-100 parts of aqueous polyurethane, 20-30 parts of filler, 10-15 parts of waste and old circuit board, 10-15 parts of deionized water, 30-40 parts of ethyl alcohol, 4-7 parts of ammonium hydroxide, 4-6 parts of ethyl orthosilicate, 5-8 parts of A151 silane coupling agent, 8-10 parts of antibacterial microballoon, 2-3 parts of antioxidant, 2-3 parts of dimethicone, 1-2 parts of cobalt iso-octoate, 3-5 parts of methyl ethyl ketone peroxide；The invention also discloses the circuit board preparation methods of antibacterial corrosion resistant composite material.The present invention is polymeric matrix by using aqueous polyurethane, use filler and waste and old circuit board for main material, it is aided with the antibacterial microballoon and processing aid of scientific matching again, the circuit board being prepared is on the basis of having good use and mechanical property, with excellent antibacterial corrosion resistance, during use the service life of circuit board is not able to ascend vulnerable to microbial attack.

Description

A kind of circuit board antibacterial corrosion resistant composite material and preparation method
Technical field
The invention belongs to circuit board technical field of composite materials, and in particular, to a kind of circuit board is multiple with antibacterial corrosion resistant Condensation material and preparation method thereof.
Background technique
As electronic product develops to the direction of miniaturization, digitlization, high frequency, high reliability, high frequency metal base electricity Road plate has more other than possessing the excellent high-fire resistance of common metal base circuit board, high-cooling property, excellent dimensional stability High frequency, insulating medium layer have good intensity, flexibility and resistance to high breakdown voltage.
Polyurethane not only possesses brilliant high-tension, high-tensile strength, tough and ageing-resistant characteristic, but also is mature environmental protection Material has been widely used in the fields such as electronic apparatus, automobile, articles for daily use at present.But exist in polyether polyols big The ester bond and urea bond of amount, the greasy dirt adsorbed during use, sweat stain etc. can provide nutrition abundant for the growth of microorganism And the energy, polyurethane material easily by microbial attack, accelerates the aging of polyurethane material during use, when it is used as Have the defects that antibiotic property is not good enough when circuit board material, declines the service life of circuit board.
Summary of the invention
The purpose of the present invention is to provide a kind of circuit board antibacterial corrosion resistant composite material and preparation method, by using Aqueous polyurethane is polymeric matrix, uses filler and waste and old circuit board for main material, then is aided with the antibacterial microballoon of scientific matching And processing aid, the circuit board being prepared are resistance to excellent antibacterial on the basis of having good use and mechanical property Corrosive nature is not able to ascend the service life of circuit board vulnerable to microbial attack during use.
The purpose of the present invention can be achieved through the following technical solutions:
A kind of circuit board antibacterial corrosion resistant composite material, is prepared: aqueous poly- ammonia by the primary raw material of following parts by weight 80-100 parts of ester, 20-30 parts of filler, 10-15 parts of waste and old circuit board, 10-15 parts of deionized water, 30-40 parts of ethyl alcohol, ammonium hydroxide 4-7 Part, 4-6 parts of ethyl orthosilicate, 5-8 parts of A151 silane coupling agent, 8-10 parts of antibacterial microballoon, 2-3 parts of antioxidant, dimethicone 2-3 parts, 1-2 parts of cobalt iso-octoate, 3-5 parts of methyl ethyl ketone peroxide；
The composite material is prepared by following steps:
Step S1, after waste and old circuit board being mechanically pulverized, washing shaking table handles to obtain waste printed circuit board nonmetal powder body, Then powder is removed into large-sized impurity by 20 meshes, ball-milling treatment is crushed with planetary ball mill, by the powder after ball milling Body crosses 200 meshes, is placed in 55 DEG C of vacuum ovens dry 10h, obtains dry powder；
Step S2, it toward the dehydrated alcohol and ammonium hydroxide of addition deionized water, half in dry powder, is stirred at 60 DEG C Then ethyl orthosilicate is slowly added dropwise with constant pressure funnel in 30min, centrifuge washing is to neutrality after reacting 135min, at 110 DEG C Vacuum oven 7h；
Step S3, the powder after taking drying is distributed in remaining half dehydrated alcohol, and A151 silane coupling agent is added, 10h is stirred to react at 80 DEG C, centrifuge washing three times, obtains modified powder；
Step S4, modified powder, antibacterial microballoon, filler are mixed with aqueous polyurethane, at room temperature high-speed stirred, after 3h Dimethicone ultrasonic bubble removing is added, sequentially adds antioxidant, cobalt iso-octoate and methyl ethyl ketone peroxide, then vacuum suction 10min is steeped, pours into Teflon mould, room temperature curing 120min, in 70 DEG C of air dry oven, solidifies 5h afterwards, is made Obtain circuit board antibacterial corrosion resistant composite material.
