A batch manufacturing method and a micro-nano injection needle based on cutting and dissolution
Through the electro-hydraulic power jet method and casting method combined with cutting and dissolution technology, the problem of high manufacturing cost and easy blockage in the existing technology is solved, and high-precision and low-cost large-area micro-nano needle manufacturing is achieved.
Patent Information
- Application Number
- CN202510092216.3
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- Filing Date
- 2025-01-21
- Publication Date
- 2025-06-17
- Estimated Expiration
- 2045-01-21
AI Technical Summary
The prior art is difficult to manufacture high-precision micro-nano needles at large areas and at low cost, and the micro-nano needles are easily blocked due to material accumulation, adhesion or deterioration during the printing process, resulting in loss.
Micron and nano-spray needle batch manufacturing method based on cutting and dissolution were used to manufacture micron and nanostructures by electro-hydraulic dynamic jet method, untreated micron and nano-spray needle channels were obtained by cutting the dissolution printed bolt.
It realizes low-cost batch manufacturing of large-area high-precision micro-nano-injection needles, improves the stability and integrity of the injection needles, and reduces production costs.
Smart Images

Figure CN119502201B_ABST
Abstract
Description
Technical Field
[0001] The present invention relates to the field of microelectromechanical technology, and particularly relates to a method for batch manufacturing of micro-nano injection needles based on cutting and dissolution and an injection needle. Background Art
[0002] Electrohydrodynamic jet printing technology uses a high-voltage electric field force to print liquid materials onto a substrate in the form of fine jets. This technology can overcome the capillary effect in traditional inkjet printing technology at small aperture sizes and achieve jet printing with a diameter much smaller than the inner diameter of the injection needle. With the development of micro-nano technology, micro-nano injection needles are increasingly widely used, and people's requirements for the size and precision of injection needles are also getting higher and higher. However, during the printing process, due to sediments, particulate matter, chemical reaction products, etc., it is extremely easy for micro-nano injection needles to have material accumulation, adhesion, or deterioration, resulting in needle blockage. Therefore, micro-nano injection needles are extremely prone to wear during the printing process.
[0003] Therefore, how to fabricate micro-nano injection needles with high precision on a large scale is a major problem that urgently needs to be solved in this field. Currently, the fabrication of high-precision micro-nano injection needles often requires expensive processing equipment and complex technological processes, resulting in high costs. How to mass-produce high-precision micro-nano injection needles at low cost is one of the key problems to be solved during the fabrication process. Summary of the Invention
[0004] The present invention overcomes the deficiencies of the prior art and provides a method for batch manufacturing of micro-nano injection needles based on cutting and dissolution and an injection needle; by using electrohydrodynamic jet printing to fabricate micro- and nano-structures, and cooperating with the casting method to obtain untrimmed micro-nano injection needles, and obtaining a micro-nano structure injection needle channel by cutting and dissolving the printed punch.
[0005] To achieve the above object, the technical solution adopted by the present invention is: a method for batch manufacturing of micro-nano injection needles based on cutting and dissolution, comprising the following steps:
[0006] Step 1, printing a plurality of groups of soluble polymer line groups on a substrate to obtain a micro-nano injection needle punch, and / or an array micro-nano injection needle punch, and entering Step 2;
[0007] Step 2, casting a casting mixed solution on the substrate printed with the soluble polymer line groups by the casting method, so that the casting mixed solution covers the cured soluble polymer line groups, and curing to obtain untrimmed micro-nano injection needles and / or untrimmed array micro-nano injection needles, and entering Step 3;
[0008] Step 3, cutting and dissolving the untrimmed micro-nano injection needles and / or untrimmed array micro-nano injection needles obtained in Step 2 by the cutting and dissolution method to obtain micro-nano injection needles having an inlet and an outlet;
[0009] The cutting and dissolution method includes:
[0010] Step 3.1: Cut the head and tail ends of the soluble polymer line groups of the untrimmed micro-nano injection needles and / or untrimmed array micro-nano injection needles, so that the head and tail ends of each group of soluble polymer line groups are exposed, and proceed to Step 3.2;
[0011] Step 3.2: Immerse the cut micro-nano injection needles and / or cut array micro-nano injection needles in the immersion solution for a period of time until the soluble polymer lines in the soluble polymer line groups are completely dissolved, obtaining conductive micro-nano injection needles.
[0012] In a preferred embodiment of the present invention, in Step 3.2, the micro-nano injection needles include one or more of single-channel micro-nano injection needles, array micro-nano injection needles, and multi-solution printing array micro-nano injection needles.
[0013] In a preferred embodiment of the present invention, in Step 1, the preparation method of the base plate includes:
[0014] Pour the casting mixed solution onto the glass substrate. After allowing the glass substrate with the casting mixed solution to stand for a period of time, heat and cure it. After cooling, obtain the base plate;
[0015] The preparation of the casting mixed solution includes:
[0016] Mix the PDMS base material and the curing agent in a weight ratio of 5:1 to 10:1, uniformly obtain the casting mixed solution, and degas the casting mixed solution to remove bubbles.
[0017] In a preferred embodiment of the present invention, the preparation method of the micro-nano injection needle convex mold includes: The preparation method of the micro-nano injection needle convex mold includes:
[0018] Perform oxygen plasma treatment on the base plate, and print soluble polymer line one on the treated base plate; then, print soluble polymer line two connecting soluble polymer line one on the basis of soluble polymer line one; then, print soluble polymer line three connecting soluble polymer line two on the basis of soluble polymer line two; repeat the above steps on the base plate several times to obtain the micro-nano injection needle convex mold; soluble polymer line one is a nano line, and soluble polymer lines two and three are micron lines.
[0019] In a preferred embodiment of the present invention, the preparation method of the array micro-nano injection needle convex mold includes:
[0020] On the substrate after oxygen plasma treatment, a soluble polymer line four is printed at intervals to obtain an array of soluble polymer lines four; then, on the basis of the array of soluble polymer lines four, a soluble polymer line five connecting the array of soluble polymer lines four is printed; then, on the basis of the soluble polymer line five, a soluble polymer line six connecting the array of soluble polymer lines five is printed; the above steps are repeated several times on the substrate after oxygen plasma treatment to obtain an array of micro-nano injection needle convex molds; the soluble polymer line four is a nano line, and the soluble polymer lines five and six are micron lines.
[0021] In a preferred embodiment of the present invention, the casting method for untrimmed micro-nano injection needles and / or untrimmed arrays of micro-nano injection needles includes:
[0022] Pour a casting mixed solution on the micro-nano injection needle convex mold and / or the array micro-nano injection needle convex mold, and place it in a vacuum oven and let it stand for a period of time to allow the casting mixed solution to fill the micro-nano injection needle convex mold and / or the array micro-nano injection needle convex mold; bake and cure, and then cool to obtain untrimmed micro-nano injection needles and / or untrimmed arrays of micro-nano injection needles.
[0023] In a preferred embodiment of the present invention, the single-channel micro-nano injection needle cutting and dissolution method includes: Step 3.1, cut the untrimmed micro-nano injection needles into pieces with a coated tool, and take the soluble polymer lines one, two, and three with different line widths connected as a group of soluble polymer line groups. During the cutting process, both ends of each group of through-soluble polymer line groups are exposed; Step 3.2, immerse the cut micro-nano injection needles in an immersion solution at a temperature of 25-50°C for 1-3 h. Among them, the immersion solution is placed in an ultrasonic cleaner to accelerate the dissolution of the soluble polymer lines, and the ultrasonic power is 80-100 W; the immersion solution is deionized water until the soluble polymer is completely dissolved to obtain micro-nano injection needles with inlets and outlets; then place them on a hot plate for a period of time to remove the moisture of the cut and trimmed micro-nano injection needles to obtain single-channel micro-nano injection needles or arrays of micro-nano injection needles;
[0024] The cutting and dissolving method of the array of micro-nano injection needles includes: Step 3.1, cutting the untrimmed micro-nano injection needles into pieces with a coated tool, taking the soluble polymer lines IV, soluble polymer line V, and soluble polymer line VI with different line widths that are connected as a group of soluble polymer lines, and exposing both ends of each group of continuous soluble polymer lines during the cutting process; Step 3.2, soaking the cut micro-nano injection needles in a soaking solution at a temperature of 25-50 °C for 1-3 h. The soaking solution is placed in an ultrasonic cleaner to accelerate the dissolution of the soluble polymer lines, and the ultrasonic power is 80-100 W; the soaking solution is deionized water until the soluble polymer is completely dissolved to obtain micro-nano injection needles with an inlet and an outlet; then, the moisture of the cut and trimmed micro-nano injection needles is removed to obtain an array of micro-nano injection needles.
[0025] And / or, the cutting and dissolving method of the multi-solution printing array of micro-nano injection needles includes:
[0026] Step 3.1, cutting the untrimmed micro-nano injection needles into pieces with a coated tool, taking soluble polymer line I, soluble polymer line II, and soluble polymer line as a group, or soluble polymer line IV, soluble polymer line V, and soluble polymer line VI as a group, cutting several groups of soluble polymer lines as a part, and exposing both ends of each group of soluble polymer lines during the cutting process. Soak the cut micro-nano injection needles in a soaking solution at a temperature of 25-50 °C for 1-3 h. The soaking solution is deionized water until the soluble polymer is completely dissolved to obtain micro-nano injection needles with an inlet and an outlet; then, the moisture of the cut and trimmed micro-nano injection needles is removed to obtain a multi-solution printing array of micro-nano injection needles.
