CN111171495A - Graphene-modified waterborne acrylic acid-grafted epoxy resin and preparation method thereof - Google Patents
Graphene-modified waterborne acrylic acid-grafted epoxy resin and preparation method thereof Download PDFInfo
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- CN111171495A CN111171495A CN202010064779.9A CN202010064779A CN111171495A CN 111171495 A CN111171495 A CN 111171495A CN 202010064779 A CN202010064779 A CN 202010064779A CN 111171495 A CN111171495 A CN 111171495A
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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
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/08—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/10—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers containing more than one epoxy radical per molecule
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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
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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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
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Abstract
The invention provides a graphene-modified waterborne acrylic acid grafted epoxy resin and a preparation method thereof, belonging to the technical field of high-molecular materials. The graphene-modified waterborne acrylic acid grafted epoxy resin solves the problems of weather resistance, storage stability and the like of the existing waterborne epoxy resin, and comprises the following raw material components in percentage by mass: 20-30% of epoxy resin, 3-15% of monomer, 0.1-2% of initiator, 10-25% of mixed solvent, 1-5% of neutralizer, 1-5% of graphene suspension and the balance of distilled water. The water-based epoxy resin provided by the invention is excellent in stability, salt mist resistance and weather resistance.
Description
Technical Field
The invention belongs to the technical field of high-molecular materials, and particularly relates to graphene-modified waterborne acrylic acid grafted epoxy resin and a preparation method thereof.
Background
Epoxy resin is one of three general thermosetting resins, has excellent adhesiveness, wear resistance, corrosion resistance, insulativity and mechanical strength, and is widely applied to the field of coating industry.
With the increasing requirements of people on environmental protection performance, the application range of the water-based epoxy resin is wider and wider. At present, the preparation method of the water-based epoxy resin mainly comprises four methods, namely a mechanical method, a phase inversion method, a curing agent emulsification method and a chemical modification method. The emulsion prepared by the method has larger particle size, usually micron-sized, and has poorer water resistance, solvent resistance and other properties than solvent type due to more emulsifiers, and short pot life. Weather resistance and gloss are common problems of various epoxy resins, and also limit the application fields of the epoxy resins.
The acrylic emulsion is widely used in various fields such as clothes, shoe materials, steel structures and the like at present, and has the advantages of good weather resistance, good storage stability and quick air drying at normal temperature. In addition, graphene is the most great discovery in the field of new materials in recent years, and the application prospects of graphene in the fields of heat dissipation, hydrophobicity, conductivity and corrosion prevention are generally concerned and accepted.
Disclosure of Invention
The first object of the present invention is to solve the above problems in the prior art, and to provide a graphene-modified waterborne acrylic acid grafted epoxy resin; the second purpose of the invention is to provide a preparation method of the graphene modified waterborne acrylic acid grafted epoxy resin.
The first object of the present invention can be achieved by the following technical solutions: the graphene-modified waterborne acrylic acid grafted epoxy resin is characterized by comprising the following raw material components in percentage by mass: 20-30% of epoxy resin, 3-15% of monomer, 0.1-2% of initiator, 10-25% of mixed solvent, 1-5% of neutralizer, 1-5% of graphene suspension and the balance of distilled water.
Preferably, the epoxy resin is bisphenol A epoxy resin.
Preferably, the bisphenol A epoxy resin is selected from one or any combination of epoxy resin E-20, epoxy resin E-14, epoxy resin E-12, epoxy resin E-06 and epoxy resin E-03.
Preferably, the monomers include 1-5% of hydrophilic monomers, 1-5% of hard monomers and 1-5% of soft monomers.
Preferably, the hydrophilic monomer is selected from one or two of acrylic acid and methacrylic acid; the hard monomer is selected from one or any combination of methyl acrylate, methyl methacrylate, ethyl methacrylate, styrene and n-butyl methacrylate; the soft monomer is selected from one or any combination of ethyl acrylate, butyl acrylate, n-octyl acrylate and isooctyl acrylate.
