WO2023120782A1 - Adhesive conductive hydrogel using radiation crosslinking method, method for preparing same, and adhesive conductive hydrogel sheet using same - Google Patents

Adhesive conductive hydrogel using radiation crosslinking method, method for preparing same, and adhesive conductive hydrogel sheet using same Download PDF

Info

Publication number
WO2023120782A1
WO2023120782A1 PCT/KR2021/019808 KR2021019808W WO2023120782A1 WO 2023120782 A1 WO2023120782 A1 WO 2023120782A1 KR 2021019808 W KR2021019808 W KR 2021019808W WO 2023120782 A1 WO2023120782 A1 WO 2023120782A1
Authority
WO
WIPO (PCT)
Prior art keywords
hydrogel
adhesive conductive
conductive hydrogel
composition
electron beam
Prior art date
Application number
PCT/KR2021/019808
Other languages
French (fr)
Korean (ko)
Inventor
하태성
박지현
정평환
이미랑
강경민
이영환
Original Assignee
서울방사선서비스주식회사
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 서울방사선서비스주식회사 filed Critical 서울방사선서비스주식회사
Priority to PCT/KR2021/019808 priority Critical patent/WO2023120782A1/en
Publication of WO2023120782A1 publication Critical patent/WO2023120782A1/en

Links

Images

Classifications

    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
    • A61B5/00—Measuring for diagnostic purposes; Identification of persons
    • A61B5/24—Detecting, measuring or recording bioelectric or biomagnetic signals of the body or parts thereof
    • A61B5/25—Bioelectric electrodes therefor
    • A61B5/263—Bioelectric electrodes therefor characterised by the electrode materials
    • A61B5/266—Bioelectric electrodes therefor characterised by the electrode materials containing electrolytes, conductive gels or pastes
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
    • A61B5/00—Measuring for diagnostic purposes; Identification of persons
    • A61B5/24—Detecting, measuring or recording bioelectric or biomagnetic signals of the body or parts thereof
    • A61B5/25—Bioelectric electrodes therefor
    • A61B5/263—Bioelectric electrodes therefor characterised by the electrode materials
    • A61B5/268—Bioelectric electrodes therefor characterised by the electrode materials containing conductive polymers, e.g. PEDOT:PSS polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
    • C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
    • C08J3/075—Macromolecular gels
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/28—Treatment by wave energy or particle radiation