Further, the filler includes nanometer calcium carbonate, wollastonite, barium sulfate, hydroxyapatite, nanometer calcium carbonate, Wollastonite, barium sulfate, hydroxyapatite mass ratio be 10:2-3:4-6:1-2.
Further, the antioxidant includes zinc dialkyl dithiophosphate, triphenyl phosphite, ultraviolet absorbing agent UV-531, zinc dialkyl dithiophosphate, triphenyl phosphite, ultraviolet absorbent UV-531 are 10:1- according to mass ratio 2:8-9 is compounded.
Further, the antibacterial microballoon is prepared by the following method:
(1) it measures 120mL dehydrated alcohol to be placed in a beaker, 3.1g nano-TiO is added2, magnetic agitation 25min received Rice TiO2Alcohol suspending liquid, by nano-TiO2Alcohol suspending liquid ultrasonic disperse 30min；
(2) N methyldiethanol amine of the Sodium Acid Pyrophosphate, 4.6g that weigh 5.0g is added in above-mentioned suspension, often Temperature stirring 30min, re-ultrasonic dispersion 30min, carry out centrifugal treating to suspension after the completion, are subsequently placed in 38 DEG C of vacuum ovens Middle dry 22h takes out grinding, crosses 650 meshes, and modified Nano TiO is made2Fine powder；
(3) in the 200mL distilled water of high-speed stirred shearing, 1-2min is stood after being slowly added to 30mg sodium alginate, is made Sodium alginate is completely dissolved to form uniform sodium alginate soln, spare；It is added in the 5.6% of 200mL aqueous acetic acid 20mg chitosan, stirring and dissolving is complete, obtains chitosan aqueous acetic acid, spare；
(4) it takes 3.6g rosin glycerides and 6.8g soybean oil in beaker, 12min is stirred in 46 DEG C of water-baths；Then plus Enter 100mL sodium alginate soln, stirs 30min；Add 37mg Ag nano particles and the modified TiO of 52mg2Fine powder, ultrasonic disperse 35min, adds 1.5g stearoyl lactate, and stirring and emulsifying 3h pours into 30mL acetone stirring 10min, stand after reaction Layering；
(5) lower layer's milky emulsion is added in 150mL chitosan aqueous acetic acid simultaneously magnetic agitation 30min, finally It is centrifuged 20min, is washed with distilled water product 3 times, antibacterial microballoon is made after freeze-drying.
A kind of circuit board preparation method of antibacterial corrosion resistant composite material, includes the following steps:
Step S1, after waste and old circuit board being mechanically pulverized, washing shaking table handles to obtain waste printed circuit board nonmetal powder body, Then powder is removed into large-sized impurity by 20 meshes, ball-milling treatment is crushed with planetary ball mill, by the powder after ball milling Body crosses 200 meshes, is placed in 55 DEG C of vacuum ovens dry 10h, obtains dry powder；
Step S2, it toward the dehydrated alcohol and ammonium hydroxide of addition deionized water, half in dry powder, is stirred at 60 DEG C Then ethyl orthosilicate is slowly added dropwise with constant pressure funnel in 30min, centrifuge washing is to neutrality after reacting 135min, at 110 DEG C Vacuum oven 7h；
Step S3, the powder after taking drying is distributed in remaining half dehydrated alcohol, and A151 silane coupling agent is added, 10h is stirred to react at 80 DEG C, centrifuge washing three times, obtains modified powder；
Step S4, modified powder, antibacterial microballoon, filler are mixed with aqueous polyurethane, at room temperature high-speed stirred, after 3h Dimethicone ultrasonic bubble removing is added, sequentially adds antioxidant, cobalt iso-octoate and methyl ethyl ketone peroxide, then vacuum suction 10min is steeped, pours into Teflon mould, room temperature curing 120min, in 70 DEG C of air dry oven, solidifies 5h afterwards, is made Obtain circuit board antibacterial corrosion resistant composite material.