Preferably, the mixed solvent is selected from a combination of any two of the following: ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, ethylene glycol butyl ether, propylene glycol monobutyl ether and n-butanol; the neutralizing agent is selected from one or any combination of ethanolamine, diethanolamine, triethanolamine, triethylamine, AMP-95, ammonia water and N, N-dimethylethanolamine.
Preferably, the mixed solvent is a mixed solution of ethylene glycol butyl ether and n-butanol; the neutralizer is N, N-dimethylethanolamine.
Preferably, the initiator is benzoyl peroxide.
Preferably, the graphene is a few-layer graphene sheet or a multi-layer graphene sheet, the graphene purity is more than 95 wt%, the thickness is between 1nm and 20nm, and the plane transverse dimension is between 1 μm and 100 μm; the graphene is prepared from graphite by a physical method, wherein the physical method comprises a micro-mechanical stripping method and a liquid-phase or gas-phase direct stripping method.
The second object of the present invention can be achieved by the following technical solutions: the preparation method of the graphene-modified waterborne acrylic acid grafted epoxy resin is characterized by comprising the following steps:
SO 1: mixing the mixed solvent with epoxy resin to obtain a mixed solution A;
SO 2: dissolving an initiator in a monomer, heating the mixed solution A in the step S01 to 110-115 ℃, dropwise adding the mixed liquid of the initiator and the monomer into the mixed solution A, keeping the reaction temperature after dropwise adding is finished for 2-4 hours, continuously reacting for 2 hours, cooling to 60 ℃, adding a neutralizer to neutralize to a pH value of 7-8, and obtaining a mixed solution B;
SO 3: dropwise adding distilled water into the mixed solution B obtained in the step S02 for emulsification, dropwise adding a graphene suspension, and stirring to obtain graphene-modified waterborne acrylic acid grafted epoxy resin;
the preparation method of the graphene suspension comprises the following steps: adding a mixture of 5: 95 of graphene and water are mixed and stirred for 0.5 to 1 hour, and a high-pressure homogenizer is used for emulsification until the viscosity exceeds 1000cps, namely the graphene suspension.
Compared with the prior art, the invention has the following advantages:
1. according to the invention, through a large number of experiments, the synthesis process and the optimal dosage composition and proportion of the raw materials are optimized, the graphene is adopted to modify the waterborne acrylic acid grafted epoxy resin, and the stability, salt mist resistance and weather resistance of the waterborne epoxy resin can be improved.
2. experiments show that the epoxy resin has no unsaturated double bonds, but α -H on a carbon atom adjacent to an ether bond and H on a tertiary carbon are relatively active, free radicals can be formed under the action of an initiator benzoyl peroxide, the epoxy resin can perform free radical polymerization with (methyl) acrylic acid and ester monomers thereof under the action of the benzoyl peroxide, and finally the formed product is a mixture of ungrafted epoxy resin, graft polymerized acrylic resin and an acrylic monomer copolymer.
3. The synthesis process of the invention also finds that: the selection of the type of epoxy resin and the molecular weight have important influences on the stability and the tolerance of the epoxy resin. According to the invention, a large number of experimental screens are adopted, the graphene suspension can be well blended into a polymerization system, and the salt spray performance of the resin can be obviously improved on the premise of not influencing the stability of the polymer.
4. The neutralizing agent adopted by the invention is an amine neutralizing agent, which not only can play a role in regulating pH, but also can convert into salt, thereby facilitating subsequent filtration and removal.
5. According to the invention, acrylic acid is grafted to the epoxy structure by a chemical grafting method, and the problems of weather resistance and storage stability of the water-based epoxy resin are improved while hydrophilicity is introduced. The graphene-modified waterborne acrylic acid grafted epoxy resin can obviously improve the weather resistance and salt spray resistance of the resin, and has a huge application prospect in the field of industrial corrosion prevention.
Detailed Description
The following are specific examples of the present invention and further describe the technical solutions of the present invention, but the present invention is not limited to these examples.