[0027] In a preferred embodiment of the present invention, the soluble polymer in the soluble polymer line is PEO;
[0028] And / or, the printing parameters of soluble polymer line I include:
[0029] Print a PEO line with a line width of 100 nm, the printing voltage is 1800-2100 V, the PEO concentration of the PEO line is 3-5 wt%, and the working distance is 600-900 μm;
[0030] The printing parameters of soluble polymer line II include:
[0031] Print a PEO line with a line width of 50 μm on the basis of the line of soluble polymer line I, and the printing parameters are a voltage of 1500-2200 V, the PEO concentration of the PEO line is 1-3 wt%, and the working distance is 500-700 μm;
[0032] The printing parameters of soluble polymer line III include:
[0033] Print a PEO line with a line width of 100 μm on the basis of the line of soluble polymer line two. The printing parameters are a voltage of 2000 - 2500 V, the PEO concentration of the PEO line is 2 - 4 wt%, and the working distance is 600 - 800 μm. Repeat the above steps on the substrate several times to obtain a micro - nano injection needle convex mold.
[0034] And / or, the printing parameters of the soluble polymer line four include:
[0035] Print a PEO line every 5 - 8 μm to obtain an array of soluble polymer line four. The printing parameters are a voltage of 1800 - 2100 V, the PEO concentration of the PEO line is 3 - 5 wt%, and the working distance is 600 - 900 μm.
[0036] The printing parameters of the soluble polymer line five include:
[0037] Print a PEO line with a line width of 50 μm on the basis of the array of soluble polymer line four. The printing parameters are a voltage of 1500 - 2200 V, the PEO concentration is 1 - 3 wt%, and the working distance is 500 - 700 μm.
[0038] The printing parameters of the soluble polymer line six include:
[0039] Print a PEO line with a line width of 100 μm on the basis of the soluble polymer line five. The printing parameters are a voltage of 2000 - 2500 V, the PEO concentration is 2 - 4 wt%, and the working distance is 600 - 800 μm.
[0040] And / or, in step 1, mix the PDMS base material and the curing agent in a weight ratio of 5:1 - 10:1, stir for 5 min to mix evenly, then place it in a vacuum box to degas and remove bubbles, and pour it on a glass substrate. Then place the poured glass substrate on a horizontal platform in an oven and let it stand for 10 - 30 min. Subsequently, adjust the oven to 60 - 80 °C to cure the PDMS mixed solution, take it out after cooling to obtain a substrate, and the substrate is a PDMS substrate.
[0041] And / or, the parameters for the oxygen plasma treatment of the substrate include: the power is 5 - 25 W, and the treatment time is 10 - 35 s.
[0042] And / or, place the micro-nano injection needle convex mold and / or the array micro-nano injection needle convex mold poured with the casting mixed solution in a vacuum oven and evacuate for 1-2 hours to ensure that the casting mixed solution completely fills the micro-nano injection needle convex mold and / or the array micro-nano injection needle convex mold; then place it in an oven at 60-85 °C and bake for 2-4 hours to cure, and then cool to room temperature to obtain untrimmed micro-nano injection needles and / or untrimmed array micro-nano injection needles.
[0043] In a preferred embodiment of the present invention, the soluble polymer in the soluble polymer line is PEO;
[0044] And / or, the printing parameters of the soluble polymer line 1 include:
[0045] Print a PEO line with a line width of 100 nm, the printing voltage is 1800-2100 V, the PEO concentration of the PEO line is 3-5 wt%, and the working distance is 600-900 μm;
[0046] The printing parameters of the soluble polymer line 2 include:
[0047] On the basis of the line of the soluble polymer line 1, print a PEO line with a line width of 50 μm, the printing parameters are a voltage of 1500-2200 V, the PEO concentration of the PEO line is 1-3 wt%, and the working distance is 500-700 μm;
[0048] The printing parameters of the soluble polymer line 3 include:
[0049] On the basis of the line of the soluble polymer line 2, print a PEO line with a line width of 100 μm, the printing parameters are a voltage of 2000-2500 V, the PEO concentration of the PEO line is 2-4 wt%, and the working distance is 600-800 μm; repeat the above steps several times on the base plate to obtain a micro-nano injection needle convex mold;
[0050] And / or, the printing parameters of the soluble polymer line 4 include:
[0051] Print a PEO line every 5-8 μm to obtain an array of soluble polymer lines 4; the printing parameters are a voltage of 1800-2100 V, the PEO concentration of the PEO line is 3-5 wt%, and the working distance is 600-900 μm;
[0052] The printing parameters of the soluble polymer line 5 include:
[0053] On the basis of the array of soluble polymer lines 4, print a PEO line with a line width of 50 μm, the printing parameters are a voltage of 1500-2200 V, the PEO concentration is 1-3 wt%, and the working distance is 500-700 μm;
[0054] The printing parameters of the soluble polymer line six include:
[0055] Based on the soluble polymer line five, print a PEO line with a line width of 100 μm. The printing parameters are a voltage of 2000 - 2500 V, a PEO concentration of 2 - 4 wt%, and a working distance of 600 - 800 μm;
[0056] And / or, in step 1, mix the PDMS base material and the curing agent in a weight ratio of 5:1 - 10:1, stir for 5 min to mix evenly, then place it in a vacuum chamber to degas and remove bubbles, and pour it on a glass substrate. Then place the poured glass substrate on a horizontal platform in an oven and let it stand for 10 - 30 min. Subsequently, adjust the oven to 60 - 80 °C to cure the PDMS mixed solution, take it out after cooling, and obtain a base plate, and the base plate is a PDMS substrate;
[0057] And / or, the parameters for the oxygen plasma treatment of the base plate include: a power of 5 - 25 W and a treatment time of 10 - 35 s;
[0058] And / or, place the micro - nano needle convex mold and / or the array micro - nano needle convex mold poured with the pouring mixed solution in a vacuum oven and evacuate for 1 - 2 h to ensure that the pouring mixed solution completely fills the micro - nano needle convex mold and / or the array micro - nano needle convex mold; then place it in an oven at 60 - 85 °C and bake for 2 - 4 h to cure, and then cool to room temperature to obtain untrimmed micro - nano needles and / or untrimmed array micro - nano needles.
[0059] Furthermore, the working distance is the printing working distance between the print head and the base plate.
[0060] In a preferred embodiment of the present invention, the soluble polymer PEO for electro - jet printing can be replaced by PVP with a concentration of 1 - 5 wt%, AZ series positive photoresist, or BP series positive photoresist; deionized water can be replaced by AZ developer or BP developer;
[0061] And / or, perform hydrophilic treatment on the base plate using an oxygen plasma asher, with a treatment power of 5 - 25 W and a treatment time of 10 - 35 s;
[0062] And / or, evacuate in a vacuum oven environment of below 10 Pa for 1 - 2 h;
[0063] And / or, treat the trimmed micro - nano needles in deionized water, with an ultrasonic power of 80 - 100 W, a temperature of 25 - 50 °C, and a time of 1 - 3 h to dissolve PEO;
[0064] And / or, place the trimmed micro - nano needles on a hot plate at 85 - 150 °C for 10 - 30 min to remove moisture.
[0065] In a preferred embodiment of the present invention, a micro - nano injection needle is prepared by a batch manufacturing method of micro - nano injection needles based on cutting and dissolution.
[0066] The present invention solves the defects existing in the technical background, and the beneficial technical effects of the present invention are:
[0067] The batch manufacturing method of micro - nano injection needles based on cutting and dissolution and the injection needles of the present invention; by using the electro - hydrodynamic jet printing method to fabricate micro - meter and nano - meter structures, large - area micro - nano injection needle convex molds and array micro - nano injection needle convex molds are obtained. Then, the untrimmed micro - nano injection needles are obtained by the casting method, that is, PDMS is cast on the large - area micro - nano injection needle convex molds and array micro - nano injection needle convex molds and cured. Subsequently, it is trimmed by a coated tool and placed in a soaking solution to dissolve the micro - nano structure of the soluble polymer, and finally, stable and complete single - channel micro - nano injection needles, array micro - nano injection needles and multi - solution printing array micro - nano injection needles are obtained. The process of the present invention is simple, low - cost and can be produced in large areas. Brief Description of the Drawings
[0068] The present invention will be further described below in conjunction with the drawings and embodiments.