Beneficial effects of the present invention:
(1) present invention is added to antibacterial microballoon in composite material raw material, passes through sodium alginate and Chitosan-coated nanometer The microballoon that Ag particle and modified TiO2 are prepared, wherein nano-TiO can be improved in the doping of Ag2Photocatalytic activity, on the one hand Due to the d track and TiO of the Ag of doping2The conduction band overlapping of the d track of Ti ion, makes TiO in lattice2Conduction band wideization move down, prohibit The band gap of band narrows, and then TiO2Visible light, under visible light illumination, TiO can be absorbed2It can produce light induced electron and hole, it is another Aspect, Ag+ are the receiving body of electronics, can capture the electronics in conduction band, and then inhibit TiO2Surface electronic and hole it is compound, Make TiO2With more photoholes and the more hydroxyl radical free radicals of its surface hydroxyl generation are aoxidized, hydroxyl radical free radical is a kind of Strong oxidizer, can enter bacterial cell internal influence cell metabolism inactivates thallus, meanwhile, the Ag+ that Ag ionization generates It may act on bacterium, therefore antibacterial microballoon has stronger antibacterial activity under visible light illumination；In addition, antibacterial microballoon is to use Effective antimicrobial component is embedded in shell by sodium alginate and chitosan as Shell Materials, can make to be embedded in antibacterial microballoon Nanometer Ag and nano-TiO2Slow release, long acting antibiotic；
(2) present invention reaches the recycling of resource, reduction is produced into using waste and old circuit board as one of main material matter This；Meanwhile waste and old circuit board is handled, make waste and old circuit board powder nonloaded silica nanoparticle, powder surface One layer of uniform silica protrusion is generated, this kind of protrusion significantly increases the specific surface area of powder, and modified powder is added to After polymeric matrix (aqueous polyurethane), the contact area between polymeric matrix will be significantly improved, and can effectively be fettered More polymer molecular chains play facilitation to the improvement of composite materials property；Meanwhile the addition of silane coupling agent It enables to the interaction between modified powder and matrix to be further enhanced, point of more unsaturated polyester (UP)s can be limited Subchain, to enhance interface cohesion effect, stress can be effectively passed to filler surface, to make the mechanical property of composite material It gets a promotion；
(3) composite material of the invention uses aqueous polyurethane for polymeric matrix, use filler and waste and old circuit board for Main material matter, then it is aided with the antibacterial microballoon and processing aid of scientific matching, the circuit board being prepared has good use and power On the basis of learning performance, there is excellent antibacterial corrosion resistance, during use not vulnerable to microbial attack, Neng Gouti Rise the service life of circuit board.
Specific embodiment
Technical solution of the present invention is clearly and completely described below in conjunction with embodiment, it is clear that described reality Applying example is only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, this field is general Logical technical staff all other embodiment obtained without creative efforts belongs to what the present invention protected Range.