Definitions

  • the present invention relates to an adhesive conductive hydrogel using a radiation crosslinking method, a method for preparing the same, and an adhesive conductive hydrogel sheet using the same. It relates to an adhesive conductive hydrogel prepared by
  • Polymer hydrogels are used in various fields because they contain a wetting agent and water in a matrix composed of cross-linked polymers.
  • a conductive polymer hydrogel containing a wetting agent and water by cross-linking polymerization of an electrolyte polymer such as polyacrylic acid has been used as an electrode for a living body.
  • the polymer matrix is hydrophilic and water permeable and contains water at the same time, the polymer hydrogel has the advantage of being easy to add an electrolyte and enabling low impedance. For this reason, it can exhibit sufficient performance as an electrode for high-precision measurement such as electrocardiogram monitoring.
  • the prior art has a disadvantage of causing skin trouble when attached to the skin for a long time by adding a crosslinking agent, an initiator, and a stabilizer to crosslink the polymer.
  • a hydrogel is prepared through UV photopolymerization by adding a UV initiator to a hydrogel composition, but the hydrogel prepared in this way cannot maintain its shape, so a base film is essential, and a photoinitiator crosslinking There is a disadvantage that is harmful to the human body by using the back.
  • a monomolecular electrolyte such as NaCl or NaOH is injected to impart conductivity to the polymer hydrogel.
  • a monomolecular electrolyte such as NaCl or NaOH is injected to impart conductivity to the polymer hydrogel.
  • the applicant of the present application intends to propose a technology capable of providing a polymer hydrogel having more improved adhesive strength and conductivity compared to existing polymer hydrogel manufacturing technologies below, and in particular, electron beam irradiation of ionic monomers to crosslink
  • a technology for a conductive hydrogel that has an appropriate degree of crosslinking without a separate initiator and can be used without a separate substrate.
  • the present invention has been devised to solve the above-mentioned conventional problems and to consider them, and by crosslinking a prehydrogel composition containing an ionic monomer by electron beam irradiation, it has an appropriate degree of crosslinking without a separate initiator and adhesive conductivity that can be used without a separate substrate.
  • the purpose is to provide a hydrogel, a manufacturing method thereof, and an adhesive conductive hydrogel sheet using the same.
  • the present invention is an ionic monomer; Preparing a pre-hydrogel composition by mixing distilled water and a pH adjusting agent; and
  • an electron beam irradiation step of crosslinking by irradiating an electron beam having an energy of 1 to 10 MeV with an absorbed dose of 5 kGy to 50 kGy; Including,
  • the ionic monomer is 2-acrylamido-2-methylpropanesulfonic acid (AMPS), 2-hydroxylethyl acrylate, 2-ethylhexyl acrylate, n-butyl Acrylate (n-butyl acrylate), n-butyl methacrylate (n-butyl methacrylate), acrylic acid (acrylic acid) and 3- (3,4-dihydroxyphenyl) -L-alanine (3- (3, 4-Dihydroxyphenyl) -L-alanine) containing any one or more,
  • AMPS 2-acrylamido-2-methylpropanesulfonic acid
  • 2-hydroxylethyl acrylate 2-ethylhexyl acrylate
  • n-butyl Acrylate n-butyl acrylate
  • n-butyl methacrylate n-butyl methacrylate
  • acrylic acid acrylic acid
  • the pH adjusting agent includes at least one of sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium chloride, and potassium chloride,
  • the conductivity is 0.5 to 5 S / m, and the adhesive force is 600 to 2000 gf / in, which provides a method for producing an adhesive conductive hydrogel.
  • the present invention is 2-acrylamido-2-methylpropanesulfonic acid (AMPS), 2-hydroxyethyl acrylate (2-hydroxylethyl acrylate), acrylic acid (acrylic acid) and 3- (3,4-dihydroxy Phenyl) -L-alanine (3- (3,4-Dihydroxyphenyl) -L-alanine) is provided by crosslinking the prehydrogel composition containing any one of the ionic monomers by electron beam irradiation,
  • the conductivity is 0.5 to 5 S / m, and the adhesive force is 600 to 2000 gf / in, characterized in that it provides an adhesive conductive hydrogel.
  • the present invention is 2-acrylamido-2-methylpropanesulfonic acid (AMPS), 2-hydroxyethyl acrylate (2-hydroxylethyl acrylate), acrylic acid (acrylic acid) and 3- (3,4-dihydroxy A prehydrogel composition containing any one ionic monomer of phenyl) -L-alanine (3- (3,4-Dihydroxyphenyl) -L-alanine), and a nonwoven fabric layer provided in the form of a sheet,
  • AMPS 2-acrylamido-2-methylpropanesulfonic acid
  • 2-hydroxyethyl acrylate (2-hydroxylethyl acrylate)
  • acrylic acid acrylic acid
  • 3- 3- (3,4-dihydroxy
  • a nonwoven fabric layer provided in the form of a sheet
  • the prehydrogel composition is applied to at least one surface of the nonwoven fabric layer and then crosslinked by electron beam irradiation to form an adhesive conductive hydrogel,
  • the non-woven fabric layer provides an adhesive conductive hydrogel sheet, characterized in that it is bonded to the adhesive conductive hydrogel by grafting.
  • the adhesive conductive hydrogel has an appropriate degree of crosslinking, can be used without a separate substrate, and has excellent conductivity by irradiating an electron beam to a prehydrogel composition in which an ionic monomer, distilled water, and a pH adjusting agent are mixed at a predetermined ratio. At the same time, it exhibits excellent adhesive strength, and it is possible to prevent skin troubles that occur when attached to the skin for a long time without using a separate initiator.
  • FIG. 1 is a schematic process diagram shown to explain a method for manufacturing an adhesive conductive hydrogel according to an embodiment of the present invention.
  • FIG. 2 is an image showing a cross-sectional view of an adhesive conductive hydrogel sheet according to an embodiment of the present invention.
  • 3 is data obtained by evaluating physical properties of an adhesive conductive hydrogel according to an embodiment of the present invention.
  • 4 and 5 are data obtained by evaluating the cytotoxicity of the adhesive conductive hydrogel according to an embodiment of the present invention.
  • the present invention an ionic monomer; Preparing a pre-hydrogel composition by mixing distilled water and a pH adjusting agent; and
  • an electron beam having an energy of 1 to 10 MeV was applied at 5 kGy to an electron beam irradiation step of crosslinking by irradiating with an absorbed dose of 50 kGy;
  • the ionic monomers are 2-acrylamido-2-methylpropanesulfonic acid (AMPS), 2-hydroxylethyl acrylate, acrylic acid and 3-(3,4-dihydroxy).
  • AMPS 2-acrylamido-2-methylpropanesulfonic acid
  • 2-hydroxylethyl acrylate 2-hydroxylethyl acrylate
  • acrylic acid 2-hydroxylethyl acrylate
  • 3-(3,4-dihydroxy) 2-acrylamido-2-methylpropanesulfonic acid
  • Phenyl) -L-alanine (3- (3,4-Dihydroxyphenyl) -L-alanine) containing any one or more,
  • the pH adjusting agent includes at least one of sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium chloride, and potassium chloride,
  • the conductivity is 0.5 to 5 S / m, and the adhesive force is 600 to 2000 gf / in, which provides a method for producing an adhesive conductive hydrogel.
  • the method for producing an adhesive conductive hydrogel may include a preliminary hydrogel composition preparation step (S100) and an electron beam irradiation step (S200).
  • the preliminary hydrogel composition preparation step (S100) is a step of preparing a preliminary hydrogel composition for preparing an adhesive conductive hydrogel by mixing an ionic monomer, distilled water, and a pH adjusting agent.
  • prehydrogel composition preparation step (S100) 40 to 70 parts by weight, 45 to 65 parts by weight, or 45 to 60 parts by weight of an ionic monomer; 30 to 60 parts by weight or 45 to 60 parts by weight of distilled water and 10 to 30 parts by weight or 15 to 25 parts by weight of a pH adjusting agent may be mixed.
  • any one of sodium hydroxide, sodium carbonate, potassium hydroxide, lithium hydroxide, sodium chloride, and potassium chloride may be used as a pH adjusting agent.
  • a pH adjusting agent By using such a pH adjusting agent, the pH of the hydrogel composition can be adjusted to 5 to 6.
  • the preliminary hydrogel composition consists of only 2-acrylamido-2-methylpropanesulfonic acid (AMPS), distilled water and sodium hydroxide, and the preliminary hydrogel composition preparation step is separately performed. It can exhibit excellent adhesiveness and conductivity without adding a photopolymerization initiator and a UV polymerization initiator.
  • AMPS 2-acrylamido-2-methylpropanesulfonic acid
  • the hydrogel composition manufacturing step (S100) is an ionic monomer; After mixing the distilled water and the pH adjusting agent, it may further include adding a crosslinking agent.
  • the crosslinking agent is poly(ethylene glycol) diacrylate (PEG-DA), 2-hydroxylethyl acrylate, acrylic acid and 3-(3,4-dihydride). It may include any one or more of hydroxyphenyl) -L-alanine (3- (3,4-Dihydroxyphenyl) -L-alanine).
  • the crosslinking agent may be mixed in an amount of 0.01 to 0.08 parts by weight, 0.02 to 0.07 parts by weight, and 0.03 to 0.06 parts by weight.
  • an adhesive conductive hydrogel having an appropriate degree of crosslinking can be prepared through the electron beam irradiation step (S200) without adding a crosslinking agent to the prehydrogel composition, but as described above, a small amount of When a crosslinking agent is included, mechanical strength can be improved without deteriorating adhesive performance.
  • the electron beam irradiation step (S200) is a step of preparing an adhesive conductive hydrogel by applying an electron beam having a certain amount of energy to crosslink after applying the prehydrogel composition.
  • an electron beam may be irradiated after applying the prehydrogel composition to a thickness of 0.5 to 10 mm or 0.5 to 5 mm.
  • an electron beam having an energy of 1 to 10 MeV or 1 to 10 MeV may be irradiated with an absorbed dose of 5 kGy to 50 kGy to crosslink.
  • the prehydrogel composition is irradiated with an absorbed dose of 5 kGy to 40 kGy, 5 kGy to 30 kGy, or 5 to 20 KGy to impart adhesiveness and conductivity at the same time when preparing the adhesive conductive hydrogel.
  • the degree of crosslinking of the ionic monomer in the adhesive conductive hydrogel prepared through the electron beam irradiation step (S200) may be 50% to 80%, 55% to 80%, or 55% to 75%.
  • the prehydrogel composition may be crosslinked by irradiation with an irradiation beam under the above-described conditions, thereby exhibiting the degree of crosslinking as described above, thereby improving mechanical strength while having excellent adhesiveness.
  • the applied prehydrogel composition is irradiated with an electron beam as described above so that the ionic monomer is crosslinked to form an adhesive conductive hydrogel without a separate substrate. Can be formed.
  • an electron beam may be irradiated after applying the prehydrogel composition on the nonwoven fabric.