[0069] Figure 1 is the preparation flow chart of the micro - nano injection needle convex mold and the array micro - nano injection needle convex mold in the preferred embodiment of the present invention;
[0070] Figure 2 is the manufacturing flow chart of manufacturing single - channel micro - nano injection needles, array micro - nano injection needles and multi - solution printing array micro - nano injection needles by the casting and dissolution method in the preferred embodiment of the present invention;
[0071] Figure 3 is the structure diagram of the single - channel micro - nano injection needle in the preferred embodiment of the present invention;
[0072] Figure 4 is the structure diagram of the array micro - nano injection needle in the preferred embodiment of the present invention;
[0073] Figure 5 is the structure schematic diagram of the multi - solution printing array micro - nano injection needle in the preferred embodiment of the present invention;
[0074] Figure 6 is the microscope image of the single - channel micro - nano injection needle convex mold in the third preferred embodiment of the present invention;
[0075] Figure 7 is the microscope image of the array micro - nano injection needle convex mold in the third preferred embodiment of the present invention;
[0076] Figure 8 is the SEM image of the cross - section of the nano - channel in the single - channel micro - nano injection needle in the third preferred embodiment of the present invention;
[0077] Figure 9 It is the SEM image of the cross-section of the nanochannel in the multi-solution printing array micro-nano injection needle in the third preferred embodiment of the present invention;
[0078] Figure 10 It is the SEM image of the cross-section of the nanochannel in the array micro-nano injection needle in the third preferred embodiment of the present invention;
[0079] In the figure: 1. Substrate; 2. Oxygen plasma asher; 3. Soluble polymer line one; 4. Soluble polymer line two; 5. Soluble polymer line three; 6. Beaker; 7. Deionized water; 8. Hot plate, 91. Soluble polymer line four; 92. Soluble polymer line five; 93. Soluble polymer line six. Detailed implementation manners
[0080] Now, the present invention will be further described in detail with reference to the accompanying drawings and embodiments. These drawings are all simplified schematic diagrams, which only illustrate the basic structure of the present invention in a schematic manner, so they only show the components related to the present invention.
[0081] It should be noted that if there are directional indications (such as up, down, bottom, top, etc.) involved in the embodiments of the present invention, then such directional indications are only used to explain the relative positional relationship and movement conditions between components in a specific posture. If this specific posture changes, then the directional indications will also change accordingly. The terms "first" and "second" are only used for descriptive purposes and cannot be understood as indicating or implying relative importance or implicitly specifying the quantity of the indicated technical features. Thus, features defined with "first" and "second" may explicitly or implicitly include one or more of such features. Unless otherwise clearly specified and defined, the terms "set", "connected", and "connected to" should be understood in a broad sense. For example, it may be a fixed connection, a detachable connection, or an integral connection; it may be directly connected or indirectly connected through an intermediate medium, and it may be the internal connection of two components. For those of ordinary skill in the art, the specific meanings of the above terms in the present invention can be understood in specific situations.
[0082] As Figures 1 - 2 shown, a batch manufacturing method of micro-nano injection needles based on cutting and dissolution includes the following steps:
[0083] Step 1, print several groups of soluble polymer line groups on the substrate 1 to obtain a micro-nano injection needle convex mold and / or an array micro-nano injection needle convex mold, and enter Step 2.
[0084] Among them, the preparation method of the substrate 1 includes: pouring a casting mixed solution on a glass substrate, then leaving the glass substrate with the poured casting mixed solution to stand for a period of time, heating and curing, and after cooling, obtaining the substrate 1;
[0085] Among them, the preparation of the casting mixed solution includes: mixing the PDMS base material and the curing agent in a weight ratio of 5:1 to 10:1, stirring for 5 min to mix evenly to obtain the casting mixed solution; then placing the casting mixed solution in a vacuum box for degassing to remove bubbles, and casting it on a glass substrate (the parameters for the oxygen plasma treatment of the base plate 1 include: power of 5-25 W and treatment time of 10-35 s), then placing the cast glass substrate on a horizontal platform in an oven and standing for 10-30 min, and then adjusting the oven to 60-80 °C to cure the PDMS mixed solution, taking it out after cooling to obtain the base plate 1, and the base plate 1 is a PDMS substrate ( Figure 1 as shown in 1a).
[0086] Furthermore, the preparation method of the micro-nano injection needle convex mold includes:
[0087] Performing oxygen plasma treatment on the base plate 1 ( Figure 1 as shown in 1b), printing the soluble polymer line 1-3 on the treated base plate 1 ( Figure 1 as shown in 1C1); then, printing the soluble polymer line 2-4 connecting the soluble polymer line 1-3 on the basis of the soluble polymer line 1-3 ( Figure 1 as shown in 1d1); then, printing the soluble polymer line 3-5 connecting the soluble polymer line 2-4 on the basis of the soluble polymer line 2-4 ( Figure 1 as shown in 1e1); repeating the above steps on the base plate 1 several times to obtain the micro-nano injection needle convex mold ( Figure 1 as shown in 1f).
[0088] More specifically, the printing parameters of the soluble polymer line 1-3 include: printing a PEO line with a line width of 100 nm, printing voltage of 1800-2100 V, PEO concentration of the PEO line of 3-5 wt%, and working distance of 600-900 μm; the printing parameters of the soluble polymer line 2-4 include: printing a PEO line with a line width of 50 μm on the basis of the line of the soluble polymer line 1-3, printing parameters of voltage of 1500-2200 V, PEO concentration of the soluble polymer line of 1-3 wt%, and working distance of 500-700 μm; the printing parameters of the soluble polymer line 3-5 include: printing a PEO line with a line width of 100 μm on the basis of the line of the soluble polymer line 2-4, printing parameters of voltage of 2000-2500 V, PEO concentration of the soluble polymer line of 2-4 wt%, and working distance of 600-800 μm. Repeating the above steps on the PDMS substrate several times to obtain the micro-nano injection needle convex mold.
[0089] Among them, the preparation method of the array micro-nano injection needle convex mold includes:
[0090] On the substrate 1 after oxygen plasma treatment, a soluble polymer line 91 is printed at intervals to obtain an array of soluble polymer lines 91 ( Figure 1 as shown in Fig. 1C2); then, on the basis of the array of soluble polymer lines 91, a soluble polymer line 92 connecting the array of soluble polymer lines 91 is printed ( Figure 1 as shown in Fig. 1d2); then, on the basis of the soluble polymer line 92, a soluble polymer line 93 connecting the array of soluble polymer lines 92 is printed ( Figure 1 as shown in Fig. 1e2); the above steps are repeated several times on the PDMS substrate after oxygen plasma treatment to obtain an array of micro-nano injection needle convex molds ( Figure 1 as shown in Fig. 1f). More specifically, the printing parameters of the soluble polymer line 91 include: a PEO line is printed every 5 - 8 μm to obtain an array of soluble polymer lines 91; the printing parameters are a voltage of 1800 - 2100 V, a PEO concentration of 3 - 5 wt%, and a working distance of 600 - 900 μm; the printing parameters of the soluble polymer line 92 include: a PEO line with a line width of 50 μm is printed on the basis of the array of soluble polymer lines 91, the printing parameters are a voltage of 1500 - 2200 V, a PEO concentration of 1 - 3 wt%, and a working distance of 500 - 700 μm; the printing parameters of the soluble polymer line 93 include: a line with a line width of 100 μm is printed on the basis of the soluble polymer line 92, the printing parameters are a voltage of 2000 - 2500 V, a PEO concentration of 2 - 4 wt%, and a working distance of 600 - 800 μm.
[0091] Step 2: Pour a pouring mixed solution on the substrate 1 printed with soluble polymer lines ( Figure 2 as shown in Fig. 2a), so that the pouring mixed solution covers the soluble polymer lines, and cure to obtain untrimmed micro-nano injection needles and / or untrimmed arrays of micro-nano injection needles, and enter Step 3.
[0092] Specifically, the pouring method for the untrimmed micro-nano injection needles and / or untrimmed arrays of micro-nano injection needles includes:
[0093] Pour the pouring mixed solution on the micro-nano injection needle convex mold and / or the array of micro-nano injection needle convex molds, and place it in a vacuum oven and let it stand for a period of time to make the pouring mixed solution fill the micro-nano injection needle convex mold and / or the array of micro-nano injection needle convex molds; bake and cure, and then cool to obtain untrimmed micro-nano injection needles and / or untrimmed arrays of micro-nano injection needles.
[0094] Further, place the micro-nano injection needle convex mold and / or the array micro-nano injection needle convex mold poured with the casting mixed solution in a vacuum oven and evacuate for 1-2 h to ensure that the casting mixed solution completely fills the micro-nano injection needle convex mold and / or the array micro-nano injection needle convex mold; then place it in an oven at 60-85 °C and bake for 2-4 h for curing (wherein, when the temperature is 60 °C, cure for 4 h, when the temperature is 70 °C, cure for 3 h, when the temperature is 80 °C, cure for 2 h), and then cool to room temperature to obtain the untrimmed micro-nano injection needles and / or the untrimmed array micro-nano injection needles.
[0095] Step 3: Cut and dissolve the untrimmed micro-nano injection needles and / or the untrimmed array micro-nano injection needles obtained in Step 2 by the cutting and dissolving method to obtain the micro-nano injection needles and / or the array micro-nano injection needles with inlets and outlets. The cutting and dissolving method includes: Step 3.1: Cut the head and tail ends of the PEO line groups of the untrimmed micro-nano injection needles and / or the untrimmed array micro-nano injection needles, so that the head and tail ends of each group of soluble polymer line groups are exposed ( Figure 2 as shown in 2b, 2c1, 2c2, 2c3 in the figure), and enter Step 3.2; Step 3.2: Immerse the cut micro-nano injection needles in the soaking solution in beaker 6 for a period of time ( Figure 2 as shown in 2d in the figure), until the soluble polymer in the soluble polymer line group is completely dissolved to obtain the conductive micro-nano injection needles. Step 3.2: The micro-nano injection needles include one or more of single-channel micro-nano injection needles, array micro-nano injection needles, and multi-solution printing array micro-nano injection needles ( Figure 2 as shown in 2e in the figure).