A kind of circuit board antibacterial corrosion resistant composite material, is prepared: aqueous poly- ammonia by the primary raw material of following parts by weight 80-100 parts of ester, 20-30 parts of filler, 10-15 parts of waste and old circuit board, 10-15 parts of deionized water, 30-40 parts of ethyl alcohol, ammonium hydroxide 4-7 Part, 4-6 parts of ethyl orthosilicate, 5-8 parts of A151 silane coupling agent, 8-10 parts of antibacterial microballoon, 2-3 parts of antioxidant, dimethicone 2-3 parts, 1-2 parts of cobalt iso-octoate, 3-5 parts of methyl ethyl ketone peroxide；
Wherein, the aqueous polyurethane solid content 29 ± 1 (%), 800Cpa/25 DEG C of viscosity；
The filler includes nanometer calcium carbonate, wollastonite, barium sulfate, hydroxyapatite, nanometer calcium carbonate, wollastonite, sulphur Sour barium, hydroxyapatite mass ratio be 10:2-3:4-6:1-2；
The antioxidant includes zinc dialkyl dithiophosphate, triphenyl phosphite, ultraviolet absorbent UV-531, dioxane Base zinc dithiophosphate, triphenyl phosphite, ultraviolet absorbent UV-531 according to mass ratio be 10:1-2:8-9 compound and At；
The antibacterial microballoon is prepared by the following method:
(1) it measures 120mL dehydrated alcohol to be placed in a beaker, 3.1g nano-TiO is added2, magnetic agitation 25min received Rice TiO2Alcohol suspending liquid, by nano-TiO2Alcohol suspending liquid ultrasonic disperse 30min；
(2) N methyldiethanol amine of the Sodium Acid Pyrophosphate, 4.6g that weigh 5.0g is added in above-mentioned suspension, often Temperature stirring 30min, re-ultrasonic dispersion 30min, carry out centrifugal treating to suspension after the completion, are subsequently placed in 38 DEG C of vacuum ovens Middle dry 22h takes out grinding, crosses 650 meshes, and modified Nano TiO is made2Fine powder；
To nano-TiO2It is modified to carry out surface, can be improved its dispersion effect；
(3) in the 200mL distilled water of high-speed stirred shearing, 1-2min is stood after being slowly added to 30mg sodium alginate, is made Sodium alginate is completely dissolved to form uniform sodium alginate soln, spare；It is added in the 5.6% of 200mL aqueous acetic acid 20mg chitosan, stirring and dissolving is complete, obtains chitosan aqueous acetic acid, spare；
(4) it takes 3.6g rosin glycerides and 6.8g soybean oil in beaker, 12min is stirred in 46 DEG C of water-baths；Then plus Enter 100mL sodium alginate soln, stirs 30min；Add 37mg Ag nano particles and the modified TiO of 52mg2Fine powder, ultrasonic disperse 35min, adds 1.5g stearoyl lactate, and stirring and emulsifying 3h pours into 30mL acetone stirring 10min, stand after reaction Layering；
(5) lower layer's milky emulsion is added in 150mL chitosan aqueous acetic acid simultaneously magnetic agitation 30min, finally It is centrifuged 20min, is washed with distilled water product 3 times, antibacterial microballoon is made after freeze-drying；
Ag and its oxide ionize out Ag+ in liquid phase environment, and positively charged Ag+ can be with the egg in bacterial cell outer membrane White enzyme (having negatively charged mercapto in protease) specifically binds, and effectively pierces through bacteria cell wall and cell Film further makes bacterial cell that can not breathe, be metabolized, breed because of protein denaturation, to achieve the effect that sterilizing；Ag's mixes It is miscellaneous that nano-TiO can be improved2Photocatalytic activity, on the one hand due to the d track and TiO of the Ag of doping2The d rail of Ti ion in lattice The conduction band in road is overlapped, and makes TiO2Conduction band wideization move down, the band gap of forbidden band narrows, and then TiO2Visible light can be absorbed, in visible light Under irradiation, TiO2It can produce light induced electron and hole, on the other hand, Ag+ is the receiving body of electronics, can capture the electricity in conduction band Son, and then inhibit TiO2Surface electronic and hole it is compound, make TiO2With more photoholes and aoxidize its surface hydroxyl More hydroxyl