  • the nonwoven fabric may have a hot melt adhesive layer formed on one surface of the nonwoven fabric, and the adhesive conductive hydrogel may be prepared by applying a composition to the surface of the nonwoven fabric on which the hot melt adhesive layer is formed and then irradiating an electron beam.
  • the hydrogel and the nonwoven fabric may be grafted while forming a hydrogel layer on the nonwoven fabric.
  • the bonding strength between the hydrogel layer and the nonwoven fabric is improved, and durability may be excellent.
  • the present invention is 2-acrylamido-2-methylpropanesulfonic acid (AMPS), 2-hydroxyethyl acrylate (2-hydroxylethyl acrylate), acrylic acid (acrylic acid) and 3- (3,4-dihydroxy Phenyl) -L-alanine (3- (3,4-Dihydroxyphenyl) -L-alanine) is provided by crosslinking the prehydrogel composition containing any one of the ionic monomers by electron beam irradiation,
  • the conductivity is 0.5 to 5 S / m, and the adhesive force is 600 to 2000 gf / in, characterized in that it provides an adhesive conductive hydrogel.
  • the adhesive conductive hydrogel is composed of 2-acrylamido-2-methylpropanesulfonic acid (AMPS), 2-hydroxylethyl acrylate, acrylic acid and 3-(3,4-dihydride). It is crosslinked by electron beam irradiation to any one ionic monomer of 3-(3,4-Dihydroxyphenyl)-L-alanine, and can exhibit excellent adhesiveness and conductivity at the same time.
  • AMPS 2-acrylamido-2-methylpropanesulfonic acid
  • 2-hydroxylethyl acrylate acrylic acid
  • 3-(3,4-dihydride) 3-(3,4-dihydride
  • the electron beam absorbed dose of the adhesive conductive hydrogel may be 5 to 20 KGy or 5 to 15 KGy, and the thickness of the adhesive conductive hydrogel may be 0.5 to 10 mm or 0.5 to 5 mm.
  • the conductivity and adhesiveness of the adhesive conductive hydrogel can be simultaneously improved.
  • the adhesive conductive hydrogel may have a conductivity of 0.5 to 5 S/m, 0.5 to 4 S/m, or 0.8 to 3 S/m, and the adhesive conductive hydrogel may have a conductivity of 600 to 2000 gf/in, 700 to 1800 gf /in or from 800 to 1700 gf/in.
  • the adhesive conductive hydrogel according to the present invention is prepared by crosslinking an ionic monomer by irradiating an electron beam without a separate initiator, and can maintain excellent adhesive strength and conductivity without a crosslinking agent.
  • the crosslinking rate is improved and the mechanical strength is excellent, but when a certain amount or more of the crosslinking agent is added, the crosslinking rate is too high and the cohesive between the main chains of the hydrogel is lowered, resulting in a lower adhesive property.
  • the degree of crosslinking of the ionic monomer in the adhesive conductive hydrogel may be 50% to 80%, 55% to 80%, or 55% to 75%. In the case of having the above degree of crosslinking, excellent conductivity and mechanical strength can be exhibited without deterioration in adhesive properties.
  • the adhesive conductive hydrogel of the present invention can exhibit the above degree of crosslinking by irradiating the prehydrogel composition with an irradiation beam under the conditions described above, thereby improving mechanical strength while having excellent adhesiveness.
  • the tensile strength of the adhesive conductive hydrogel may be 200 kPa to 300 kPa, 200 kPa to 290 kPa, or 200 kPa to 280 kPa.
  • the present invention is 2-acrylamido-2-methylpropanesulfonic acid (AMPS), 2-hydroxyethyl acrylate (2-hydroxylethyl acrylate), acrylic acid (acrylic acid) and 3- (3,4-dihydroxy A prehydrogel composition containing any one ionic monomer of phenyl) -L-alanine (3- (3,4-Dihydroxyphenyl) -L-alanine), and a nonwoven fabric layer provided in the form of a sheet,
  • AMPS 2-acrylamido-2-methylpropanesulfonic acid
  • 2-hydroxyethyl acrylate (2-hydroxylethyl acrylate)
  • acrylic acid acrylic acid
  • 3- 3- (3,4-dihydroxy
  • a nonwoven fabric layer provided in the form of a sheet
  • the prehydrogel composition is applied to at least one surface of the nonwoven fabric layer and then crosslinked by electron beam irradiation to form an adhesive conductive hydrogel,
  • the non-woven fabric layer provides an adhesive conductive hydrogel sheet, characterized in that it is bonded to the adhesive conductive hydrogel by grafting.
  • the adhesive conductive hydrogel sheet according to an embodiment of the present invention may have a structure in which a hydrogel layer 10, a hot melt adhesive layer 21, and a nonwoven fabric layer 22 are stacked in this order.
  • the adhesive conductive hydrogel sheet of the present invention may further include a nonwoven fabric layer 22 on at least one surface of the adhesive conductive hydrogel 10.
  • the nonwoven fabric may have a hot melt adhesive layer 21 formed on one surface of the nonwoven fabric, and an adhesive conductive hydrogel 10 may be laminated on the surface of the nonwoven fabric on which the hot melt adhesive layer 21 is formed.
  • the nonwoven fabric layer can be grafted and combined with the adhesive conductive hydrogel. Accordingly, the bonding force between the adhesive conductive hydrogel and the nonwoven fabric layer is improved, and durability may be excellent.
  • the hydrogel of the example for the test is a mixed solution by mixing ionic monomer 2-acrylamido-2-methylpropanesulfonic acid (AMPS), distilled water, sodium hydroxide, a crosslinking agent, an electrolyte and an adhesion promoter as shown in Table 1 below. manufactured.
  • AMPS ionic monomer 2-acrylamido-2-methylpropanesulfonic acid
  • distilled water sodium hydroxide
  • a crosslinking agent sodium hydroxide
  • an electrolyte an electrolyte and an adhesion promoter as shown in Table 1 below. manufactured.
  • the prepared mixture was subjected to an electron beam crosslinking process at room temperature using an electron beam accelerator of 10 MeV linear accelerator (8kW, Mevex) under conditions of an electron beam irradiation dose of 15 kGy to prepare a hydrogel.
  • Example 1 Example 2 Example 3 Example 4 Comparative Example 1 ionic monomer AMPS 50 50 50 50 50 50 50 50 menstruum H 2 O 50 50 50 66.5 66.5 pH regulator 50% NaOH 20 20 20 20 20 20 KCl - - 5 - - cross-linking agent PEG-DA - 0.04 - - - adhesion synergist HEA - - - 17 - DOPA - - - - 17 Thickness (mm) 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5
  • Comparative Example 2 As a comparative group, in Comparative Example 2, a hydrogel was prepared using a hydrogel composition using UV photopolymerization from Sekisui, and in Comparative Example 3, a 0.7-thick hydrogel obtained commercially from 3M red dot gel was used.
  • the hydrogels of Examples 1 to 4 and Comparative Example 1 and Comparative Example 2 were cut into squares of 1 ⁇ 1 cm 2 and inserted between ITO electrodes, and 0.1 Impedance was measured when an excitation voltage of 10 mV was applied at a frequency of 100 kHz in Hz, and the results are shown in Table 2 below.
  • the adhesive strength of the hydrogel of Examples 1 to 5 and Comparative Example 1 was measured according to ASTM D3330. Specifically, the hydrogel sample lined on the non-woven fabric was cut into a strip of 25.4 ⁇ 300 mm 2 , then adhered to the bakelite plate substrate, and then peeled off at an angle of 90 degrees at a rate of 500 mm/min to measure the adhesive strength. It is shown in Table 2 below.
  • the hydrogels of Examples 1 to 5 and Comparative Example 1 were cut to a certain size and then weighed. Then, the measured sample was placed in a 100 ml bottle containing purified water, operated in a shaking constant temperature water bath at 37 ° C and 60 rpm for 72 hours, then the sample was taken out and put in an oven at 75 ° C and dried until it reached a certain weight. After measuring the weight of the dried gel, the gelation rate was calculated as in Equation 1 below, and the results are shown in Table 2 below.
  • Equation 1 W i- is the initial weight and W d is the dry weight.
  • the hydrogel of Examples 1 to 5 and Comparative Example 1 was cut into a rectangle of 2.5 cm (width) ⁇ 10 cm (length) to prepare a sample, After fixing the upper and lower jigs while maintaining an appropriate gauge distance (7 ⁇ 10cm) in the testing machine, the sample was pulled at a speed of 300mm/min to measure the maximum tensile load for 1 minute, and the resulting value was converted into the load value of the desired width. , and the results are shown in Table 2 below.
  • Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Comparative Example 3 conductivity (S/m) 1.74 0.74 1.94 0.92 0.82 0.12 0.022 adhesiveness (gf/in) 1480 820 1002 1680 1520 488 470 Gelation rate (%) 65 75 42 53 61.3 not measurable not measurable tensile strength (kPa) 252.3 280.2 200.2 248.4 245.2 not measurable not measurable
  • Example 1 showed excellent adhesive strength and conductivity.
  • 3M adhesive Comparative Example 3
  • the adhesive conductive hydrogel prepared through electron beam crosslinking had better adhesive strength than that product.
  • the tackifier In the case of Example 4 and Comparative Example 1 in which the tackifier was added, it was confirmed that they had better adhesive properties than the basic composition. It can be seen that this is the cause of the increase in adhesive properties due to the addition of a hydroxyl group in the tackifier.
  • Example 4 in which a small amount of HEA was added is most suitable as a transparent conductive hydrogel.
  • the adhesive conductive hydrogels of Examples 1 to 4 exhibit excellent mechanical strength by exhibiting tensile strength of 200.2 kPa to 280.2 kPa without a separate substrate (nonwoven fabric), whereas Comparative Example 2 (Sekisui hydrogel) Without the substrate, the shape is not maintained, making it difficult to measure the tensile strength and gelation rate of the hydrogel alone. does not exist.
  • the adhesive conductive hydrogel according to the present invention not only has excellent conductivity and adhesive strength, but also improves mechanical strength without a separate substrate.
  • samples cut into 1 ⁇ 1 cm 2 squares from the hydrogel of Example 1 were incubated in 5.0 mL of cell culture medium at a temperature of 37 ° C. It was cultured for 48 hours and 72 hours with gentle shaking, and the culture medium was seeded HaCaT cells or SK-MEL-28 cells at 4x10 4 cells/500 ⁇ l.
  • samples treated with only the CCK-8 reagent were simultaneously tested, and the results are shown in FIGS. 4 and 5 below.
  • Figure 4 is a scanning electron microscope image of the cell morphology after performing a cytotoxicity test on HaCaT cells and SK-MEL-28 cells.
  • (a) is the result of the experiment on HaCaT cells
  • (b) is the result of the experiment on SK-MEL-28 cells.
  • the hydrogel according to the present invention is treated, there is no significant change compared to the control group.
  • Figure 5 is a graph measuring the cell ratio after conducting a cytotoxicity test on HaCaT cells and SK-MEL-28 cells.
  • (a) is the result of the experiment on HaCaT cells
  • (b) is the result of the experiment on SK-MEL-28 cells.
  • HaCaT cells showed no significant change compared to the control group
  • SK-MEL-28 cells showed a cell viability of 90% or more compared to the control group.
  • the adhesive conductive hydrogel according to the present invention is harmless even when applied to the human body.

