Analysis Method of Organic Matter in Electronic Slurry

Abstract

The present invention relates to the technical field of component analysis, and specifically to an analysis method for organic matter in electronic paste, which comprises at least the following steps: S1, separation of organic components and inorganic components: (1) placing the electronic paste in a centrifuge tube, adding a non-protonic solvent, ultrasonically treating and centrifuging, and extracting the supernatant liquid of the centrifuge tube into a beaker; (2) repeating step (1) until the mass of the residue in the centrifuge tube does not change; (3) drying the enriched supernatant liquid and the residue in the centrifuge tube to obtain organic components and inorganic components respectively; S2, re-separation of organic components: separating the organic components dried in step S1 again by gradient washing; S3, parameter information analysis of organic components: drying the soluble matter obtained by gradient washing in step S2, and measuring the parameters respectively. The technical scheme of the present invention can basically separate the resin components in the sintered conductive paste, thereby obtaining their respective parameters such as molecular weight.

Description

Technical Field

[0001] The present invention relates to the technical field of component analysis, in particular to IPC classification number H01B1 / 22, and more particularly to an analysis method for organic matter in electronic slurry. Background Art

[0002] In recent years, domestic electronics, photovoltaics and other industries have developed rapidly, and the electronic paste products used in them have also been rapidly updated, and product performance requirements have continued to increase. Component analysis is used by more and more companies as an effective means to assist in the development of new electronic paste products and improve performance.

[0003] Since there are many resin components in sintered conductive silver paste and the content is low, the parameters of different resins have a great influence on the viscosity and performance of the product. The components of sintered conductive silver paste include organic carrier, conductive powder, glass powder, solvent, and additive. The content of organic carrier is relatively low (generally the total amount of resin is less than 2%), and generally contains 2-4 different types of resin components. Patent CN201710359227.9 discloses a sample pretreatment method and use for electron microscopy detection of conductive silver paste: (1) mixing the conductive silver paste with a first organic solvent, ultrasonicating once, and standing to separate layers; (2) removing the upper layer of liquid of the product after separation in step (1), adding a second organic solvent, and performing a second ultrasonication to obtain a sample for electron microscopy detection; wherein the volume of the second organic solvent is 1 to 4 times the volume of the conductive silver paste. This patent obtains a sample suitable for electron microscope observation by ultrasonically dispersing a conductive silver paste in a solvent, removing an organic layer, and then dispersing the solid matter in the solvent again and selecting a suitable concentration. This method obtains the type and amount of silver particles and additives by removing the organic layer, but does not analyze the organic components in the system.

[0004] In addition, in the current analysis process, it is difficult to obtain information such as the content and molecular weight parameters of different resin components in the sample through the method of overall sampling. However, the gradient separation process often cannot accurately obtain the respective parameter information due to incomplete separation. Summary of the invention

[0005] In view of the above-mentioned technical problems, the present invention provides a method for analyzing organic matter in electronic slurry, which at least comprises the following steps:

[0006] S1. Separation of organic and inorganic components

[0007] (1) placing the electronic slurry in a centrifuge tube, adding an aprotic solvent, performing ultrasonic treatment and centrifugation, and extracting the supernatant liquid from the centrifuge tube into a beaker;

[0008] (2) Repeat step (1) until the mass of the residue in the centrifuge tube does not change;

[0009] (3) drying the enriched supernatant and the residue in the centrifuge tube to obtain organic components and inorganic components, respectively;

[0010] S2. Re-separation of organic components

[0011] The organic components dried in step S1 are separated again by gradient washing;

[0012] S3. Parameter information analysis of organic components

[0013] The soluble matter obtained by gradient washing in step S2 is dried and then parameters are measured respectively.

[0014] In some embodiments, the components of the electronic paste include, by mass percentage, 0-1% ethyl cellulose, 0-1% acrylate copolymer, 0-1% poly-α-methylstyrene resin, 0-1% dimethyl silicone oil, 1-4% diethylene glycol butyl ether acetate, 0-1% alcohol ester dodecanol, 0-1% pineol, 85-90% silver powder, 1-3% glass powder, 0-0.5% polyamide wax, and 0-0.3% polyhydroxystearic acid dispersant.