radical free radicals are generated, hydroxyl radical free radical is a kind of strong oxidizer, and it is newly old can to enter bacterial cell internal influence cell Metabolism inactivates thallus, meanwhile, the Ag+ that Ag ionization generates may also act on bacterium, therefore antibacterial microballoon is under visible light illumination With stronger antibacterial activity；In addition, antibacterial microballoon is as Shell Materials using sodium alginate and chitosan by effective antibacterial Ingredient is embedded in shell, can make the nanometer Ag being embedded in antibacterial microballoon and nano-TiO2Slow release, long acting antibiotic；
The preparation method of the composite material, includes the following steps:
Step S1, after waste and old circuit board being mechanically pulverized, washing shaking table handles to obtain waste printed circuit board nonmetal powder body, Then powder is removed into large-sized impurity by 20 meshes, ball-milling treatment is crushed with planetary ball mill, by the powder after ball milling Body crosses 200 meshes, is placed in 55 DEG C of vacuum ovens dry 10h, obtains dry powder；
Step S2, it toward the dehydrated alcohol and ammonium hydroxide of addition deionized water, half in dry powder, is stirred at 60 DEG C Then ethyl orthosilicate is slowly added dropwise with constant pressure funnel in 30min, centrifuge washing is to neutrality after reacting 135min, at 110 DEG C Vacuum oven 7h；
Step S3, the powder after taking drying is distributed in remaining half dehydrated alcohol, and A151 silane coupling agent is added, 10h is stirred to react at 80 DEG C, centrifuge washing three times, obtains modified powder；
Step S4, modified powder, antibacterial microballoon, filler are mixed with aqueous polyurethane, at room temperature high-speed stirred, after 3h Dimethicone ultrasonic bubble removing is added, sequentially adds antioxidant, cobalt iso-octoate and methyl ethyl ketone peroxide, then vacuum suction 10min is steeped, pours into Teflon mould, room temperature curing 120min, in 70 DEG C of air dry oven, solidifies 5h afterwards, is made Obtain circuit board antibacterial corrosion resistant composite material；
Ethyl orthosilicate can decomposite silica in water, after nonloaded silica nanoparticle, waste and old circuit board Powder surface generates one layer of uniform silica protrusion, and this kind of protrusion significantly increases the specific surface area of powder, modified powder After body is added to polymeric matrix (aqueous polyurethane), the contact area between polymeric matrix will be significantly improved, Neng Gouyou Effect ground fetters more polymer molecular chains, plays facilitation to the improvement of composite materials property；Meanwhile it is silane coupled The addition of agent enables to the interaction between modified powder and matrix to be further enhanced, and can limit more how unsaturated The strand of polyester, to enhance interface cohesion effect, stress can be effectively passed to filler surface, to make composite material Mechanical property gets a promotion.
Embodiment 1
A kind of circuit board antibacterial corrosion resistant composite material, is prepared: aqueous poly- ammonia by the primary raw material of following parts by weight 80 parts of ester, 20 parts of filler, 10 parts of waste and old circuit board, 10 parts of deionized water, 30 parts of ethyl alcohol, 4 parts of ammonium hydroxide, 4 parts of ethyl orthosilicate, 5 parts of A151 silane coupling agent, 8 parts of antibacterial microballoon, 2 parts of antioxidant, 2 parts of dimethicone, 1 part of cobalt iso-octoate, peroxidating first and second 3 parts of ketone；
The filler includes nanometer calcium carbonate, wollastonite, barium sulfate, hydroxyapatite, nanometer calcium carbonate, wollastonite, sulphur Sour barium, hydroxyapatite mass ratio be 10:2:4:1；
The antioxidant includes zinc dialkyl dithiophosphate, triphenyl phosphite, ultraviolet absorbent UV-531, dioxane Base zinc dithiophosphate, triphenyl phosphite, ultraviolet absorbent UV-531 are that 10:1:8 is compounded according to mass ratio；