[0096] Specifically, the cutting and dissolving method for single-channel micro-nano injection needles includes: Step 3.1: Cut the untrimmed micro-nano injection needles into pieces with a coating tool, and take the soluble polymer line 3 with different line widths, soluble polymer line 4, and soluble polymer line 5 that are connected as a group of PEO line groups. During the cutting process, make the head and tail ends of each group of through PEO lines exposed; Step 3.2: Immerse the cut micro-nano injection needles in the soaking solution at a temperature of 25-50 °C for 1-3 h. The soaking solution is deionized water 7 until the PEO is completely dissolved to obtain the micro-nano injection needles with inlets and outlets; then remove the moisture from the cut and trimmed micro-nano injection needles to obtain single-channel micro-nano injection needles or array micro-nano injection needles. Among them, the soaking solution is placed in an ultrasonic cleaner to accelerate the dissolution of the PEO lines, and the ultrasonic power is 80-100 W.
[0097] Specifically, the cutting and dissolving method of the array of micro-nano injection needles includes: Step 3.1, cutting the untrimmed micro-nano injection needles into pieces with a coated tool, taking the soluble polymer lines with different line widths, namely Soluble Polymer Line Four 91, Soluble Polymer Line Five 92, and Soluble Polymer Line Six 93, which are connected, as a group of PEO line groups. During the cutting process, the head and tail ends of each group of continuous PEO lines are exposed; Step 3.2, soaking the cut micro-nano injection needles in a soaking solution at a temperature of 25-50°C for 1-3 h ( Figure 2 as shown in 2d), and the soaking solution is deionized water 7 until the PEO is completely dissolved to obtain micro-nano injection needles with an inlet and an outlet; subsequently, the cut and trimmed micro-nano injection needles are dehydrated to obtain an array of micro-nano injection needles ( Figure 2 as shown in 2e). Among them, the soaking solution is placed in an ultrasonic cleaner to accelerate the dissolution of the PEO lines, and the ultrasonic power is 80-100 W.
[0098] Specifically, the cutting and dissolving method of the multi-solution printing array of micro-nano injection needles includes: Step 3.1, cutting the untrimmed micro-nano injection needles into pieces with a coated tool, taking three connected soluble polymer lines with different line widths, namely Soluble Polymer Line One 3, Soluble Polymer Line Two 4, and Soluble Polymer Line as a group, or Soluble Polymer Line Four 91, Soluble Polymer Line Five 92, and Soluble Polymer Line Six 93 as a group. Every 2-3 groups of PEO lines are cut as a part. During the cutting process, the head and tail ends of each group of PEO lines are exposed. The cut micro-nano injection needles are soaked in a soaking solution at a temperature of 25-50°C for 1-3 h, and the soaking solution is deionized water 7 until the PEO is completely dissolved to obtain micro-nano injection needles with an inlet and an outlet; subsequently, the cut and trimmed micro-nano injection needles are dehydrated to obtain a multi-solution printing array of micro-nano injection needles. Among them, the soaking solution is placed in an ultrasonic cleaner to accelerate the dissolution of the PEO lines, and the ultrasonic power is 80-100 W. Example 1
[0099] As Figures 1 - 2 shown, a batch manufacturing method of micro-nano injection needles based on cutting and dissolving includes the following steps:
[0100] Step 1, printing several groups of soluble polymer line groups on the base plate 1 to obtain a micro-nano injection needle convex mold and / or an array micro-nano injection needle convex mold, and then entering Step 2.
[0101] Among them, the preparation method of the base plate 1 includes: pouring a casting mixed solution on a glass substrate, then allowing the glass substrate with the poured casting mixed solution to stand for a period of time, heating and curing, and after cooling, obtaining the base plate 1;
[0102] Among them, the preparation of the casting mixed solution includes: mixing the PDMS base material and the curing agent in a weight ratio of 5:1, stirring for 5 min to mix evenly to obtain the casting mixed solution; then placing the casting mixed solution in a vacuum box for degassing to remove bubbles, and casting it on a glass substrate (the parameters for the oxygen plasma treatment of the base plate 1 include: power of 5 W, treatment time of 10 s), then placing the cast glass substrate on a horizontal platform in an oven and standing for 10 min, then adjusting the oven to 60 °C and curing for 4 h to cure the PDMS mixed solution, taking it out after cooling to obtain the base plate 1, and the base plate 1 is a PDMS substrate.
[0103] Further, the preparation method of the micro-nano injection needle convex mold includes:
[0104] Performing oxygen plasma treatment on the base plate 1, and printing a soluble polymer line 1-3 on the treated base plate 1; then, printing a soluble polymer line 2-4 on the basis of the soluble polymer line 1-3; then, printing a soluble polymer line 3-5 on the basis of the soluble polymer line 2-4; repeating the above steps on the base plate 1 several times to obtain the micro-nano injection needle convex mold. More specifically, the printing parameters of the soluble polymer line 1-3 include: printing a PEO line with a line width of 100 nm, printing voltage of 1800 V, PEO concentration of the PEO line of 3 wt%, and working distance of 600 μm; the printing parameters of the soluble polymer line 2-4 include: printing a line with a line width of 50 μm on the basis of the line of the soluble polymer line 1-3, and the printing parameters are voltage of 1500 V, PEO concentration of the PEO line of 1 wt%, and working distance of 500 μm; the printing parameters of the soluble polymer line 3-5 include: printing a line with a line width of 100 μm on the basis of the line of the soluble polymer line 2-4, and the printing parameters are voltage of 2000 V, PEO concentration of the PEO line of 2 wt%, and working distance of 600 μm. Repeating the above steps on the PDMS substrate several times to obtain the micro-nano injection needle convex mold.
[0105] Among them, the preparation method of the array micro-nano injection needle convex mold includes:
[0106] After the oxygen plasma treatment of the substrate 1, a soluble polymer line four 91 is printed at regular intervals to obtain an array of soluble polymer lines four 91; then, on the basis of the array of soluble polymer lines four 91, a soluble polymer line five 92 connecting the array of soluble polymer lines four 91 is printed; then, on the basis of the soluble polymer line five 92, a soluble polymer line six 93 connecting the array of soluble polymer lines five 92 is printed; the above steps are repeated several times on the PDMS substrate after oxygen plasma treatment to obtain an array of micro-nano injection needle convex molds. More specifically, the printing parameters of the soluble polymer line four 91 include: printing a soluble polymer line four 91 every 5 μm to obtain an array of soluble polymer lines four 91; the printing parameters are a voltage of 1800 V, a PEO concentration of 3 wt%, and a working distance of 600 μm; the printing parameters of the soluble polymer line five 92 include: printing a line with a width of 50 μm on the basis of the array of soluble polymer lines four 91, and the printing parameters are a voltage of 1500 V, a PEO concentration of 1 wt%, and a working distance of 500 μm; the printing parameters of the soluble polymer line six 93 include: printing a line with a width of 100 μm on the basis of the soluble polymer line five 92, and the printing parameters are a voltage of 2000 V, a PEO concentration of 2 wt%, and a working distance of 600 μm.
[0107] Step 2, pour a casting mixed solution on the substrate 1 printed with PEO lines by the casting method, so that the casting mixed solution covers the PEO lines, and cure to obtain untrimmed micro-nano injection needles and / or untrimmed arrays of micro-nano injection needles, and enter Step 3.
[0108] Specifically, the casting method for untrimmed micro-nano injection needles and / or untrimmed arrays of micro-nano injection needles includes:
[0109] Pour the casting mixed solution on the micro-nano injection needle convex mold and / or the array micro-nano injection needle convex mold, and place it in a vacuum oven and let it stand for a period of time to allow the casting mixed solution to fill the micro-nano injection needle convex mold and / or the array micro-nano injection needle convex mold; bake and cure, and then cool to obtain untrimmed micro-nano injection needles and / or untrimmed arrays of micro-nano injection needles.
[0110] Furthermore, place the micro-nano injection needle convex mold and / or the array micro-nano injection needle convex mold poured with the casting mixed solution in a vacuum oven and evacuate for 1 h to ensure that the casting mixed solution completely fills the micro-nano injection needle convex mold and / or the array micro-nano injection needle convex mold; then place it in an oven at 60 °C and bake for 4 h to cure, and then cool to room temperature to obtain untrimmed micro-nano injection needles and / or untrimmed arrays of micro-nano injection needles.
[0111] Step 3: Obtain the micro-nano injection needles and / or array micro-nano injection needles with inlets and outlets by cutting and dissolving the untrimmed micro-nano injection needles and / or untrimmed array micro-nano injection needles obtained in Step 2. The cutting and dissolving method includes: Step 3.1: Cut the head and tail ends of the PEO line groups of the untrimmed micro-nano injection needles and / or untrimmed array micro-nano injection needles, so that the head and tail ends of each group of PEO line groups are exposed, and proceed to Step 3.2; Step 3.2: Immerse the cut micro-nano injection needles in the soaking solution in beaker 6 for a period of time until the PEO in the PEO line groups is completely dissolved, obtaining conductive micro-nano injection needles. Step 3.2: The micro-nano injection needles include one or more of single-channel micro-nano injection needles, array micro-nano injection needles, and multi-solution printing array micro-nano injection needles.