Landscapes

  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Pathology (AREA)
  • Biomedical Technology (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Biophysics (AREA)
  • Dispersion Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Medicinal Chemistry (AREA)
  • Heart & Thoracic Surgery (AREA)
  • Medical Informatics (AREA)
  • Molecular Biology (AREA)
  • Surgery (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Measurement And Recording Of Electrical Phenomena And Electrical Characteristics Of The Living Body (AREA)

Abstract

The present invention relates to a conductive hydrogel comprising an ionic monomer and a method for preparing same. The conductive hydrogel has an appropriate degree of crosslinking by irradiating, with electron beams, a composition in which an ionic monomer, distilled water, and a pH adjusting agent are mixed at a certain ratio, can be used without a separate substrate, has excellent conductivity and at the same time, exhibits excellent adhesion, and can prevent skin troubles that occur when attached to the skin for a long period of time, since no separate initiator is used.

Description

방사선 가교방법을 이용한 점착 전도성 하이드로겔, 이의 제조방법 및 이를 이용한 점착 전도성 하이드로겔 시트Adhesive conductive hydrogel using radiation cross-linking method, manufacturing method thereof, and adhesive conductive hydrogel sheet using the same
본 발명은 방사선 가교방법을 이용한 점착 전도성 하이드로겔, 이의 제조방법 및 이를 이용한 점착 전도성 하이드로겔 시트에 관한 것으로서, 구체적으로는 이온성 모노머, 증류수 및 pH 조절제를 일정비율로 혼합한 조성물에 전자빔을 조사하여 제조한 점착 전도성 하이드로겔에 관한 것이다.The present invention relates to an adhesive conductive hydrogel using a radiation crosslinking method, a method for preparing the same, and an adhesive conductive hydrogel sheet using the same. It relates to an adhesive conductive hydrogel prepared by
고분자 하이드로겔은 가교 중합된 폴리머로 구성된 매트릭스에 습윤제와 물을 함유하고 있어 다양한 분야에 사용된다. 종래부터 폴리아크릴산 등의 전해질 폴리머를 가교 중합하여 습윤제와 물을 함유시킨 도전성 고분자 하이드로겔을 생체용 전극으로 사용해왔다. 특히, 고분자 하이드로겔은 고분자 매트릭스가 친수성이고 수분 침투성이 있으면서 동시에 물을 함유하기 때문에 전해질의 첨가가 용이하여 저 임피던스화가 가능한 장점이 있다. 이러한 이유로 심전도 모니터링과 같은 고정밀도 측정용 전극으로 충분한 성능을 발휘할 수 있다.Polymer hydrogels are used in various fields because they contain a wetting agent and water in a matrix composed of cross-linked polymers. Conventionally, a conductive polymer hydrogel containing a wetting agent and water by cross-linking polymerization of an electrolyte polymer such as polyacrylic acid has been used as an electrode for a living body. In particular, since the polymer matrix is hydrophilic and water permeable and contains water at the same time, the polymer hydrogel has the advantage of being easy to add an electrolyte and enabling low impedance. For this reason, it can exhibit sufficient performance as an electrode for high-precision measurement such as electrocardiogram monitoring.
그러나, 종래 기술은 고분자를 가교하기 위해 가교제, 개시제 및 안정제를 첨가하여 장시간 피부 부착 시 피부 트러블을 유발하는 단점이 있다.However, the prior art has a disadvantage of causing skin trouble when attached to the skin for a long time by adding a crosslinking agent, an initiator, and a stabilizer to crosslink the polymer.
구체적으로, 고분자 하이드로겔을 제조하기 위해 하이드로겔 조성물에 UV 개시제를 첨가하여 UV 광중합을 통해 하이드로겔을 제조하고 있지만 이러한 방법으로 제조된 하이드로겔은 형상 유지를 못해 기재 필름이 반드시 필요하고, 광개시제 가교 등을 사용하여 인체에 유해한 단점이 있다.Specifically, in order to prepare a polymer hydrogel, a hydrogel is prepared through UV photopolymerization by adding a UV initiator to a hydrogel composition, but the hydrogel prepared in this way cannot maintain its shape, so a base film is essential, and a photoinitiator crosslinking There is a disadvantage that is harmful to the human body by using the back.
또한, 고분자 하이드로겔에 전도성을 부여하기 위해 NaCl, NaOH와 같은 단분자 전해질을 주입하는데, 상기와 같은 단분자 전해질은 작동시간이 길수록 열화와 함께 외부로 유출되는 현상이 발생하고 전도성이 저하되는 문제점이 있다.In addition, a monomolecular electrolyte such as NaCl or NaOH is injected to impart conductivity to the polymer hydrogel. The longer the operating time, the more the monomolecular electrolyte deteriorates and leaks out to the outside, and the conductivity deteriorates. there is
이에, 본원출원인은 기존의 고분자 하이드로겔 제조 기술들과 비교하여 더욱 향상되고 우수한 점착력 및 전도성을 갖는 고분자 하이드로겔을 제공할 수 있는 기술을 이하에 제안하려고 하며, 특히 이온성 모노머를 전자빔 조사하여 가교시킴으로써 별도의 개시제 없이도 적정한 가교도를 갖고 별도의 기재 없이도 사용가능한 전도성 하이드로겔에 대한 기술을 제안하려고 한다.Accordingly, the applicant of the present application intends to propose a technology capable of providing a polymer hydrogel having more improved adhesive strength and conductivity compared to existing polymer hydrogel manufacturing technologies below, and in particular, electron beam irradiation of ionic monomers to crosslink By doing so, we intend to propose a technology for a conductive hydrogel that has an appropriate degree of crosslinking without a separate initiator and can be used without a separate substrate.
본 발명은 상술한 종래의 문제점을 해소 및 이를 감안하여 안출된 것으로서, 이온성 모노머를 포함하는 예비하이드로겔 조성물에 전자빔 조사하여 가교시킴으로써 별도의 개시제 없이도 적정한 가교도를 갖고 별도의 기재 없이도 사용가능한 점착 전도성 하이드로겔, 이의 제조방법 및 이를 이용한 점착 전도성 하이드로겔 시트를 제공하는데 그 목적이 있다.The present invention has been devised to solve the above-mentioned conventional problems and to consider them, and by crosslinking a prehydrogel composition containing an ionic monomer by electron beam irradiation, it has an appropriate degree of crosslinking without a separate initiator and adhesive conductivity that can be used without a separate substrate. The purpose is to provide a hydrogel, a manufacturing method thereof, and an adhesive conductive hydrogel sheet using the same.
본 발명은 이온성 모노머; 증류수 및 pH 조절제를 혼합하는 예비하이드로겔 조성물 제조단계; 및The present invention is an ionic monomer; Preparing a pre-hydrogel composition by mixing distilled water and a pH adjusting agent; and
제조된 상기 예비하이드로겔 조성물을 도포한 후 1 내지 10 MeV 크기의 에너지를 갖는 전자빔을 5 kGy 내지 50 kGy의 흡수선량으로 조사하여 가교시키는 전자빔 조사단계;를 포함하고,After coating the prepared prehydrogel composition, an electron beam irradiation step of crosslinking by irradiating an electron beam having an energy of 1 to 10 MeV with an absorbed dose of 5 kGy to 50 kGy; Including,