The composite material that embodiment 1 is prepared is respectively 4ug/mL, 8ug/mL to MIC, MBC of Escherichia coli, to gold MIC, MBC of staphylococcus aureus are respectively 8ug/mL, 16ug/mL, and MIC, MBC to pseudomonas aeruginosa are respectively 7ug/ mL,15ug/mL；
Embodiment 2
A kind of circuit board antibacterial corrosion resistant composite material, is prepared: aqueous poly- ammonia by the primary raw material of following parts by weight 90 parts of ester, 25 parts of filler, 13 parts of waste and old circuit board, 12 parts of deionized water, 35 parts of ethyl alcohol, 5 parts of ammonium hydroxide, 5 parts of ethyl orthosilicate, 7 parts of A151 silane coupling agent, 9 parts of antibacterial microballoon, 2.5 parts of antioxidant, 2.5 parts of dimethicone, 1.5 parts of cobalt iso-octoate, peroxide Change 4 parts of methyl ethyl ketone；
The filler includes nanometer calcium carbonate, wollastonite, barium sulfate, hydroxyapatite, nanometer calcium carbonate, wollastonite, sulphur Sour barium, hydroxyapatite mass ratio be 10:2.5:5:1.5；
The antioxidant includes zinc dialkyl dithiophosphate, triphenyl phosphite, ultraviolet absorbent UV-531, dioxane Base zinc dithiophosphate, triphenyl phosphite, ultraviolet absorbent UV-531 according to mass ratio be 10:1.5:8.5 compound and At；
The composite material that embodiment 2 is prepared is respectively 10ug/mL, 16ug/mL to MIC, MBC of Escherichia coli, right MIC, MBC of staphylococcus aureus are respectively 15ug/mL, 24ug/mL, and MIC, MBC to pseudomonas aeruginosa are respectively 17ug/mL,22ug/mL；
Embodiment 3
A kind of circuit board antibacterial corrosion resistant composite material, is prepared: aqueous poly- ammonia by the primary raw material of following parts by weight 100 parts of ester, 30 parts of filler, 15 parts of waste and old circuit board, 15 parts of deionized water, 40 parts of ethyl alcohol, 7 parts of ammonium hydroxide, 6 parts of ethyl orthosilicate, 8 parts of A151 silane coupling agent, 10 parts of antibacterial microballoon, 3 parts of antioxidant, 3 parts of dimethicone, 2 parts of cobalt iso-octoate, peroxidating first and second 5 parts of ketone；
The filler includes nanometer calcium carbonate, wollastonite, barium sulfate, hydroxyapatite, nanometer calcium carbonate, wollastonite, sulphur Sour barium, hydroxyapatite mass ratio be 10:3:6:2；
The antioxidant includes zinc dialkyl dithiophosphate, triphenyl phosphite, ultraviolet absorbent UV-531, dioxane Base zinc dithiophosphate, triphenyl phosphite, ultraviolet absorbent UV-531 are that 10:2:9 is compounded according to mass ratio；
The composite material that embodiment 3 is prepared is respectively 7ug/mL, 12ug/mL to MIC, MBC of Escherichia coli, to gold MIC, MBC of staphylococcus aureus are respectively 11ug/mL, 20ug/mL, and MIC, MBC to pseudomonas aeruginosa are respectively 15ug/ mL,19ug/mL；
The composite material that the present invention is prepared to the MIC (minimum inhibitory concentration) of Escherichia coli, (minimum bactericidal is dense by MBC Degree) it is respectively 4-10ug/mL, 8-16ug/mL, MIC, MBC to staphylococcus aureus are respectively 8-15ug/mL, 16- 24ug/mL, MIC, MBC to pseudomonas aeruginosa are respectively 7-17ug/mL, 15-22ug/mL, with excellent antibacterial, sterilization Performance.
Present invention disclosed above preferred embodiment is only intended to help to illustrate the present invention.There is no detailed for preferred embodiment All details are described, are not limited the invention to the specific embodiments described.Obviously, according to the content of this specification, It can make many modifications and variations.These embodiments are chosen and specifically described to this specification, is in order to better explain the present invention Principle and practical application, so that skilled artisan be enable to better understand and utilize the present invention.The present invention is only It is limited by claims and its full scope and equivalent.