Graphene suspension: adding a mixture of 5: 95 of graphene and water are mixed and stirred for 0.5 to 1 hour, and the mixture is emulsified by a high-pressure homogenizer (the high-pressure homogenizer is commercially available) until the viscosity exceeds 1000cps to obtain graphene suspension.
Example 1
A preparation method of graphene modified waterborne acrylic acid grafted epoxy resin comprises the following steps:
(1) in a four-necked flask equipped with a stirrer, a condenser, a thermometer and a constant pressure dropping funnel, ethylene glycol butyl ether, n-butanol and epoxy resin E-06 of the following Table 1 were added;
(2) mixing a certain amount of methyl methacrylate, butyl acrylate, methacrylic acid and initiator Benzoyl Peroxide (BPO) according to the table 1, uniformly stirring, and putting into a dropping funnel;
(3) and (3) heating the solvent in the flask to 110-115 ℃, and then dropwise adding the acrylic monomer and the initiator mixed in the step (2) for about 3 hours. Keeping the temperature, continuously reacting for 2 hours, cooling to 60 ℃, adding an amine neutralizer in the table 1, converting into salt, adding distilled water with a certain amount in the table 1 under high-speed stirring, emulsifying, dropwise adding graphene suspension in the table 1, stirring for 15min, cooling to below 35 ℃, filtering, discharging, and thus obtaining the graphene-modified waterborne acrylic acid grafted epoxy resin.
Table 1 example 1 raw material composition of graphene-modified waterborne acrylic grafted epoxy resin
| Serial number | Composition of | Percent by weight% |
| 1 | Epoxy resin | 25 |
| 2 | Ethylene glycol methyl ether | 10 |
| 3 | Butanol | 5 |
| 4 | Methyl Methacrylate (MMA) | 8 |
| 5 | Butyl Acrylate (BA) | 3 |
| 6 | Methacrylic acid (MAA) | 1.5 |
| 7 | Benzoyl Peroxide (BPO) | 1.5 |
| 8 | N, N-dimethylethanolamine | 2 |
| 9 | Water (W) | 43 |
| 10 | Graphene suspension | 1 |
Example 2
A preparation method of graphene modified waterborne acrylic acid grafted epoxy resin comprises the following steps:
(1) in a four-necked flask equipped with a stirrer, a condenser, a thermometer and a constant pressure dropping funnel, ethylene glycol butyl ether, butanol and epoxy resin E-06 of the following Table 2 were added;
(2) mixing a certain amount of methyl methacrylate, butyl acrylate, methacrylic acid and initiator Benzoyl Peroxide (BPO) according to the table 2, uniformly stirring, and putting into a dropping funnel;
(3) and (3) heating the solvent in the flask to 110-115 ℃, and then dropwise adding the acrylic monomer and the initiator mixed in the step (2) for about 3 hours. Keeping the temperature, continuously reacting for 2 hours, cooling to 60 ℃, adding an amine neutralizer in the table 2, converting into salt, adding distilled water with a certain amount in the table 1 under high-speed stirring, emulsifying, dropwise adding graphene suspension in the table 2, stirring for 15min, cooling to below 35 ℃, filtering, discharging, and thus obtaining the graphene-modified waterborne acrylic acid grafted epoxy resin.