상기 이온성 모노머는 2-아크릴아미도-2-메틸프로판술폰산(AMPS), 2-하이드록시에틸아크릴레이드(2-hydroxylethyl acrylate), 2-에틸헥실아크릴레이드(2-ethylhexyl acrylate), n-부틸아크릴레이드(n-butyl acrylate), n-부틸메타크릴레이트(n-butyl methacrylate), 아크릴산(acrylic acid) 및 3-(3,4-디하이드록시페닐)-L-알라닌(3-(3,4-Dihydroxyphenyl)-L-alanine) 중 어느 하나 이상을 포함하고,The ionic monomer is 2-acrylamido-2-methylpropanesulfonic acid (AMPS), 2-hydroxylethyl acrylate, 2-ethylhexyl acrylate, n-butyl Acrylate (n-butyl acrylate), n-butyl methacrylate (n-butyl methacrylate), acrylic acid (acrylic acid) and 3- (3,4-dihydroxyphenyl) -L-alanine (3- (3, 4-Dihydroxyphenyl) -L-alanine) containing any one or more,
상기 pH 조절제는 수산화나트륨, 수산화칼륨, 수산화 리튬, 염화나트륨, 및 염화칼륨 중 어느 하나 이상을 포함하고, The pH adjusting agent includes at least one of sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium chloride, and potassium chloride,
전도성은 0.5 내지 5 S/m이며, 점착력은 600 내지 2000 gf/in인 것인, 점착 전도성 하이드로겔의 제조방법을 제공한다.The conductivity is 0.5 to 5 S / m, and the adhesive force is 600 to 2000 gf / in, which provides a method for producing an adhesive conductive hydrogel.
또한, 본 발명은 2-아크릴아미도-2-메틸프로판술폰산(AMPS), 2-하이드록시에틸아크릴레이드(2-hydroxylethyl acrylate), 아크릴산(acrylic acid) 및 3-(3,4-디하이드록시페닐)-L-알라닌(3-(3,4-Dihydroxyphenyl)-L-alanine) 중 어느 하나의 이온성 모노머를 포함하는 예비하이드로겔 조성물에 전자빔 조사하여 가교시켜 구비되고,In addition, the present invention is 2-acrylamido-2-methylpropanesulfonic acid (AMPS), 2-hydroxyethyl acrylate (2-hydroxylethyl acrylate), acrylic acid (acrylic acid) and 3- (3,4-dihydroxy Phenyl) -L-alanine (3- (3,4-Dihydroxyphenyl) -L-alanine) is provided by crosslinking the prehydrogel composition containing any one of the ionic monomers by electron beam irradiation,
전도성은 0.5 내지 5 S/m이며, 점착력은 600 내지 2000 gf/in인 것을 특징으로 하는 점착 전도성 하이드로겔을 제공한다.The conductivity is 0.5 to 5 S / m, and the adhesive force is 600 to 2000 gf / in, characterized in that it provides an adhesive conductive hydrogel.
아울러, 본 발명은 2-아크릴아미도-2-메틸프로판술폰산(AMPS), 2-하이드록시에틸아크릴레이드(2-hydroxylethyl acrylate), 아크릴산(acrylic acid) 및 3-(3,4-디하이드록시페닐)-L-알라닌(3-(3,4-Dihydroxyphenyl)-L-alanine) 중 어느 하나의 이온성 모노머를 포함하는 예비하이드로겔 조성물과, 시트형태로 구비되는 부직포층을 포함하고,In addition, the present invention is 2-acrylamido-2-methylpropanesulfonic acid (AMPS), 2-hydroxyethyl acrylate (2-hydroxylethyl acrylate), acrylic acid (acrylic acid) and 3- (3,4-dihydroxy A prehydrogel composition containing any one ionic monomer of phenyl) -L-alanine (3- (3,4-Dihydroxyphenyl) -L-alanine), and a nonwoven fabric layer provided in the form of a sheet,
상기 예비하이드로겔 조성물은 상기 부직포층의 적어도 일면에 도포된 후 전자빔 조사에 의하여 가교되어 점착 전도성 하이드로겔로 제조되며,The prehydrogel composition is applied to at least one surface of the nonwoven fabric layer and then crosslinked by electron beam irradiation to form an adhesive conductive hydrogel,
상기 부직포층은 상기 점착 전도성 하이드로겔과 그라프팅(grafting)되어 결합되는 것을 특징으로 하는 점착 전도성 하이드로겔 시트를 제공한다.The non-woven fabric layer provides an adhesive conductive hydrogel sheet, characterized in that it is bonded to the adhesive conductive hydrogel by grafting.
본 발명에 따르면, 상기 점착 전도성 하이드로겔은 이온성 모노머, 증류수 및 pH 조절제를 일정비율로 혼합한 예비하이드로겔 조성물에 전자빔을 조사함으로써 적정한 가교도를 갖고, 별도의 기재 없이도 사용 가능하며, 우수한 전도성을 가짐과 동시에 우수한 점착력을 나타내고, 별도의 개시제를 사용하지 않아 장시간 피부 부착시 발생하는 피부 트러블을 방지할 수 있다.According to the present invention, the adhesive conductive hydrogel has an appropriate degree of crosslinking, can be used without a separate substrate, and has excellent conductivity by irradiating an electron beam to a prehydrogel composition in which an ionic monomer, distilled water, and a pH adjusting agent are mixed at a predetermined ratio. At the same time, it exhibits excellent adhesive strength, and it is possible to prevent skin troubles that occur when attached to the skin for a long time without using a separate initiator.
도 1은 본 발명의 실시예에 따른 점착 전도성 하이드로겔의 제조방법을 설명하기 위해 나타낸 개략적 공정도이다.1 is a schematic process diagram shown to explain a method for manufacturing an adhesive conductive hydrogel according to an embodiment of the present invention.
도 2는 본 발명의 실시예에 따른 점착 전도성 하이드로겔 시트의 단면도를 나타낸 이미지이다.2 is an image showing a cross-sectional view of an adhesive conductive hydrogel sheet according to an embodiment of the present invention.
도 3는 본 발명의 실시예에 따른 점착 전도성 하이드로겔에 대한 물성 평가를 실시한 데이터이다.3 is data obtained by evaluating physical properties of an adhesive conductive hydrogel according to an embodiment of the present invention.
도 4 및 도 5는 본 발명의 일실시예에 따른 점착 전도성 하이드로겔의 세포 독성 평가를 실시한 데이터이다.4 and 5 are data obtained by evaluating the cytotoxicity of the adhesive conductive hydrogel according to an embodiment of the present invention.
**도면의 주요 부호에 대한 설명****Description of major symbols in the drawing**
10: 점착 전도성 하이드로겔10: adhesive conductive hydrogel
21: 핫멜트 점착층21: hot melt adhesive layer
22: 부직포층22: non-woven fabric layer
S100: 조성물 제조단계S100: composition preparation step
S200: 전자빔 조사단계S200: electron beam irradiation step
본 발명에 대해 첨부한 도면을 참조하여 바람직한 실시예를 설명하면 다음과 같으며, 이와 같은 상세한 설명을 통해서 본 발명의 목적과 구성 및 그에 따른 특징들을 보다 잘 이해할 수 있게 될 것이다.Preferred embodiments of the present invention will be described with reference to the accompanying drawings, and through this detailed description, the purpose and configuration of the present invention and the characteristics thereof will be better understood.
본 발명은, 이온성 모노머; 증류수 및 pH 조절제를 혼합하는 예비하이드로겔 조성물 제조단계; 및The present invention, an ionic monomer; Preparing a pre-hydrogel composition by mixing distilled water and a pH adjusting agent; and
제조된 상기 예비하이드로겔 조성물을 도포한 후 1 내지 10 MeV 크기의 에너지를 갖는 전자빔을 5 kGy 내지 50 kGy의 흡수선량으로 조사하여 가교시키는 전자빔 조사단계;를 포함하고,After applying the prepared prehydrogel composition, an electron beam having an energy of 1 to 10 MeV was applied at 5 kGy to an electron beam irradiation step of crosslinking by irradiating with an absorbed dose of 50 kGy;
상기 이온성 모노머는 2-아크릴아미도-2-메틸프로판술폰산(AMPS), 2-하이드록시에틸아크릴레이드(2-hydroxylethyl acrylate), 아크릴산(acrylic acid) 및 3-(3,4-디하이드록시페닐)-L-알라닌(3-(3,4-Dihydroxyphenyl)-L-alanine) 중 어느 하나 이상을 포함하고,The ionic monomers are 2-acrylamido-2-methylpropanesulfonic acid (AMPS), 2-hydroxylethyl acrylate, acrylic acid and 3-(3,4-dihydroxy). Phenyl) -L-alanine (3- (3,4-Dihydroxyphenyl) -L-alanine) containing any one or more,
상기 pH 조절제는 수산화나트륨, 수산화칼륨, 수산화 리튬, 염화나트륨, 및 염화칼륨 중 어느 하나 이상을 포함하고, The pH adjusting agent includes at least one of sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium chloride, and potassium chloride,