Claims (5)

1. a kind of circuit board antibacterial corrosion resistant composite material, which is characterized in that be prepared by the primary raw material of following parts by weight: 80-100 parts of aqueous polyurethane, 20-30 parts of filler, 10-15 parts of waste and old circuit board, 10-15 parts of deionized water, 30-40 parts of ethyl alcohol, 4-7 parts of ammonium hydroxide, 4-6 parts of ethyl orthosilicate, 5-8 parts of A151 silane coupling agent, 8-10 parts of antibacterial microballoon, 2-3 parts of antioxidant, diformazan 2-3 parts of base silicone oil, 1-2 parts of cobalt iso-octoate, 3-5 parts of methyl ethyl ketone peroxide；
The composite material is prepared by following steps:
Step S1, after waste and old circuit board being mechanically pulverized, washing shaking table handles to obtain waste printed circuit board nonmetal powder body, then By powder by 20 meshes, remove large-sized impurity, ball-milling treatment is crushed with planetary ball mill, by the powder mistake after ball milling 200 meshes are placed in 55 DEG C of vacuum ovens dry 10h, obtain dry powder；
Step S2, toward the dehydrated alcohol and ammonium hydroxide of addition deionized water, half in dry powder, 30min is stirred at 60 DEG C, so Ethyl orthosilicate is slowly added dropwise with constant pressure funnel afterwards, centrifuge washing is dried to neutrality in 110 DEG C of vacuum after reacting 135min Dry 7h in case；
Step S3, the powder after taking drying is distributed in remaining half dehydrated alcohol, A151 silane coupling agent is added, at 80 DEG C Under be stirred to react 10h, centrifuge washing three times, obtains modified powder；
Step S4, modified powder, antibacterial microballoon, filler are mixed, at room temperature high-speed stirred with aqueous polyurethane, is added after 3h Dimethicone ultrasonic bubble removing sequentially adds antioxidant, cobalt iso-octoate and methyl ethyl ketone peroxide, and then vacuum suction steeps 10min is poured into Teflon mould, and room temperature curing 120min solidifies 5h in 70 DEG C of air dry oven afterwards, is made Circuit board antibacterial corrosion resistant composite material.
2. a kind of circuit board according to claim 1 antibacterial corrosion resistant composite material, which is characterized in that the filler includes Nanometer calcium carbonate, wollastonite, barium sulfate, hydroxyapatite, the quality of nanometer calcium carbonate, wollastonite, barium sulfate, hydroxyapatite The ratio between be 10:2-3:4-6:1-2.
3. a kind of circuit board according to claim 1 antibacterial corrosion resistant composite material, which is characterized in that the antioxidant packages Include zinc dialkyl dithiophosphate, triphenyl phosphite, ultraviolet absorbent UV-531, zinc dialkyl dithiophosphate, phosphorous Triphenyl phosphate ester, ultraviolet absorbent UV-531 are that 10:1-2:8-9 is compounded according to mass ratio.
4. a kind of circuit board according to claim 1 antibacterial corrosion resistant composite material, which is characterized in that the antibacterial microballoon It prepares by the following method:
(1) it measures 120mL dehydrated alcohol to be placed in a beaker, 3.1g nano-TiO is added2, magnetic agitation 25min obtains nano-TiO2 Alcohol suspending liquid, by nano-TiO2Alcohol suspending liquid ultrasonic disperse 30min；
(2) N methyldiethanol amine of the Sodium Acid Pyrophosphate, 4.6g that weigh 5.0g is added in above-mentioned suspension, and room temperature stirs 30min, re-ultrasonic dispersion 30min are mixed, centrifugal treating is carried out to suspension after the completion, is subsequently placed in 38 DEG C of vacuum ovens and does Dry 22h takes out grinding, crosses 650 meshes, and modified Nano TiO is made2Fine powder；
(3) in the 200mL distilled water of high-speed stirred shearing, 1-2min is stood after being slowly added to 30mg sodium alginate, makes seaweed Sour sodium is completely dissolved to form uniform sodium alginate soln, spare；20mg is added in the 5.6% of 200mL aqueous acetic acid Chitosan, stirring and dissolving is complete, obtains chitosan aqueous acetic acid, spare；
(4) it takes 3.6g rosin glycerides and 6.8g soybean oil in beaker, 12min is stirred in 46 DEG C of water-baths；Then it is added 100mL sodium alginate soln stirs 30min；Add 37mg Ag nano particles and the modified TiO of 52mg2Fine powder, ultrasonic disperse 35min, adds 1.5g stearoyl lactate, and stirring and emulsifying 3h pours into 30mL acetone stirring 10min, stand after reaction Layering；
(5) lower layer's milky emulsion is added in 150mL chitosan aqueous acetic acid simultaneously magnetic agitation 30min, be finally centrifuged 20min is washed with distilled water product 3 times, and antibacterial microballoon is made after freeze-drying.