Table 2 example 2 raw material composition of graphene-modified waterborne acrylic grafted epoxy resin
| Serial number | Composition of | Percent by weight% |
| 1 | Epoxy resin | 25 |
| 2 | Ethylene glycol methyl ether | 10 |
| 3 | Butanol | 5 |
| 4 | MMA | 8 |
| 5 | BA | 3 |
| 6 | MAA | 1.5 |
| 7 | BPO | 1.5 |
| 8 | N, N-dimethylethanolamine | 2 |
| 9 | Water (W) | 42 |
| 10 | Graphene suspension | 2 |
Example 3
A preparation method of graphene modified waterborne acrylic acid grafted epoxy resin comprises the following steps:
(1) in a four-necked flask equipped with a stirrer, a condenser, a thermometer and a constant pressure dropping funnel, ethylene glycol butyl ether, butanol and epoxy resin E-06 of the following Table 3 were added;
(2) mixing a certain amount of methyl methacrylate, butyl acrylate, methacrylic acid and initiator Benzoyl Peroxide (BPO) according to the table 3, uniformly stirring, and putting into a dropping funnel;
(3) and (3) heating the solvent in the flask to 110-115 ℃, and then dropwise adding the acrylic monomer and the initiator mixed in the step (2) for about 3 hours. Keeping the temperature, continuously reacting for 2 hours, cooling to 60 ℃, adding an amine neutralizer in the table 3, converting into salt, adding a certain amount of deionized water in the table 3 under high-speed stirring, emulsifying, dropwise adding graphene suspension in the table 3, stirring for 15min, cooling to below 35 ℃, filtering, discharging, and thus obtaining the graphene-modified waterborne acrylic acid grafted epoxy resin.
Table 3 example 3 raw material composition of graphene-modified waterborne acrylic grafted epoxy resin
| Serial number | Composition of | Percent by weight% |
| 1 | Epoxy resin | 25 |
| 2 | Ethylene glycol methyl ether | 10 |
| 3 | Butanol | 5 |
| 4 | MMA | 8 |
| 5 | BA | 3 |
| 6 | MAA | 1.5 |
| 7 | BPO | 1.5 |
| 8 | N, N-dimethylethanolamine | 2 |
| 9 | Water (W) | 41 |
| 10 | Graphene suspension | 3 |
Example 4
A preparation method of graphene modified waterborne acrylic acid grafted epoxy resin comprises the following steps:
(2) in a four-necked flask equipped with a stirrer, a condenser, a thermometer and a constant pressure dropping funnel, ethylene glycol butyl ether, n-butanol and epoxy resin E-06 of the following Table 4 were added;
(2) mixing a certain amount of methyl methacrylate, butyl acrylate, methacrylic acid and initiator Benzoyl Peroxide (BPO) according to the table 4, uniformly stirring, and putting into a dropping funnel;
(3) and (3) heating the solvent in the flask to 110-115 ℃, and then dropwise adding the acrylic monomer and the initiator mixed in the step (2) for about 3 hours. Keeping the temperature, continuously reacting for 2 hours, cooling to 60 ℃, adding an amine neutralizer in the table 4, converting into salt, adding a certain amount of deionized water in the table 4 under high-speed stirring, emulsifying, dropwise adding graphene suspension in the table 4, stirring for 15min, cooling to below 35 ℃, filtering, discharging, and thus obtaining the graphene modified waterborne acrylic acid grafted epoxy resin.
Table 4 example 4 raw material composition of graphene-modified waterborne acrylic grafted epoxy resin
| Serial number | Composition of | Percent by weight% |
| 1 | Epoxy resin | 25 |
| 2 | Ethylene glycol methyl ether | 10 |
| 3 | Butanol | 5 |
| 4 | MMA | 8 |
| 5 | BA | 3 |
| 6 | MAA | 1.5 |
| 7 | BPO | 1.5 |
| 8 | N, N-dimethylethanolamine | 2 |
| 9 | Water (W) | 40 |
| 10 | Graphene suspension | 4 |
To further illustrate the performance characteristics of the graphene-modified waterborne acrylic acid grafted epoxy resin of the present invention, the performance of the epoxy emulsions prepared in examples 1, 2, 3 and 4 was tested by the following test methods:
emulsion solid content reference GB1725-79
The adhesive force of the paint film is measured according to the GB/T9286-1998 method and is tested by a grid cutting method;
the impact property of the paint film is tested by adopting BGD302 paint film impact test according to the method of GB/T1732-1993;
the pH value is measured by a glass mercury electrode pH meter calibrated by a buffer solution;
the viscometer measures CPS with a rotary viscometer;
storage stability: placing in a constant temperature oven at 50 deg.C for 7 days, taking out, placing at room temperature, observing whether gel and delamination occur, if not, determining that the storage stability is qualified, and determining to pass;
dilution stability: and (3) mixing the emulsion: mixing water at a ratio of 1/10, standing for 2d, and allowing dilution to pass if no gel appears and layering;
emulsion particle size and distribution: measuring by using a laser scattering particle size distribution instrument;
the corrosion resistance of the paint film is measured according to the GB/T1771-2007 method;
the artificial aging resistance of the paint film is determined according to the GB/T1865-80 method.