[0112] Specifically, the cutting and dissolving method for single-channel micro-nano injection needles includes: Step 3.1: Cut the untrimmed micro-nano injection needles in blocks with a coated tool, and take the connected soluble polymer lines with different line widths, namely soluble polymer line 3, soluble polymer line 4, and soluble polymer line 5, as a group of PEO line groups. During the cutting process, expose the head and tail ends of each group of through PEO lines; Step 3.2: Immerse the cut micro-nano injection needles in the soaking solution at a temperature of 25°C for 3 hours. The soaking solution is deionized water 7 until the PEO is completely dissolved, obtaining micro-nano injection needles with inlets and outlets; then remove the moisture from the cut and trimmed micro-nano injection needles to obtain single-channel micro-nano injection needles or array micro-nano injection needles. Among them, the soaking solution is placed in an ultrasonic cleaner to accelerate the dissolution of the PEO lines, and the ultrasonic power is 80-100W; in this embodiment, the ultrasonic power is 80W.
[0113] Specifically, the cutting and dissolving method for array micro-nano injection needles includes: Step 3.1: Cut the untrimmed micro-nano injection needles in blocks with a coated tool, and take the connected soluble polymer lines with different line widths, namely soluble polymer line 491, soluble polymer line 492, and soluble polymer line 493, as a group of PEO line groups. During the cutting process, expose the head and tail ends of each group of through PEO lines; Step 3.2: Immerse the cut micro-nano injection needles in the soaking solution at a temperature of 25°C for 3 hours. The soaking solution is deionized water 7 until the PEO is completely dissolved, obtaining micro-nano injection needles with inlets and outlets; then remove the moisture from the cut and trimmed micro-nano injection needles to obtain array micro-nano injection needles. Among them, the soaking solution is placed in an ultrasonic cleaner to accelerate the dissolution of the PEO lines, and the ultrasonic power is 80-100W; in this embodiment, the ultrasonic power is 80W.
[0114] Specifically, the cutting and dissolving method for the multi-solution printing array micro-nano injection needles includes: Step 3.1, using a coating tool to cut the untrimmed micro-nano injection needles into pieces, with three connected soluble polymer lines of different line widths, namely soluble polymer line 3, soluble polymer line 4, and PEO line as a group, or soluble polymer line 91, soluble polymer line 92, and soluble polymer line 93 as a group. Every 2 or 3 groups of PEO lines are cut as a part. During the cutting process, the head and tail ends of each group of PEO lines are exposed. The cut micro-nano injection needles are soaked in a soaking solution at a temperature of 25°C for 3 hours. The soaking solution is deionized water 7 until the PEO is completely dissolved, obtaining micro-nano injection needles with inlets and outlets. Subsequently, the moisture of the cut and trimmed micro-nano injection needles is removed to obtain the multi-solution printing array micro-nano injection needles. Among them, the soaking solution is placed in an ultrasonic cleaner to accelerate the dissolution of the PEO lines, and the ultrasonic power is 80 - 100W. In this embodiment, the ultrasonic power is 80W. Embodiment 2
[0115] As Figures 1 - 2 shown, a batch manufacturing method for micro-nano injection needles based on cutting and dissolving includes the following steps:
[0116] Step 1, print several groups of soluble polymer line groups on the base plate 1 to obtain a micro-nano injection needle convex mold and / or an array micro-nano injection needle convex mold, and proceed to Step 2.
[0117] Among them, the preparation method of the base plate 1 includes: pouring a casting mixed solution on a glass substrate, then leaving the glass substrate with the poured casting mixed solution to stand for a period of time, heating and curing, and after cooling, obtaining the base plate 1;
[0118] Among them, the preparation of the casting mixed solution includes: mixing PDMS base material and curing agent in a weight ratio of 10:1, stirring for 5 minutes to mix evenly to obtain the casting mixed solution; subsequently, placing the casting mixed solution in a vacuum box to degas and remove bubbles, and pouring it on the glass substrate (the parameters for the oxygen plasma treatment of the base plate 1 include: power of 25W, treatment time of 35s). Then, place the poured glass substrate on the horizontal platform in the oven and let it stand for 30 minutes. Subsequently, adjust the oven to 80°C and cure for 2 hours to cure the PDMS mixed solution. After cooling, take it out to obtain the base plate 1, and the base plate 1 is a PDMS substrate.
[0119] Furthermore, the preparation method of the micro-nano injection needle convex mold includes:
[0120] The base substrate 1 is subjected to oxygen plasma treatment, and a soluble polymer line 1-3 is printed on the treated base substrate 1; then, a soluble polymer line 2-4 is printed on the basis of the soluble polymer line 1-3; then, a soluble polymer line 3-5 is printed on the basis of the soluble polymer line 2-4; the above steps are repeated several times on the base substrate 1 to obtain a micro-nano injection needle convex mold. More specifically, the soluble polymer in the soluble polymer line 1-3 is PEO, and the specific printing parameters include: printing a PEO line with a line width of 100 nm, the printing voltage is 2100 V, the PEO concentration of the PEO line is 5 wt%, and the working distance is 900 μm; the printing parameters of the soluble polymer line 2-4 include: printing a PEO line with a line width of 50 μm on the basis of the line of the soluble polymer line 1-3, the printing parameters are a voltage of 2200 V, the PEO concentration of the PEO line is 3 wt%, and the working distance is 700 μm; the printing parameters of the soluble polymer line 3-5 include: printing a PEO line with a line width of 100 μm on the basis of the line of the soluble polymer line 2-4, the printing parameters are a voltage of 2500 V, the PEO concentration of the PEO line is 4 wt%, and the working distance is 800 μm. The above steps are repeated several times on the PDMS substrate to obtain a micro-nano injection needle convex mold.
[0121] Among them, the preparation method of the array micro-nano injection needle convex mold includes:
[0122] At regular intervals on the base substrate 1 after oxygen plasma treatment, a soluble polymer line 4-91 is printed to obtain an array of soluble polymer lines 4-91; then, a soluble polymer line 5-92 connecting the array of soluble polymer lines 4-91 is printed on the basis of the array of soluble polymer lines 4-91; then, a soluble polymer line 6-93 connecting the array of soluble polymer lines 5-92 is printed on the basis of the soluble polymer line 5-92; the above steps are repeated several times on the PDMS substrate after oxygen plasma treatment to obtain an array micro-nano injection needle convex mold. More specifically, the printing parameters of the soluble polymer line 4-91 include: printing a PEO line every 8 μm to obtain an array of soluble polymer lines 4-91; the printing parameters are a voltage of 2100 V, a PEO concentration of 5 wt%, and a working distance of 900 μm; the printing parameters of the soluble polymer line 5-92 include: printing a PEO line with a line width of 50 μm on the basis of the array of soluble polymer lines 4-91, the printing parameters are a voltage of 1500-2200 V, a PEO concentration of 3 wt%, and a working distance of 700 μm; the printing parameters of the soluble polymer line 6-93 include: printing a PEO line with a line width of 100 μm on the basis of the soluble polymer line 5-92, the printing parameters are a voltage of 2500 V, a PEO concentration of 4 wt%, and a working distance of 800 μm.
[0123] Step 2: Pour the casting mixed solution onto the base plate 1 printed with the soluble polymer line groups by the casting method, so that the casting mixed solution covers the soluble polymer line groups, and cure to obtain the untrimmed micro-nano injector needles and / or untrimmed array micro-nano injector needles, then proceed to Step 3.
[0124] Specifically, the casting method for the untrimmed micro-nano injector needles and / or untrimmed array micro-nano injector needles includes:
[0125] Pour the casting mixed solution onto the micro-nano injector needle convex mold and / or array micro-nano injector needle convex mold, and place it in a vacuum oven and let it stand for a period of time to allow the casting mixed solution to fill the micro-nano injector needle convex mold and / or array micro-nano injector needle convex mold; bake and cure, then cool to obtain the untrimmed micro-nano injector needles and / or untrimmed array micro-nano injector needles.
[0126] Further, place the micro-nano injector needle convex mold and / or array micro-nano injector needle convex mold poured with the casting mixed solution in a vacuum oven and evacuate for 2 h to ensure that the casting mixed solution completely fills the micro-nano injector needle convex mold and / or array micro-nano injector needle convex mold; then place it in an 85 °C oven and bake for 1.5 h for curing, and then cool to room temperature to obtain the untrimmed micro-nano injector needles and / or untrimmed array micro-nano injector needles.
[0127] Step 3: Cut and dissolve the untrimmed micro-nano injector needles and / or untrimmed array micro-nano injector needles obtained in Step 2 by the cutting and dissolving method to obtain the micro-nano injector needles and / or array micro-nano injector needles with inlets and outlets. The cutting and dissolving method includes: Step 3.1: Cut the head and tail ends of the PEO line groups of the untrimmed micro-nano injector needles and / or untrimmed array micro-nano injector needles, so that the head and tail ends of each group of PEO line groups are exposed, and then proceed to Step 3.2; Step 3.2: Immerse the cut micro-nano injector needles in the soaking solution in the beaker 6 for a period of time until the PEO in the soluble polymer line groups is completely dissolved to obtain the conductive micro-nano injector needles. Step 3.2: The micro-nano injector needles include one or more of single-channel micro-nano injector needles, array micro-nano injector needles, and multi-solution printing array micro-nano injector needles.