전도성은 0.5 내지 5 S/m이며, 점착력은 600 내지 2000 gf/in인 것인, 점착 전도성 하이드로겔의 제조방법을 제공한다.The conductivity is 0.5 to 5 S / m, and the adhesive force is 600 to 2000 gf / in, which provides a method for producing an adhesive conductive hydrogel.
본 발명의 실시예에 따른 점착 전도성 하이드로겔의 제조방법은 도 1에 나타낸 바와 같이, 예비하이드로겔 조성물 제조단계(S100)와 전자빔 조사단계(S200)로 이루어질 수 있다.As shown in FIG. 1, the method for producing an adhesive conductive hydrogel according to an embodiment of the present invention may include a preliminary hydrogel composition preparation step (S100) and an electron beam irradiation step (S200).
상기 예비하이드로겔 조성물 제조단계(S100)는 이온성 모노머, 증류수 및 pH 조절제를 혼합하여 점착 전도성 하이드로겔을 제조하기 위한 예비하이드로겔 조성물을 제조하는 단계이다.The preliminary hydrogel composition preparation step (S100) is a step of preparing a preliminary hydrogel composition for preparing an adhesive conductive hydrogel by mixing an ionic monomer, distilled water, and a pH adjusting agent.
구체적으로, 상기 예비하이드로겔 조성물 제조단계(S100)는 이온성 모노머 40 내지 70중량부, 45 내지 65중량부 또는 45 내지 60중량부; 증류수 30 내지 60 중량부 또는 45 내지 60 중량부 및 pH 조절제 10 내지 30 중량부 또는 15 내지 25 중량부로 혼합할 수 있다.Specifically, in the prehydrogel composition preparation step (S100), 40 to 70 parts by weight, 45 to 65 parts by weight, or 45 to 60 parts by weight of an ionic monomer; 30 to 60 parts by weight or 45 to 60 parts by weight of distilled water and 10 to 30 parts by weight or 15 to 25 parts by weight of a pH adjusting agent may be mixed.
상기 하이드로겔 조성물 제조단계(S100)는 pH 조절제로 수산화나트륨, 탄산나트륨, 수산화칼륨, 수산화 리튬, 염화나트륨, 및 염화칼륨 중 어느 하나를 사용할 수 있다. 이와 같은 pH 조절제를 사용함으로써, 하이드로겔 조성물의 pH를 5 내지 6으로 조절할 수 있다.In the hydrogel composition preparation step (S100), any one of sodium hydroxide, sodium carbonate, potassium hydroxide, lithium hydroxide, sodium chloride, and potassium chloride may be used as a pH adjusting agent. By using such a pH adjusting agent, the pH of the hydrogel composition can be adjusted to 5 to 6.
상기 예비하이드로겔 조성물 제조단계(S100)에서, 상기 예비하이드로겔 조성물은 2-아크릴아미도-2-메틸프로판술폰산(AMPS), 증류수 및 수산화나트륨만으로 이루어져 있고, 상기 예비하이드로겔 조성물 제조단계는 별도의 광중합 개시제 및 UV중합 개시제를 첨가하지 않아도 우수한 점착성 및 전도성을 나타낼 수 있다.In the preliminary hydrogel composition preparation step (S100), the preliminary hydrogel composition consists of only 2-acrylamido-2-methylpropanesulfonic acid (AMPS), distilled water and sodium hydroxide, and the preliminary hydrogel composition preparation step is separately performed. It can exhibit excellent adhesiveness and conductivity without adding a photopolymerization initiator and a UV polymerization initiator.
상기 하이드로겔 조성물 제조단계(S100)는 이온성 모노머; 증류수 및 pH 조절제를 혼합한 후, 가교제를 첨가하는 것을 더 포함할 수 있다. 상기 가교제는 폴리에틸렌글리콜 디아크릴레이트(poly(ethylene glycol) diacrylate, PEG-DA), 2-하이드록시에틸아크릴레이드(2-hydroxylethyl acrylate), 아크릴산(acrylic acid) 및 3-(3,4-디하이드록시페닐)-L-알라닌(3-(3,4-Dihydroxyphenyl)-L-alanine) 중 어느 하나 이상을 포함할 수 있다. 구체적으로, 상기 가교제는 0.01 내지 0.08 중량부, 0.02 내지 0.07 중량부 및 0.03 내지 0.06 중량부로 혼합할 수 있다.The hydrogel composition manufacturing step (S100) is an ionic monomer; After mixing the distilled water and the pH adjusting agent, it may further include adding a crosslinking agent. The crosslinking agent is poly(ethylene glycol) diacrylate (PEG-DA), 2-hydroxylethyl acrylate, acrylic acid and 3-(3,4-dihydride). It may include any one or more of hydroxyphenyl) -L-alanine (3- (3,4-Dihydroxyphenyl) -L-alanine). Specifically, the crosslinking agent may be mixed in an amount of 0.01 to 0.08 parts by weight, 0.02 to 0.07 parts by weight, and 0.03 to 0.06 parts by weight.
상기 하이드로겔 조성물 제조단계(S100)는 예비하이드로겔 조성물에 가교제 첨가 없이도 전자빔 조사단계(S200)를 통해 적정한 가교도를 갖는 점착 전도성 하이드로겔을 제조할 수 있으나, 상기와 같이 예비하이드로겔 조성물에 미량의 가교제를 포함하는 경우 점착 성능을 저하시키지 않으면서 기계적 강도를 향상시킬 수 있다.In the hydrogel composition preparation step (S100), an adhesive conductive hydrogel having an appropriate degree of crosslinking can be prepared through the electron beam irradiation step (S200) without adding a crosslinking agent to the prehydrogel composition, but as described above, a small amount of When a crosslinking agent is included, mechanical strength can be improved without deteriorating adhesive performance.
상기 전자빔 조사단계(S200)는 상기 예비하이드로겔 조성물을 도포한 후 일정 크기의 에너지를 갖는 전자빔을 조사하여 가교시켜 점착 전도성 하이드로겔을 제조하는 단계이다.The electron beam irradiation step (S200) is a step of preparing an adhesive conductive hydrogel by applying an electron beam having a certain amount of energy to crosslink after applying the prehydrogel composition.
상기 전자빔 조사단계(S200)는 상기 예비하이드로겔 조성물을 0.5 내지 10 mm 또는 0.5 내지 5 mm의 두께로 도포한 후 전자빔을 조사할 수 있다.In the electron beam irradiation step (S200), an electron beam may be irradiated after applying the prehydrogel composition to a thickness of 0.5 to 10 mm or 0.5 to 5 mm.
상기 전자빔 조사단계(S200)는 상기 예비하이드로겔 조성물을 도포한 후 1 내지 10 MeV 또는 1 내지 10 MeV 크기의 에너지를 갖는 전자빔을 5 kGy 내지 50 kGy의 흡수선량으로 조사하여 가교시킬 수 있다.In the electron beam irradiation step (S200), after applying the prehydrogel composition, an electron beam having an energy of 1 to 10 MeV or 1 to 10 MeV may be irradiated with an absorbed dose of 5 kGy to 50 kGy to crosslink.
상기 전자빔 조사단계(S200)에서, 상기 예비하이드로겔 조성물이 5 kGy 내지 40 kGy, 5 kGy 내지 30 kGy 또는 5 내지 20 KGy의 흡수선량으로 조사하여 점착 전도성 하이드로겔 제조시 점착성 및 전도성을 동시에 부여할 수 있다.In the electron beam irradiation step (S200), the prehydrogel composition is irradiated with an absorbed dose of 5 kGy to 40 kGy, 5 kGy to 30 kGy, or 5 to 20 KGy to impart adhesiveness and conductivity at the same time when preparing the adhesive conductive hydrogel. can
상기 전자빔 조사단계(S200)를 거쳐 제조된 점착 전도성 하이드로겔 내의 이온성 모노머의 가교도는 50% 내지 80%, 55% 내지 80% 또는 55% 내지 75%일 수 있다. 상기 서술한 조건의 조사빔을 조사하여 예비하이드로겔 조성물을 가교시켜 상기와 같은 가교도를 나타낼 수 있고, 이에 따라 점착성이 우수하면서도 기계적 강도를 향상시킬 수 있다.The degree of crosslinking of the ionic monomer in the adhesive conductive hydrogel prepared through the electron beam irradiation step (S200) may be 50% to 80%, 55% to 80%, or 55% to 75%. The prehydrogel composition may be crosslinked by irradiation with an irradiation beam under the above-described conditions, thereby exhibiting the degree of crosslinking as described above, thereby improving mechanical strength while having excellent adhesiveness.