[0015] In some embodiments, the aprotic solvent in step (1) comprises tetrahydrofuran.

[0016] In some embodiments, the ultrasonic treatment time in step (1) is 3-7 min.

[0017] Preferably, the ultrasonic treatment time in step (1) is 5 min.

[0018] In some embodiments, the centrifugal speed is 1-1.5 Wr / min.

[0019] Preferably, the centrifugal speed is 1.2Wr / min.

[0020] In some embodiments, the centrifugation time is 5-15 min.

[0021] Preferably, the centrifugation time is 10 min.

[0022] In some embodiments, step (2) is repeated at least 5 times.

[0023] In some embodiments, the drying conditions in step (3) are: temperature 150-170° C., time 1-3 h.

[0024] Preferably, the drying conditions in step (3) are: temperature 160° C., time 2 h.

[0025] The applicant found in the study that the separation of organic components and inorganic components in step S1 has a great influence on the accuracy of subsequent analysis of organic components. If the separation effect of this step is not good, inorganic impurities may be doped and interfere with the qualitative and quantitative analysis of organic components. After a lot of research, the applicant found that a specific treatment of step S1, especially the addition of aprotic solvent tetrahydrofuran, ultrasonic treatment for 5 minutes, followed by high-speed centrifugation at a speed of 1.2Wr / min, extraction of the upper solution, and repeated 5 times until the mass of the residue in the centrifuge tube no longer changes, can achieve a thorough separation of organic components from inorganic components. The applicant believes that the possible reason is that the addition of tetrahydrofuran solution can well dissolve the organic matter in the silver paste, but some silver powder or glass powder in the silver paste is wrapped by resin and has a certain adhesion. The applicant combines ultrasonic treatment and high-speed centrifugation to achieve a good peeling between the resin and the silver powder or glass powder, avoiding the problem of trace amounts of resin adhering to the surface of the inorganic powder and being taken away, thereby ensuring a more thorough separation of the inorganic and organic components, and further ensuring the accuracy of the subsequent analysis of the organic components.

[0026] In some embodiments, the S2 step specifically includes:

[0027] (a) taking the dried organic component in step S1 and placing it in a centrifuge tube, adding n-hexane, ultrasonically treating, centrifuging, extracting the supernatant in the centrifuge tube into a beaker, and repeating this step 5 times;

[0028] (b) adding toluene to the residue in the centrifuge tube obtained in step (a), ultrasonically treating, centrifuging, extracting the supernatant in the centrifuge tube into a beaker, and repeating this step 5 times;

[0029] (c) Methanol was added to the residue in the centrifuge tube obtained in step (b), and the mixture was ultrasonically treated and centrifuged. The supernatant in the centrifuge tube was extracted into a beaker, and this step was repeated 5 times.

[0030] Preferably, the S2 step specifically includes:

[0031] (a) 0.5-1 g of the dried organic component in step S1 was placed in a centrifuge tube, 2-4 ml of n-hexane was added, ultrasonic treatment was performed for 10-20 min, and centrifugation was performed at 1-1.5 Wr / min for 5-15 min. The supernatant in the centrifuge tube was extracted into a beaker, and this step was repeated 5 times;

[0032] (b) adding 2-4 ml of toluene to the residue in the centrifuge tube obtained in step (a), ultrasonically treating for 10-20 min, centrifuging at 1-1.5 Wr / min for 5-15 min, extracting the supernatant in the centrifuge tube into a beaker, and repeating this step 5 times;

[0033] (c) Add 2-4 ml of methanol to the residue in the centrifuge tube obtained in step (b), perform ultrasonic treatment for 10-20 min, centrifuge at 1-1.5 Wr / min for 5-15 min, extract the supernatant in the centrifuge tube into a beaker, and repeat this step 5 times.