Salt spray resistance test the neutral salt spray test was followed using a 5% aqueous solution of sodium chloride salt.
The test results of the graphene-modified waterborne acrylic grafted epoxy resin prepared in each of the above examples are shown in table 5:
TABLE 5 Properties of graphene-modified waterborne acrylic grafted epoxy resins of examples 1-4
From the data, it can be found that the salt spray resistance and weather resistance of the graphene-modified waterborne acrylic grafted epoxy resin are improved along with the increase of the content of the graphene suspension, and the flexibility of the resin is also improved because the graphene is a material with better flexibility, so that the final impact resistance is also improved.
In order to illustrate the effect of the molecular weight of the epoxy resin on the stability and viscosity of the prepared epoxy emulsion in detail, the invention also performs the experiments of examples 5-8, the content of each component and the graphene suspension used in examples 5-8 are not different from those in examples 1-4, but the molecular weight of the epoxy resin is selected differently, and the formula proportion of each example is specifically shown in table 6:
table 6 examples 5 to 8
The viscosity, particle size, corrosion resistance and storage stability at room temperature of the epoxy emulsion obtained by the experiment of examples 5 to 8 of the present invention are shown in the following table 7:
TABLE 7 Properties of graphene-modified waterborne acrylic grafted epoxy resins of examples 5-8
From the test data in Table 7, it can be seen that as the relative molecular weight of the epoxy resin increases, the stability of the emulsion increases, as indicated by the general formula for bisphenol A epoxy resin: m (epoxy resin average molecular weight) + 340+284n (n is the number of repeating units in the epoxy resin molecule), it is known that as the epoxy resin average molecular weight increases, the number of grafting points which can be grafted in the epoxy molecule increases, and enough carboxyl groups are introduced by grafting, so that the graft polymer can be stably dispersed in water to form an emulsion, and meanwhile, as the epoxy resin molecular weight increases, the grafting points increase, so that the main chain of the polymer is lengthened, the branched chains are more complicated, the paint film is more compact, the viscosity of the emulsion is increased, and the corrosion resistance of the emulsion paint film is enhanced.
The specific embodiments described herein are merely illustrative of the spirit of the invention. Various modifications or additions may be made to the described embodiments or alternatives may be employed by those skilled in the art without departing from the spirit or ambit of the invention as defined in the appended claims.
Claims (10)
1. The graphene-modified waterborne acrylic acid grafted epoxy resin is characterized by comprising the following raw material components in percentage by mass: 20-30% of epoxy resin, 3-15% of monomer, 0.1-2% of initiator, 10-25% of mixed solvent, 1-5% of neutralizer, 1-5% of graphene suspension and the balance of distilled water.
2. The graphene-modified waterborne acrylic grafted epoxy resin according to claim 1, wherein the epoxy resin is a bisphenol a epoxy resin.
3. The graphene-modified waterborne acrylic grafted epoxy resin according to claim 2, wherein the bisphenol a epoxy resin is selected from one or any combination of epoxy resin E-20, epoxy resin E-14, epoxy resin E-12, epoxy resin E-06 and epoxy resin E-03.
4. The graphene-modified waterborne acrylic acid grafted epoxy resin according to claim 1, wherein the monomers comprise 1-5% of hydrophilic monomers, 1-5% of hard monomers and 1-5% of soft monomers.
5. The graphene-modified waterborne acrylic acid grafted epoxy resin according to claim 4, wherein the hydrophilic monomer is selected from one or a combination of two of acrylic acid and methacrylic acid; the hard monomer is selected from one or any combination of methyl acrylate, methyl methacrylate, ethyl methacrylate, styrene and n-butyl methacrylate; the soft monomer is selected from one or any combination of ethyl acrylate, butyl acrylate, n-octyl acrylate and isooctyl acrylate.