상기 전자빔 조사단계(S200)는 도포된 예비하이드로겔 조성물에 상기와 같이 전자빔을 조사하여 이온성 모노머가 가교되어 점착 전도성 하이드로겔을 형성하도록 하여 별도의 기재 없이도 점착 전도성 하이드로겔을 형성할 수 있다.In the electron beam irradiation step (S200), the applied prehydrogel composition is irradiated with an electron beam as described above so that the ionic monomer is crosslinked to form an adhesive conductive hydrogel without a separate substrate. Can be formed.
상기 전자빔 조사단계(S200)는 부직포 상에 상기 예비하이드로겔 조성물을 도포한 후 전자빔을 조사할 수 있다. 구체적으로, 상기 부직포는 부직포 일면에 핫멜트 점착층이 형성된 것일 수 있고, 부직포의 핫멜트 점착층이 형성된 면에 조성물을 도포한 후 전자빔을 조사하여 점착 전도성 하이드로겔을 제조할 수 있다.In the electron beam irradiation step (S200), an electron beam may be irradiated after applying the prehydrogel composition on the nonwoven fabric. Specifically, the nonwoven fabric may have a hot melt adhesive layer formed on one surface of the nonwoven fabric, and the adhesive conductive hydrogel may be prepared by applying a composition to the surface of the nonwoven fabric on which the hot melt adhesive layer is formed and then irradiating an electron beam.
상기와 같이 핫멜트 점착층이 형성된 부직포 상에 상기 제조된 조성물을 도포한 후 전자빔을 조사하면 부직포 상에 하이드로겔층이 형성되면서 하이드로겔과 부직포가 그라프팅될 수 있다. 이에, 하이드로겔층과 부직포 간의 결합력이 향상되어 내구성이 우수할 수 있다.As described above, when the prepared composition is applied onto the nonwoven fabric having the hot melt adhesive layer and then electron beam is irradiated, the hydrogel and the nonwoven fabric may be grafted while forming a hydrogel layer on the nonwoven fabric. Thus, the bonding strength between the hydrogel layer and the nonwoven fabric is improved, and durability may be excellent.
또한, 본 발명은 2-아크릴아미도-2-메틸프로판술폰산(AMPS), 2-하이드록시에틸아크릴레이드(2-hydroxylethyl acrylate), 아크릴산(acrylic acid) 및 3-(3,4-디하이드록시페닐)-L-알라닌(3-(3,4-Dihydroxyphenyl)-L-alanine) 중 어느 하나의 이온성 모노머를 포함하는 예비하이드로겔 조성물에 전자빔 조사하여 가교시켜 구비되고,In addition, the present invention is 2-acrylamido-2-methylpropanesulfonic acid (AMPS), 2-hydroxyethyl acrylate (2-hydroxylethyl acrylate), acrylic acid (acrylic acid) and 3- (3,4-dihydroxy Phenyl) -L-alanine (3- (3,4-Dihydroxyphenyl) -L-alanine) is provided by crosslinking the prehydrogel composition containing any one of the ionic monomers by electron beam irradiation,
전도성은 0.5 내지 5 S/m이며, 점착력은 600 내지 2000 gf/in인 것을 특징으로 하는 점착 전도성 하이드로겔을 제공한다.The conductivity is 0.5 to 5 S / m, and the adhesive force is 600 to 2000 gf / in, characterized in that it provides an adhesive conductive hydrogel.
상기 점착 전도성 하이드로겔은 2-아크릴아미도-2-메틸프로판술폰산(AMPS), 2-하이드록시에틸아크릴레이드(2-hydroxylethyl acrylate), 아크릴산(acrylic acid) 및 3-(3,4-디하이드록시페닐)-L-알라닌(3-(3,4-Dihydroxyphenyl)-L-alanine) 중 어느 하나의 이온성 모노머에 전자빔 조사하여 가교시킨 것으로 우수한 점착성 및 전도성을 동시에 나타낼 수 있다.The adhesive conductive hydrogel is composed of 2-acrylamido-2-methylpropanesulfonic acid (AMPS), 2-hydroxylethyl acrylate, acrylic acid and 3-(3,4-dihydride). It is crosslinked by electron beam irradiation to any one ionic monomer of 3-(3,4-Dihydroxyphenyl)-L-alanine, and can exhibit excellent adhesiveness and conductivity at the same time.
상기 점착 전도성 하이드로겔의 전자빔 흡수선량은 5 내지 20 KGy 또는 5 내지 15 KGy일 수 있고, 상기 점착 전도성 하이드로겔의 두께는 0.5 내지 10 mm 또는 0.5 내지 5 mm일 수 있다. 상기와 같은 조건의 점착 전도성 하이드로겔을 형성한 경우 점착 전도성 하이드로겔의 전도성 및 점착성을 동시에 향상시킬 수 있다.The electron beam absorbed dose of the adhesive conductive hydrogel may be 5 to 20 KGy or 5 to 15 KGy, and the thickness of the adhesive conductive hydrogel may be 0.5 to 10 mm or 0.5 to 5 mm. When the adhesive conductive hydrogel is formed under the above conditions, the conductivity and adhesiveness of the adhesive conductive hydrogel can be simultaneously improved.
상기 점착 전도성 하이드로겔은 0.5 내지 5 S/m, 0.5 내지 4 S/m 또는 0.8 내지 3 S/m의 전도성을 가질 수 있고, 상기 점착 전도성 하이드로겔은 600 내지 2000 gf/in, 700 내지 1800 gf/in 또는 800 내지 1700 gf/in의 점착력을 가질 수 있다.The adhesive conductive hydrogel may have a conductivity of 0.5 to 5 S/m, 0.5 to 4 S/m, or 0.8 to 3 S/m, and the adhesive conductive hydrogel may have a conductivity of 600 to 2000 gf/in, 700 to 1800 gf /in or from 800 to 1700 gf/in.
본 발명에 따른 점착 전도성 하이드로겔은 이온성 모노머를 별도의 개시제 없이 전자빔을 조사하여 가교시켜 제조한 것으로 가교제 없이도 우수한 점착력 및 전도성을 유지할 수 있다. 여기서 미량의 가교제를 첨가하는 경우 가교율이 향상되면서 기계적 강도가 우수한 특성을 나타내나 일정량 이상이 가교제를 첨가하면 가교율이 너무 높아져 하이드로겔 주쇄간의 cohesive가 저하되어 점착 특성이 낮아질 수 있다.The adhesive conductive hydrogel according to the present invention is prepared by crosslinking an ionic monomer by irradiating an electron beam without a separate initiator, and can maintain excellent adhesive strength and conductivity without a crosslinking agent. Here, when a small amount of the crosslinking agent is added, the crosslinking rate is improved and the mechanical strength is excellent, but when a certain amount or more of the crosslinking agent is added, the crosslinking rate is too high and the cohesive between the main chains of the hydrogel is lowered, resulting in a lower adhesive property.
상기 점착 전도성 하이드로겔 내 이온성 모노머의 가교도는 50% 내지 80%, 55% 내지 80% 또는 55% 내지 75%일 수 있다. 상기와 같은 가교도를 가지는 경우 점착 특성이 저하되지 않으면서 우수한 전도성 및 기계적 강도를 나타낼 수 있다.The degree of crosslinking of the ionic monomer in the adhesive conductive hydrogel may be 50% to 80%, 55% to 80%, or 55% to 75%. In the case of having the above degree of crosslinking, excellent conductivity and mechanical strength can be exhibited without deterioration in adhesive properties.
본 발명의 점착 전도성 하이드로겔은 예비하이드로겔 조성물에 상기 서술한 조건의 조사빔을 조사하여 가교시켜 상기와 같은 가교도를 나타낼 수 있고, 이에 따라 점착성이 우수하면서도 기계적 강도를 향상시킬 수 있다.The adhesive conductive hydrogel of the present invention can exhibit the above degree of crosslinking by irradiating the prehydrogel composition with an irradiation beam under the conditions described above, thereby improving mechanical strength while having excellent adhesiveness.
구체적으로, 상기 점착 전도성 하이드로겔의 인장강도는 200 kPa 내지 300 kPa, 200 kPa 내지 290 kPa 또는 200 kPa 내지 280 kPa일 수 있다.Specifically, the tensile strength of the adhesive conductive hydrogel may be 200 kPa to 300 kPa, 200 kPa to 290 kPa, or 200 kPa to 280 kPa.