5. a kind of circuit board preparation method of antibacterial corrosion resistant composite material, which comprises the steps of:
Step S1, after waste and old circuit board being mechanically pulverized, washing shaking table handles to obtain waste printed circuit board nonmetal powder body, then By powder by 20 meshes, remove large-sized impurity, ball-milling treatment is crushed with planetary ball mill, by the powder mistake after ball milling 200 meshes are placed in 55 DEG C of vacuum ovens dry 10h, obtain dry powder；
Step S2, toward the dehydrated alcohol and ammonium hydroxide of addition deionized water, half in dry powder, 30min is stirred at 60 DEG C, so Ethyl orthosilicate is slowly added dropwise with constant pressure funnel afterwards, centrifuge washing is dried to neutrality in 110 DEG C of vacuum after reacting 135min Dry 7h in case；
Step S3, the powder after taking drying is distributed in remaining half dehydrated alcohol, A151 silane coupling agent is added, at 80 DEG C Under be stirred to react 10h, centrifuge washing three times, obtains modified powder；
Step S4, modified powder, antibacterial microballoon, filler are mixed, at room temperature high-speed stirred with aqueous polyurethane, is added after 3h Dimethicone ultrasonic bubble removing sequentially adds antioxidant, cobalt iso-octoate and methyl ethyl ketone peroxide, and then vacuum suction steeps 10min is poured into Teflon mould, and room temperature curing 120min solidifies 5h in 70 DEG C of air dry oven afterwards, is made Circuit board antibacterial corrosion resistant composite material.
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112492765A (en) * 2020-11-17 2021-03-12 中国电子科技集团公司第四十六研究所 Preparation method of novel composite medium substrate
CN116355386A (en) * 2023-05-31 2023-06-30 广州市赞晨新材料科技有限公司 Polyurethane resin composition and application thereof in display screen packaging

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CN106009577A (en) * 2016-05-31 2016-10-12 华南理工大学 Waste printed circuit board nonmetal powder modified room temperature cured unsaturated polyester resin composite material and preparation method thereof
CN106674946A (en) * 2016-12-31 2017-05-17 华南理工大学 Waste printed-circuit-board nonmetallic powder loaded silicon dioxide hybrid filler and preparation method and application thereof

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TW200424259A (en) * 2003-05-14 2004-11-16 Eternal Chemical Co Ltd Resin composition having high dielectric constant and uses thereof
CN106009577A (en) * 2016-05-31 2016-10-12 华南理工大学 Waste printed circuit board nonmetal powder modified room temperature cured unsaturated polyester resin composite material and preparation method thereof
CN106674946A (en) * 2016-12-31 2017-05-17 华南理工大学 Waste printed-circuit-board nonmetallic powder loaded silicon dioxide hybrid filler and preparation method and application thereof

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112492765A (en) * 2020-11-17 2021-03-12 中国电子科技集团公司第四十六研究所 Preparation method of novel composite medium substrate
CN116355386A (en) * 2023-05-31 2023-06-30 广州市赞晨新材料科技有限公司 Polyurethane resin composition and application thereof in display screen packaging

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