[0128] Specifically, the single-channel micro-nano injection needle cutting and dissolution method includes: Step 3.1: Use a coated tool to cut the untrimmed micro-nano injection needle into pieces. The soluble polymer lines with different line widths, namely soluble polymer line 1-3, soluble polymer line 2-4, and soluble polymer line 3-5, which are connected, are used as a group of PEO line groups. During the cutting process, the head and tail ends of each group of continuous PEO lines are exposed; Step 3.2: Immerse the cut micro-nano injection needle in a soaking solution at a temperature of 50°C for 1 h. The soaking solution is deionized water 7 until the PEO is completely dissolved to obtain a micro-nano injection needle with an inlet and an outlet. Subsequently, remove the moisture from the cut and trimmed micro-nano injection needle to obtain a single-channel micro-nano injection needle or an array of micro-nano injection needles. Among them, the soaking solution is placed in an ultrasonic cleaner to accelerate the dissolution of the PEO lines, and the ultrasonic power is 80-100 W; in this embodiment, the ultrasonic power is 100 W.
[0129] Specifically, the cutting and dissolution method of the array of micro-nano injection needles includes: Step 3.1: Use a coated tool to cut the untrimmed micro-nano injection needle into pieces. The soluble polymer lines with different line widths, namely soluble polymer line 4-91, soluble polymer line 5-92, and soluble polymer line 6-93, which are connected, are used as a group of PEO line groups. During the cutting process, the head and tail ends of each group of continuous PEO lines are exposed; Step 3.2: Immerse the cut micro-nano injection needle in a soaking solution at a temperature of 50°C for 1 h. The soaking solution is deionized water 7 until the PEO is completely dissolved to obtain a micro-nano injection needle with an inlet and an outlet. Subsequently, remove the moisture from the cut and trimmed micro-nano injection needle to obtain an array of micro-nano injection needles. Among them, the soaking solution is placed in an ultrasonic cleaner to accelerate the dissolution of the PEO lines, and the ultrasonic power is 80-100 W; in this embodiment, the ultrasonic power is 100 W.
[0130] Specifically, the cutting and dissolution method of the multi-solution printing array of micro-nano injection needles includes: Step 3.1: Use a coated tool to cut the untrimmed micro-nano injection needle into pieces. Take 3 segments of connected soluble polymer lines with different line widths, namely soluble polymer line 1-3, soluble polymer line 2-4, and the PEO line as a group, or 3 segments of connected soluble polymer lines with different line widths, namely soluble polymer line 4-91, soluble polymer line 5-92, and soluble polymer line 6-93 as a group. Cut every 2 or 3 groups of PEO lines as a part. During the cutting process, the head and tail ends of each group of PEO lines are exposed. Immerse the cut micro-nano injection needle in a soaking solution at a temperature of 50°C for 1 h. The soaking solution is deionized water 7 until the PEO is completely dissolved to obtain a micro-nano injection needle with an inlet and an outlet. Subsequently, remove the moisture from the cut and trimmed micro-nano injection needle to obtain a multi-solution printing array of micro-nano injection needles. Among them, the soaking solution is placed in an ultrasonic cleaner to accelerate the dissolution of the PEO lines, and the ultrasonic power is 80-100 W; in this embodiment, the ultrasonic power is 100 W. Example 3
[0131] AsFigures 1 - 10 As shown, a method for batch manufacturing of micro-nano injection needles based on cutting and dissolution includes the following steps:
[0132] Step 1: Print several groups of soluble polymer line groups on the base plate 1 to obtain a micro-nano injection needle convex mold and / or an array micro-nano injection needle convex mold, and then proceed to Step 2.
[0133] Among them, the preparation method of the base plate 1 includes: pouring a casting mixed solution on a glass substrate, then leaving the glass substrate with the poured casting mixed solution to stand for a period of time, heating and curing, and after cooling, obtaining the base plate 1;
[0134] Among them, the preparation of the casting mixed solution includes: mixing PDMS base material and curing agent in a weight ratio of 8:1, stirring for 5 min to mix evenly to obtain the casting mixed solution; then placing the casting mixed solution in a vacuum box to degas and remove bubbles, and pouring it on the glass substrate (the parameters for oxygen plasma treatment of the base plate 1 include: power of 15 W, treatment time of 25 s), then placing the poured glass substrate on a horizontal platform in an oven and standing for 20 min, then adjusting the oven to 70 °C and curing for 3 h to cure the PDMS mixed solution, taking it out after cooling, obtaining the base plate 1, and the base plate 1 is a PDMS substrate.
[0135] Furthermore, the preparation method of the micro-nano injection needle convex mold includes:
[0136] Perform oxygen plasma treatment on the base plate 1, and print soluble polymer line 1-3 on the treated base plate 1; then, print soluble polymer line 2-4 on the basis of soluble polymer line 1-3; then, print soluble polymer line 3-5 on the basis of soluble polymer line 2-4; repeat the above steps on the base plate 1 several times to obtain the micro-nano injection needle convex mold. More specifically, the printing parameters of soluble polymer line 1-3 include: printing a PEO line with a line width of 100 nm, printing voltage of 1950 V, PEO concentration of the PEO line of 4.5 wt%, and working distance of 750 μm; the printing parameters of soluble polymer line 2-4 include: printing a PEO line with a line width of 50 μm on the basis of the line of soluble polymer line 1-3, the printing parameters being voltage of 1800 V, PEO concentration of the PEO line of 2 wt%, and working distance of 600 μm; the printing parameters of soluble polymer line 3-5 include: printing a PEO line with a line width of 100 μm on the basis of the line of soluble polymer line 2-4, the printing parameters being voltage of 2250 V, PEO concentration of the PEO line of 3 wt%, and working distance of 700 μm. Repeat the above steps on the PDMS substrate several times to obtain the micro-nano injection needle convex mold.
[0137] Among them, the preparation method of the array micro-nano injection needle convex mold includes:
[0138] On the oxygen plasma-treated substrate 1, a soluble polymer line four 91 is printed at intervals to obtain an array of soluble polymer lines four 91; then, on the basis of the array of soluble polymer lines four 91, a soluble polymer line five 92 connecting the array of soluble polymer lines four 91 is printed; then, on the basis of the soluble polymer line five 92, a soluble polymer line six 93 connecting the array of soluble polymer lines five 92 is printed; the above steps are repeated several times on the PDMS substrate after oxygen plasma treatment to obtain an array of micro-nano injection needle convex molds. More specifically, the printing parameters of the soluble polymer line four 91 include: printing a soluble polymer line four 91 every 7 μm to obtain an array of soluble polymer lines four 91; the printing parameters are a voltage of 1950 V, a PEO concentration of 4.5 wt%, and a working distance of 800 μm; the printing parameters of the soluble polymer line five 92 include: printing a PEO line with a line width of 50 μm on the basis of the array of soluble polymer lines four 91, and the printing parameters are a voltage of 2250 V, a PEO concentration of 2 wt%, and a working distance of 600 μm; the printing parameters of the soluble polymer line six 93 include: printing a PEO line with a line width of 100 μm on the basis of the soluble polymer line five 92, and the printing parameters are a voltage of 2250 V, a PEO concentration of 3 wt%, and a working distance of 700 μm.
[0139] Step 2, a casting mixed solution is cast on the substrate 1 printed with the soluble polymer line group by the casting method, so that the casting mixed solution covers the soluble polymer line group, and after curing, an untrimmed micro-nano injection needle and / or an untrimmed array of micro-nano injection needles are obtained, and step 3 is entered.
[0140] Specifically, the casting method for the untrimmed micro-nano injection needle and / or the untrimmed array of micro-nano injection needles includes:
[0141] The casting mixed solution is cast on the micro-nano injection needle convex mold and / or the array of micro-nano injection needle convex molds, and placed in a vacuum oven and left standing for a period of time to allow the casting mixed solution to fill the micro-nano injection needle convex mold and / or the array of micro-nano injection needle convex molds; baked and cured, and then cooled to obtain an untrimmed micro-nano injection needle and / or an untrimmed array of micro-nano injection needles.
[0142] Further, the micro-nano injection needle convex mold and / or the array of micro-nano injection needle convex molds cast with the casting mixed solution are placed in a vacuum oven and evacuated for 1.5 h to ensure that the casting mixed solution completely fills the micro-nano injection needle convex mold and / or the array of micro-nano injection needle convex molds; then placed in an oven at 70 °C and baked for 3 h for curing, and then cooled to room temperature to obtain an untrimmed micro-nano injection needle and / or an untrimmed array of micro-nano injection needles.
[0143] Step 3: Obtain the micro / nano injection needles and / or array micro / nano injection needles with inlets and outlets by cutting and dissolving the untrimmed micro / nano injection needles and / or untrimmed array micro / nano injection needles obtained in Step 2. The cutting and dissolving method includes: Step 3.1: Cut the head and tail ends of the PEO line groups of the untrimmed micro / nano injection needles and / or untrimmed array micro / nano injection needles, so that the head and tail ends of each group of PEO line groups are exposed, and proceed to Step 3.2; Step 3.2: Immerse the cut micro / nano injection needles in the soaking solution in beaker 6 for a period of time until the PEO in the PEO line groups is completely dissolved, obtaining the conductive micro / nano injection needles. Step 3.2: The micro / nano injection needles include one or more of single-channel micro / nano injection needles, array micro / nano injection needles, and multi-solution printing array micro / nano injection needles.