[0034] More preferably, the S2 step specifically includes:

[0035] (a) 0.5-1 g of the dried organic component in step S1 was placed in a centrifuge tube, 3 ml of n-hexane was added, ultrasonic treatment was performed for 15 min, and centrifugation was performed at 1.2 Wr / min for 10 min. The supernatant in the centrifuge tube was extracted and transferred to a beaker. This step was repeated 5 times;

[0036] (b) adding 3 ml of toluene to the residue in the centrifuge tube obtained in step (a), ultrasonically treating for 15 min, centrifuging at 1.2 Wr / min for 10 min, extracting the supernatant in the centrifuge tube into a beaker, and repeating this step 5 times;

[0037] (c) Add 3 ml of methanol to the residue in the centrifuge tube obtained in step (b), ultrasonicate for 15 min, centrifuge at 1.2 Wr / min for 10 min, extract the supernatant in the centrifuge tube into a beaker, and repeat this step 5 times.

[0038] The applicant found in the process of gradient washing the organic components dried in step S1 that the choice of solvent is related to the ability to separate the resin components in the sintered conductive paste. After a large number of experiments and summaries, the applicant found that, especially for the selection of n-hexane as the solvent in step (a), followed by specific ultrasonic treatment and high-speed centrifugation treatment, the soluble matter that can be obtained is a single resin. At the same time, the applicant found in the experimental process that the use of acetone as a solvent in step (a) cannot achieve the separation between the resin components. The possible reason is that n-hexane gives the system a more suitable polarity, so that dimethyl silicone oil has excellent solubility in it, while other resins are insoluble, thereby achieving the separation of a single component. However, acetone can dissolve multiple resins due to its own polarity, so that the obtained soluble matter contains multiple resins, and thus the separation between the resin components cannot be achieved, so the parameter information such as their respective molecular weights cannot be obtained. In addition, certain amounts of toluene and methanol are respectively selected in step (b) and step (c) to obtain single soluble substances of acrylic resin and ethyl cellulose, respectively, thereby achieving basic separation of the resin components in the sintered conductive paste, which is helpful for analyzing the viscosity and performance of the electronic paste for the product, and has important application value for the research and development or performance optimization of the electronic paste.

[0039] In some embodiments, the determination of the parameters in step S3 includes at least one of GPC, NMR, and infrared spectrum determination.

[0040] Beneficial effects:

[0041] (1) By taking specific treatments for step S1, especially adding aprotic solvent tetrahydrofuran, performing ultrasonic treatment for 5 min, and then high-speed centrifugation at a speed of 1.2 Wr / min to extract the upper layer solution, and repeating this process 5 times until the mass of the residue in the centrifuge tube no longer changes, the organic component and the inorganic component can be completely separated;

[0042] (2) In step (a) of the present invention, the solvent is selected as n-hexane, followed by specific ultrasonic treatment and high-speed centrifugation treatment, and the soluble matter obtained is a single resin;

[0043] (3) In the step (b) and step (c) of the present invention, certain toluene and methanol are respectively selected to obtain single soluble substances of acrylic resin and ethyl cellulose, respectively;

[0044] (4) The technical solution of the present invention can basically separate the resin components in the sintered conductive paste, thereby obtaining their respective molecular weight and other parameters;

[0045] (5) The method of the present invention is helpful for analyzing the viscosity and performance of electronic paste for products, and has important application value for the research and development or performance optimization of electronic paste. BRIEF DESCRIPTION OF THE DRAWINGS

[0046] Figure 1 This is the GPC parameter spectrum of the soluble substance A obtained by gradient washing in Example 1 after drying;

[0047] Figure 2 This is the GPC parameter spectrum of the soluble substance B obtained by gradient washing in Example 1 after drying;

[0048] Figure 3 This is the GPC parameter spectrum of the soluble matter C obtained by gradient washing in Example 1 after drying. DETAILED DESCRIPTION

[0049] Example 1

[0050] The method for analyzing organic matter in electronic slurry comprises the following steps:

[0051] S1. Separation of organic and inorganic components

[0052] (1) Place the electronic slurry in a centrifuge tube, add tetrahydrofuran, perform ultrasonic treatment for 5 min, centrifuge at a speed of 1.2 Wr / min for 10 min, and extract the supernatant on the centrifuge tube into a clean beaker;

[0053] (2) Repeat step (1) 5 times until the mass of the residue in the centrifuge tube does not change;

[0054] (3) drying the enriched supernatant and the residue in the centrifuge tube at 160° C. for 2 h to obtain organic components and inorganic components, respectively;

[0055] S2. Re-separation of organic components

[0056] The organic components dried in step S1 are separated again by gradient washing, specifically comprising:

[0057] (a) 0.8 g of the dried organic component in step S1 was placed in a centrifuge tube, 3 ml of n-hexane was added, ultrasonic treatment was performed for 15 min, and centrifugation was performed at 1.2 Wr / min for 10 min. The supernatant in the centrifuge tube was extracted into a beaker, and this step was repeated 5 times. The supernatants obtained were combined to obtain soluble matter A;

[0058] (b) adding 3 ml of toluene to the residue in the centrifuge tube obtained in step (a), ultrasonically treating for 15 min, centrifuging at 1.2 Wr / min for 10 min, extracting the supernatant in the centrifuge tube into a beaker, repeating this step 5 times, combining the obtained supernatants to obtain soluble matter B;

[0059] (c) adding 3 ml of methanol to the residue in the centrifuge tube obtained in step (b), ultrasonically treating for 15 min, centrifuging at 1.2 Wr / min for 10 min, extracting the supernatant in the centrifuge tube into a beaker, repeating this step 5 times, combining the obtained supernatants to obtain soluble matter C;

[0060] S3. Parameter information analysis of organic components

[0061] The soluble matter A, soluble matter B and soluble matter C obtained by gradient washing in step S2 were dried at 160°C / 2h and then subjected to GPC parameter determination. The results are as follows: Figure 1-Figure 3 shown.

[0062] Conclusion: Figure 1-3 It can be seen that the technical solution provided by the present invention can basically separate the resin components in the sintered conductive paste, and the GPC parameter information of soluble matter A, soluble matter B and soluble matter C can be obtained from the spectrum, which are dimethyl silicone oil, acrylate copolymer and ethyl cellulose respectively.

Claims

1. Analysis method of organic matter in electronic paste, It is characterized in that At least the following steps are included: S1. Separation of organic and inorganic components (1) placing the electronic slurry in a centrifuge tube, adding an aprotic solvent, performing ultrasonic treatment and centrifugation, and extracting the supernatant liquid from the centrifuge tube into a beaker; (2) Repeat step (1) until the mass of the residue in the centrifuge tube does not change; (3) drying the enriched supernatant and the residue in the centrifuge tube to obtain organic components and inorganic components, respectively; In the step (1), the aprotic solvent comprises tetrahydrofuran; The ultrasonic treatment time in step (1) is 3-7 min; The centrifugal speed is 1-1.5Wr / min; The centrifugation time is 5-15min; The number of repetitions in step (2) is at least 5 times; S2. Re-separation of organic components The organic components dried in step S1 are separated again by gradient washing; The S2 step specifically includes: (a) taking the dried organic component in step S1 and placing it in a centrifuge tube, adding n-hexane, ultrasonically treating, centrifuging, extracting the supernatant in the centrifuge tube into a beaker, and repeating this step 5 times; (b) adding toluene to the residue in the centrifuge tube obtained in step (a), ultrasonically treating, centrifuging, extracting the supernatant in the centrifuge tube into a beaker, and repeating this step 5 times; (c) adding methanol to the residue in the centrifuge tube obtained in step (b), ultrasonically treating, centrifuging, extracting the supernatant in the centrifuge tube into a beaker, and repeating this step 5 times; S3. Parameter information analysis of organic components The soluble matter obtained by gradient washing in step S2 is dried and then parameters are measured respectively.

2. The method for analyzing organic matter in electronic paste according to claim 1, It is characterized in that Measured by mass percentage, the components of the electronic paste include 0-1% ethyl cellulose, 0-1% acrylate copolymer, 0-1% poly-α-methylstyrene resin, 0-1% dimethyl silicone oil, 1-4% diethylene glycol butyl ether acetate, 0-1% alcohol ester dodecahydrate, 0-1% pineol, 85-90% silver powder, 1-3% glass powder, 0-0.5% polyamide wax, and 0-0.3% polyhydroxystearic acid dispersant.

3. The method for analyzing organic matter in electronic paste according to claim 1, It is characterized in that The drying conditions in step (3) are: temperature 150-170° C., time 1-3 h.

4. The method for analyzing organic matter in electronic paste according to claim 1, It is characterized in that The determination of the parameters in step S3 includes at least one of GPC, NMR, and infrared spectrum determination.

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