6. The graphene-modified waterborne acrylic acid grafted epoxy resin according to claim 1, wherein the mixed solvent is selected from the group consisting of any two of the following: ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, ethylene glycol butyl ether, propylene glycol monobutyl ether and n-butanol; the neutralizing agent is selected from one or any combination of ethanolamine, diethanolamine, triethanolamine, triethylamine, AMP-95, ammonia water and N, N-dimethylethanolamine.
7. The graphene-modified waterborne acrylic acid grafted epoxy resin as claimed in claim 6, wherein the mixed solvent is a mixed solution of ethylene glycol butyl ether and n-butanol; the neutralizer is N, N-dimethylethanolamine.
8. The graphene-modified waterborne acrylic grafted epoxy resin according to claim 1, wherein the initiator is benzoyl peroxide.
9. The graphene-modified aqueous acrylic acid grafted epoxy resin according to claim 1, wherein the graphene is a few-layer graphene sheet or a multi-layer graphene sheet, the graphene purity is greater than 95 wt%, the thickness is between 1nm and 20nm, and the planar transverse dimension is between 1 μm and 100 μm; the graphene is prepared from graphite by a physical method, wherein the physical method comprises a micro-mechanical stripping method and a liquid-phase or gas-phase direct stripping method.
10. A method for preparing the graphene-modified waterborne acrylic acid grafted epoxy resin according to any one of claims 1 to 9, comprising the steps of:
SO 1: mixing the mixed solvent with epoxy resin to obtain a mixed solution A;
SO 2: dissolving an initiator in a monomer, heating the mixed solution A in the step S01 to 110-115 ℃, dropwise adding the mixed liquid of the initiator and the monomer into the mixed solution A, keeping the reaction temperature after dropwise adding is finished for 2-4 hours, continuously reacting for 2 hours, cooling to 60 ℃, adding a neutralizer to neutralize to a pH value of 7-8, and obtaining a mixed solution B;
SO 3: dropwise adding distilled water into the mixed solution B obtained in the step S02 for emulsification, dropwise adding a graphene suspension, and stirring to obtain graphene-modified waterborne acrylic acid grafted epoxy resin;
the preparation method of the graphene suspension comprises the following steps: adding a mixture of 5: 95 of graphene and water are mixed and stirred for 0.5 to 1 hour, and a high-pressure homogenizer is used for emulsification until the viscosity exceeds 1000cps, namely the graphene suspension.
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| CN112724601A (en) * | 2020-12-25 | 2021-04-30 | 北京化工大学 | Carbon fiber reinforced composite material with high interface strength and strong interface conductivity and preparation method thereof |
| CN113683938A (en) * | 2021-08-23 | 2021-11-23 | 亚士创能科技(上海)股份有限公司 | Epoxy graphene intermediate and preparation method and application thereof |
| CN114181407A (en) * | 2021-12-07 | 2022-03-15 | 杭州烯创科技有限公司 | Graphene modified acrylic acid bisphenol F type epoxy emulsion and preparation method thereof |
| CN114231115A (en) * | 2021-12-23 | 2022-03-25 | 杭州烯创科技有限公司 | Graphene single-component aqueous epoxy resin emulsion and preparation method thereof |
| CN114449775A (en) * | 2022-03-17 | 2022-05-06 | 广德三生科技有限公司 | High-resistance precise carbon ink treatment process for PCB (printed circuit board) |
| CN115386048A (en) * | 2021-10-14 | 2022-11-25 | 常州全睿聚合物新材料有限公司 | Weather-resistant water-based epoxy resin and preparation method and application thereof |
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| CN114449775A (en) * | 2022-03-17 | 2022-05-06 | 广德三生科技有限公司 | High-resistance precise carbon ink treatment process for PCB (printed circuit board) |
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Application publication date: 20200519 |