[0144] Specifically, the cutting and dissolving method for single-channel micro / nano injection needles includes: Step 3.1: Cut the untrimmed micro / nano injection needles in blocks with a coated tool, and take the connected soluble polymer lines with different line widths, namely soluble polymer line 3, soluble polymer line 4, and soluble polymer line 5, as a group of PEO line groups. During the cutting process, expose the head and tail ends of each group of through PEO lines; Step 3.2: Immerse the cut micro / nano injection needles in the soaking solution at a temperature of 35°C for 2 h. The soaking solution is deionized water 7 until the PEO is completely dissolved, obtaining the micro / nano injection needles with inlets and outlets; then remove the moisture from the cut and trimmed micro / nano injection needles to obtain single-channel micro / nano injection needles or array micro / nano injection needles. Among them, the soaking solution is placed in an ultrasonic cleaner to accelerate the dissolution of the PEO lines, and the ultrasonic power is 80 - 100 W; in this embodiment, the ultrasonic power is 90 W.
[0145] Specifically, the cutting and dissolving method for array micro / nano injection needles includes: Step 3.1: Cut the untrimmed micro / nano injection needles in blocks with a coated tool, and take the connected soluble polymer lines with different line widths, namely soluble polymer line 91, soluble polymer line 92, and soluble polymer line 93, as a group of PEO line groups. During the cutting process, expose the head and tail ends of each group of through PEO lines; Step 3.2: Immerse the cut micro / nano injection needles in the soaking solution at a temperature of 35°C for 2 h. The soaking solution is deionized water 7 until the PEO is completely dissolved, obtaining the micro / nano injection needles with inlets and outlets; then remove the moisture from the cut and trimmed micro / nano injection needles to obtain array micro / nano injection needles. Among them, the soaking solution is placed in an ultrasonic cleaner to accelerate the dissolution of the PEO lines, and the ultrasonic power is 80 - 100 W; in this embodiment, the ultrasonic power is 90 W.
[0146] Specifically, the cutting and dissolving method for the multi-solution printing array micro-nano injection needles includes: Step 3.1, using a coating tool to cut the untrimmed micro-nano injection needles into pieces, so that three connected soluble polymer lines with different line widths, i.e., soluble polymer line three 3, soluble polymer line two 4, and PEO line, are grouped together, or soluble polymer line four 91, soluble polymer line five 92, and soluble polymer line six 93 are grouped together. Every 2 or 3 groups of PEO lines are cut as a part. During the cutting process, the head and tail ends of each group of PEO lines are exposed. Immerse the cut micro-nano injection needles in the immersion liquid at a temperature of 35°C for 2 h. The immersion liquid is deionized water 7 until the PEO is completely dissolved to obtain micro-nano injection needles with inlets and outlets. Subsequently, remove the moisture from the cut and trimmed micro-nano injection needles to obtain the multi-solution printing array micro-nano injection needles. Among them, the immersion liquid is placed in an ultrasonic cleaner to accelerate the dissolution of the PEO lines, and the ultrasonic power is 80 - 100 W. In this embodiment, the ultrasonic power is 90 W. Example Four
[0147] Based on Example One, the soluble polymer PEO in the soluble polymer line group for electrohydrodynamic printing can be replaced with PVP with a concentration of 1 wt%. Example Five
[0148] Based on Example Three, the PEO ink for electrohydrodynamic printing can be replaced with PVP with a concentration of 5 wt%. Example Six
[0149] Based on Example Two, the PEO ink for electrohydrodynamic printing can be replaced with PVP with a concentration of 3 wt%. Example Seven
[0150] Based on Example One, the soluble polymer PEO in the soluble polymer line group for electrohydrodynamic printing can be replaced with AZ series positive photoresist. Deionized water can be replaced with AZ developer. Example Eight
[0151] Based on Example Two, the soluble polymer PEO in the soluble polymer line group for electrohydrodynamic printing can be replaced with BP series positive photoresist. Deionized water can be replaced with BP developer. Example Nine
[0152] Based on Example One, the substrate 1 is subjected to hydrophilic treatment using an oxygen plasma asher 2 with a treatment power of 5 W and a treatment time of 10 s. Vacuum is pumped in a vacuum oven environment below 10 Pa for 1 h. The trimmed micro-nano injection needles are treated in deionized water 7 at a temperature of 25°C for 1 h to dissolve the PEO; the trimmed micro-nano injection needles are placed on a hot plate 8 at 85°C for 30 min to remove moisture. Example Ten
[0153] On the basis of Example 2, the base plate 1 is subjected to hydrophilic treatment using an oxygen plasma asher 2 with a treatment power of 25 W and a treatment time of 35 s. It is evacuated for 2 h in a vacuum oven environment below 10 Pa. The trimmed micro-nano injection needles are treated in deionized water 7 at a temperature of 50 °C for 1 - 3 h to dissolve PEO; the trimmed micro-nano injection needles are placed on a hot plate 8 at 100 °C for 20 min to remove moisture. Example XI
[0154] On the basis of Example 3, the base plate 1 is subjected to hydrophilic treatment using an oxygen plasma asher 2 with a treatment power of 15 W and a treatment time of 25 s. It is evacuated for 1.5 h in a vacuum oven environment below 10 Pa. The trimmed micro-nano injection needles are treated in deionized water 7 at a temperature of 35 °C for 2 h to dissolve PEO; the trimmed micro-nano injection needles are placed on a hot plate 8 at 150 °C for 10 min to remove moisture. Example XII
[0155] An injection needle is prepared by using the method for batch manufacturing of micro-nano injection needles based on cutting and dissolution in Example 3.
[0156] Working principle:
[0157] The present invention is a method for batch manufacturing of micro-nano injection needles based on cutting and dissolution and an injection needle; micron and nano structures are printed and manufactured by the electrohydrodynamic jet method, and an untrimmed micro-nano injection needle is obtained by cooperating with the casting method. By cutting and dissolving the printed punch, a stable and complete micro-nano structure injection needle channel is obtained. The process of the present invention is simple, low in cost, and can be mass-produced. Figure 3 It is a structural diagram of a single-channel micro-nano injection needle; Figure 4 It is a structural diagram of an array micro-nano injection needle; Figure 5 It is a schematic structural diagram of an array micro-nano injection needle printed with multiple solutions; Figure 6 It is a microscope image of a single-channel micro-nano injection needle punch; Figure 7 It is a microscope image of an array micro-nano injection needle punch; Figure 8 It is a SEM image of the cross-section of the nano-channel in a single-channel micro-nano injection needle; Figure 9 It is a SEM image of the cross-section of the nano-channel in an array micro-nano injection needle printed with multiple solutions; Figure 10It is the SEM image of the cross-section of the nanochannel in the array of micro-nano injection needles. The present invention manufactures micro- and nano-structures by electrohydrodynamic jet printing to obtain large-area micro-nano injection needle convex molds and array micro-nano injection needle convex molds. Then, the untrimmed micro-nano injection needles are obtained by the casting method, that is, PDMS is cast on the large-area micro-nano injection needle convex mold and the array micro-nano injection needle convex mold and cured. Subsequently, it is trimmed by a coated tool, and the PEO micro-nano structure is dissolved in deionized water 7, and finally, stable and complete single-channel micro-nano injection needles, array micro-nano injection needles, and multi-solution printing array micro-nano injection needles are obtained.
[0158] The above specific implementation manners are the specific supports for the proposed solution idea of the present invention, and the protection scope of the present invention cannot be limited thereby. Any equivalent change or equivalent modification made on the basis of this technical solution according to the technical idea proposed by the present invention still belongs to the protection scope of the technical solution of the present invention.
Claims
1. A method for batch manufacturing of micro-nano spray needles based on cutting and dissolution, characterized in that: The following steps are involved: Step 1, printing a plurality of groups of soluble polymer line groups on a substrate to obtain a micro-nano spray needle convex mold and / or an array micro-nano spray needle convex mold, and then proceeding to step 2; Step 2, pouring a pouring mixed solution on the substrate plate printed with the soluble polymer line group by pouring method, so that the pouring mixed solution covers the solidified soluble polymer line group, and solidifying to obtain untrimmed micro-nano spray needles and / or untrimmed array micro-nano spray needles, and then proceeding to step 3; Step 3, cutting and dissolving the untrimmed micro-nano spray needle and / or the untrimmed array micro-nano spray needle obtained in step 2 by a cutting and dissolving method to obtain a micro-nano spray needle and / or an array micro-nano spray needle having an inlet and an outlet; The cutting and dissolving method comprises: Step 3.1, cutting the untrimmed micro-nano spray needles and / or the untrimmed array micro-nano spray needles at both ends of the soluble polymer line group, so that both ends of each group of soluble polymer line groups are exposed, and proceeding to step 3.2; Step 3.2, soaking the cut micro-nano spray needles and / or the cut array micro-nano spray needles in a soaking solution for a period of time until the soluble polymer lines in the soluble polymer line group are completely dissolved to obtain conductive micro-nano spray needles and / or array micro-nano spray needles; The micro-nano spray needle is a single-channel micro-nano spray needle; the cutting and dissolving method of the single-channel micro-nano spray needle comprises: step 3.1, cutting the untrimmed micro-nano spray needle into blocks with a coated tool, and connecting the soluble polymer line 1, the soluble polymer line 2, and the soluble polymer line 3 with different line widths as a group of soluble polymer line groups, and exposing both ends of each group of connected soluble polymer line groups during the cutting process; step 3.2, soaking the cut micro-nano spray needle in a soaking liquid with a temperature of 25-50° C. for 1-3 hours, wherein the soaking liquid is placed in an ultrasonic cleaning machine to accelerate the dissolution of the soluble polymer line, and the ultrasonic power is 80-100W; the soaking liquid is deionized water, until the soluble polymer is completely dissolved, and a micro-nano spray needle with an inlet and an outlet is obtained; then the cut and trimmed micro-nano spray needle is placed on a hot plate for a period of time to remove the moisture of the cut and trimmed micro-nano spray needle, and a single-channel micro-nano spray needle or an array micro-nano spray needle is obtained; And / or, the cutting and dissolving method of the array micro-nano spray needle includes: step 3.1, cutting the untrimmed micro-nano spray needle into blocks with a coated tool, and connecting the soluble polymer line four, soluble polymer line five, and soluble polymer line six with different line widths as a group of soluble polymer line groups, and exposing both ends of each group of connected soluble polymer line groups during the cutting process; step 3.2, soaking the cut micro-nano spray needle in a soaking liquid with a temperature of 25~50℃ for 1~3h, wherein the soaking liquid is placed in an ultrasonic cleaning machine to accelerate the dissolution of the soluble polymer line, and the ultrasonic power is 80~100W; the soaking liquid is deionized water, until the soluble polymer is completely dissolved to obtain a micro-nano spray needle with an inlet and an outlet; then, the cut and trimmed micro-nano spray needle is dehydrated to obtain an array micro-nano spray needle.
2. The method for batch manufacturing of micro-nano spray needles based on cutting and dissolution according to claim 1, characterized in that: In step 1, the method for preparing the base plate includes: Casting the casting mixed solution on a glass substrate, leaving the glass substrate cast with the casting mixed solution to stand for a period of time, heating and solidifying it, and cooling it to obtain a substrate plate; The preparation of the casting mixed solution comprises: The PDMS base material and the curing agent are mixed in a weight ratio of 5:1 to 10:1 to uniformly obtain a casting mixed solution, and the casting mixed solution is degassed to remove bubbles.
3. The method for batch manufacturing of micro-nano spray needles based on cutting and dissolution according to claim 2 is characterized in that: The preparation method of the micro-nano spray needle convex mold comprises: The substrate is subjected to oxygen plasma treatment, and a soluble polymer line one is printed on the treated substrate; then, a soluble polymer line two connected to the soluble polymer line one is printed on the basis of the soluble polymer line one; then, a soluble polymer line three connected to the soluble polymer line two is printed on the basis of the soluble polymer line two; Repeat the above steps several times on the substrate to obtain a micro-nano spray needle convex mold; The soluble polymer line one is a nano line, and the soluble polymer line two and the soluble polymer line three are micrometer lines.
4. The method for batch manufacturing of micro-nano spray needles based on cutting and dissolution according to claim 3 is characterized in that: The preparation method of the micro-nano spray needle convex mold comprises: Printing a soluble polymer line four at intervals on the substrate plate treated with oxygen plasma to obtain soluble polymer line four of the array; then, printing a soluble polymer line five connecting the soluble polymer line four of the array on the basis of the soluble polymer line four of the array; then, printing a soluble polymer line six connecting the soluble polymer line five of the array on the basis of the soluble polymer line five; Repeat the above steps several times on the substrate plate treated with oxygen plasma to obtain an array micro-nano spray needle convex mold; The soluble polymer line four is a nanometer line, and the soluble polymer line five and the soluble polymer line six are micrometer lines.
5. The method for batch manufacturing of micro-nano spray needles based on cutting and dissolution according to claim 4 is characterized in that: The casting method of the untrimmed micro-nano spray needle and / or the untrimmed array micro-nano spray needle comprises: The casting mixed solution is cast on the micro-nano spray needle convex mold and / or the array micro-nano spray needle convex mold, and the mold is placed in a vacuum oven for a period of time to allow the casting mixed solution to fill the micro-nano spray needle convex mold and / or the array micro-nano spray needle convex mold; baked and solidified, and then cooled to obtain untrimmed micro-nano spray needles and / or untrimmed array micro-nano spray needles.
6. The method for batch manufacturing of micro-nano spray needles based on cutting and dissolution according to claim 5, characterized in that: The untrimmed micro-nano spray needle is cut into blocks with a coated tool, so that soluble polymer line one, soluble polymer line two, and soluble polymer line three with different line widths are grouped together, or soluble polymer line four, soluble polymer line five, and soluble polymer line six are grouped together, and several groups of soluble polymer line groups are cut as a part, and the ends of each group of soluble polymer line groups are exposed during the cutting process; the cut micro-nano spray needle is immersed in an immersion solution with a temperature of 25-50°C for 1-3 hours, and the immersion solution is deionized water, until the soluble polymer is completely dissolved, and a micro-nano spray needle with an inlet and an outlet is obtained; then the cut and trimmed micro-nano spray needle is dehydrated to obtain a multi-solution printing array micro-nano spray needle.
7. The method for batch manufacturing of micro-nano spray needles based on cutting and dissolution according to claim 6, characterized in that: The soluble polymer in the soluble polymer line is PEO; And / or, the printing parameters of the soluble polymer line one include: Print a 100nm PEO line with a printing voltage of 1800-2100V, a PEO concentration of 3-5wt%, and a working distance of 600-900μm; The printing parameters for soluble polymer line 2 include: A PEO line with a line width of 50 μm is printed on the basis of the line of the soluble polymer line 1, and the printing parameters are voltage 1500~2200 V, PEO concentration of the PEO line is 1~3wt%, and working distance is 500~700 μm; The printing parameters for soluble polymer line three include: A PEO line with a line width of 100 μm is printed on the basis of the line of the soluble polymer line 2, and the printing parameters are a voltage of 2000-2500 V, a PEO concentration of 2-4 wt % of the PEO line, and a working distance of 600-800 μm; the above steps are repeated several times on the substrate to obtain a micro-nano spray needle convex mold; And / or, the printing parameters of the soluble polymer line four include: A PEO line was printed every 5-8 μm to obtain array soluble polymer line four; the printing parameters were voltage 1800-2100 V, PEO concentration of the PEO line was 3-5 wt%, and working distance was 600-900 μm; The printing parameters for soluble polymer line five include: A PEO line with a line width of 50 μm was printed on the basis of the array soluble polymer line 4, and the printing parameters were voltage 1500~2200 V, PEO concentration 1~3wt%, and working distance 500~700 μm; The printing parameters for soluble polymer line six include: A PEO line with a line width of 100 μm was printed on the basis of the soluble polymer line 5, and the printing parameters were voltage 2000-2500 V, PEO concentration 2-4 wt%, and working distance 600-800 μm; And / or, in step 1, the PDMS base material and the curing agent are mixed together in a weight ratio of 5:1 to 10:1, stirred for 5 minutes to mix evenly, then placed in a vacuum box for degassing to remove bubbles, and poured on a glass substrate, then the poured glass substrate is placed on a horizontal platform in an oven and left to stand for 10 to 30 minutes, then the oven is adjusted at 60 to 80° C. to cure the PDMS mixed solution, and taken out after cooling to obtain a substrate plate, wherein the substrate plate is a PDMS substrate; And / or, the parameters of the oxygen plasma treatment of the substrate include: power of 5 to 25 W, treatment time of 10 to 35 s; And / or, the micro-nano spray needle convex mold and / or the array micro-nano spray needle convex mold cast with the casting mixed solution is placed in a vacuum oven for 1-2 hours to ensure that the casting mixed solution completely fills the micro-nano spray needle convex mold and / or the array micro-nano spray needle convex mold; then placed in a 60-85ºC oven for 2-4 hours to cure, and then cooled to room temperature to obtain untrimmed micro-nano spray needles and / or untrimmed array micro-nano spray needles.
8. The method for batch manufacturing of micro-nano spray needles based on cutting and dissolution according to claim 7, characterized in that: The soluble polymer PEO of electrojet printing can be replaced by PVP, AZ series positive photoresist, and BP series positive photoresist with a concentration of 1~5wt%; Deionized water can be replaced by AZ developer and BP developer; and / or, using an oxygen plasma ashing apparatus to perform hydrophilic treatment on the substrate, with a treatment power of 5 to 25 W and a treatment time of 10 to 35 seconds; And / or, evacuate the environment in a vacuum oven below 10Pa for 1-2 hours; and / or, treating the trimmed micro-nano spray needle in deionized water with an ultrasonic power of 80-100 W, a temperature of 25-50° C., and a time of 1-3 h to dissolve PEO; and / or, placing the trimmed micro-nano spray needle on a hot plate at 85-150° C. for 10-30 min to remove moisture.
9. A spray needle, characterized in that: The micro-nano spray needle is prepared by the batch manufacturing method of micro-nano spray needle based on cutting and dissolution as described in any one of claims 1 to 8.
Citation Information
Patent Citations
Manufacturing method for large-size seamless micro-nano soft mold
CN108162425A