아울러, 본 발명은 2-아크릴아미도-2-메틸프로판술폰산(AMPS), 2-하이드록시에틸아크릴레이드(2-hydroxylethyl acrylate), 아크릴산(acrylic acid) 및 3-(3,4-디하이드록시페닐)-L-알라닌(3-(3,4-Dihydroxyphenyl)-L-alanine) 중 어느 하나의 이온성 모노머를 포함하는 예비하이드로겔 조성물과, 시트형태로 구비되는 부직포층을 포함하고,In addition, the present invention is 2-acrylamido-2-methylpropanesulfonic acid (AMPS), 2-hydroxyethyl acrylate (2-hydroxylethyl acrylate), acrylic acid (acrylic acid) and 3- (3,4-dihydroxy A prehydrogel composition containing any one ionic monomer of phenyl) -L-alanine (3- (3,4-Dihydroxyphenyl) -L-alanine), and a nonwoven fabric layer provided in the form of a sheet,
상기 예비하이드로겔 조성물은 상기 부직포층의 적어도 일면에 도포된 후 전자빔 조사에 의하여 가교되어 점착 전도성 하이드로겔로 제조되며,The prehydrogel composition is applied to at least one surface of the nonwoven fabric layer and then crosslinked by electron beam irradiation to form an adhesive conductive hydrogel,
상기 부직포층은 상기 점착 전도성 하이드로겔과 그라프팅(grafting)되어 결합되는 것을 특징으로 하는 점착 전도성 하이드로겔 시트를 제공한다.The non-woven fabric layer provides an adhesive conductive hydrogel sheet, characterized in that it is bonded to the adhesive conductive hydrogel by grafting.
본 발명의 실시예에 따른 점착 전도성 하이드로겔 시트는 도 2에 나타낸 바와 같이, 하이드로겔층(10), 핫멜트 점착층(21) 및 부직포층(22) 순으로 적층된 구조를 가질 수 있다.As shown in FIG. 2, the adhesive conductive hydrogel sheet according to an embodiment of the present invention may have a structure in which a hydrogel layer 10, a hot melt adhesive layer 21, and a nonwoven fabric layer 22 are stacked in this order.
본 발명의 점착 전도성 하이드로겔 시트는 상기 점착 전도성 하이드로겔(10)의 적어도 일면에 부직포층(22)을 더 포함할 수 있다. 구체적으로, 상기 부직포는 부직포 일면에 핫멜트 점착층(21)이 형성된 것일 수 있고, 부직포의 핫멜트 점착층(21)이 형성된 면에 점착 전도성 하이드로겔(10)이 적층된 구조일 수 있다.The adhesive conductive hydrogel sheet of the present invention may further include a nonwoven fabric layer 22 on at least one surface of the adhesive conductive hydrogel 10. Specifically, the nonwoven fabric may have a hot melt adhesive layer 21 formed on one surface of the nonwoven fabric, and an adhesive conductive hydrogel 10 may be laminated on the surface of the nonwoven fabric on which the hot melt adhesive layer 21 is formed.
상기와 같이 핫멜트 점착층이 형성된 부직포 상에 예비하이드로겔 조성물을 도포한 후 전자빔을 조사에 의해 가교되어 점착 전도성 하이드로겔을 제조하는 경우 부직포층이 상기 점착 전도성 하이드로겔과 그라프팅되어 결합될 수 있다. 이에, 점착 전도성 하이드로겔과 부직포층 간의 결합력이 향상되어 내구성이 우수할 수 있다.As described above, when the prehydrogel composition is applied on the nonwoven fabric having the hot melt adhesive layer and then crosslinked by electron beam irradiation to prepare the adhesive conductive hydrogel, the nonwoven fabric layer can be grafted and combined with the adhesive conductive hydrogel. . Accordingly, the bonding force between the adhesive conductive hydrogel and the nonwoven fabric layer is improved, and durability may be excellent.
한편, 이하에서는 상술한 단계의 구성으로 이루어지는 본 발명에 따른 점착 전도성 하이드로겔의 제조방법에 있어, 이러한 방법에 의해 점착 전도성 하이드로겔에 대한 물성 특성 및 평가를 위한 테스트를 실시하였으며, 그 결과는 표 2 및 도 3에 나타내었다.On the other hand, in the following, in the manufacturing method of the adhesive conductive hydrogel according to the present invention consisting of the above-described steps, a test for physical properties and evaluation of the adhesive conductive hydrogel was conducted by this method, and the results are shown in Table 2 and Fig. 3.
테스트를 위한 실시예의 하이드로겔은 이온성 모노머인 2-아크릴아미도-2-메틸프로판설폰산(AMPS), 증류수, 수산화나트륨, 가교제, 전해질 및 접착 상승제를 하기 표 1과 같이 혼합하여 혼합액을 제조하였다. 이렇게 제조된 혼합액을 상온에서 전자빔 가속기 10 MeV Linear accelerator(8kW, Mevex)를 사용하여 전자빔 조사 선량 15 kGy의 조건으로 전자빔 가교 공정을 수행하여 하이드로겔을 제조하였다.The hydrogel of the example for the test is a mixed solution by mixing ionic monomer 2-acrylamido-2-methylpropanesulfonic acid (AMPS), distilled water, sodium hydroxide, a crosslinking agent, an electrolyte and an adhesion promoter as shown in Table 1 below. manufactured. The prepared mixture was subjected to an electron beam crosslinking process at room temperature using an electron beam accelerator of 10 MeV linear accelerator (8kW, Mevex) under conditions of an electron beam irradiation dose of 15 kGy to prepare a hydrogel.
실시예 1Example 1 실시예 2Example 2 실시예 3Example 3 실시예 4Example 4 비교예 1Comparative Example 1
이온성 모노머ionic monomer AMPSAMPS 5050 5050 5050 5050 5050
용매menstruum H2OH 2 O 5050 5050 5050 66.566.5 66.566.5
pH조절제pH regulator 50%NaOH50% NaOH 2020 2020 2020 2020 2020
KClKCl -- -- 55 -- --
가교제cross-linking agent PEG-DAPEG-DA -- 0.040.04 -- -- --
접착 상승제adhesion synergist HEAHEA -- -- -- 1717 --
DOPADOPA -- -- -- -- 1717
두께(mm)Thickness (mm) 1.51.5 1.51.5 1.51.5 1.51.5 1.51.5
비교군으로서, 비교예 2는 세키스이사의 UV광중합을 이용한 하이드로겔 조성으로 하이드로겔을 제조하였고, 비교예 3은 3M 사의 red dot gel을 상업적으로 입수하여 0.7 두께의 하이드로겔을 사용하였다.본 발명에 있어 하이드로겔의 전도성 물성을 평가하기 위해서, 상기 실시예 1 내지 4, 비교예 1 및 비교예 2의 하이드로겔을 대상으로 1×1 cm2의 사각형으로 절단하여 ITO 전극 사이에 삽입하고 0.1Hz에서 100kHz의 주파수에서 10 mV의 여기 전압을 인가하였을 때 임피던스를 측정하였으며, 그 결과를 하기 표 2에 나타내었다.As a comparative group, in Comparative Example 2, a hydrogel was prepared using a hydrogel composition using UV photopolymerization from Sekisui, and in Comparative Example 3, a 0.7-thick hydrogel obtained commercially from 3M red dot gel was used. In order to evaluate the conductive properties of the hydrogel in the present invention, the hydrogels of Examples 1 to 4 and Comparative Example 1 and Comparative Example 2 were cut into squares of 1 × 1 cm 2 and inserted between ITO electrodes, and 0.1 Impedance was measured when an excitation voltage of 10 mV was applied at a frequency of 100 kHz in Hz, and the results are shown in Table 2 below.
또한, 본 발명에 있어 하이드로겔의 점착성 물성을 평가하기 위해서, 상기 실시예 1 내지 5 및 비교예 1의 하이드로겔을 대상으로 ASTM D3330에 의거하여 하이드로겔의 점착력을 측정하였다. 구체적으로, 부직포에 배접한 하이드로겔 샘플을 25.4×300 mm2의 스트립형으로 잘라낸 다음 베이크라이트판 기판에 밀착시킨 후 90도의 각도로 500 mm/min 속도로 박리시켜 점착력을 측정하였으며, 그 결과를 하기 표 2에 나타내었다.In addition, in order to evaluate the adhesive properties of the hydrogel in the present invention, the adhesive strength of the hydrogel of Examples 1 to 5 and Comparative Example 1 was measured according to ASTM D3330. Specifically, the hydrogel sample lined on the non-woven fabric was cut into a strip of 25.4 × 300 mm 2 , then adhered to the bakelite plate substrate, and then peeled off at an angle of 90 degrees at a rate of 500 mm/min to measure the adhesive strength. It is shown in Table 2 below.
아울러, 본 발명에 있어 하이드로겔의 겔화율을 측정하기 위해서, 상기 실시예 1 내지 5 및 비교예 1의 하이드로겔을 일정 크기로 자른 후, 무게를 측정하였다. 그런 다음 측정된 샘플을 정제수가 담긴 100 ml병에 넣고, 진탕 항온수조에서 37℃, 60 rpm으로 72시간 동안 작동시킨 후, 샘플을 꺼내 75℃의 오븐에 넣고 일정 무게에 이를 때까지 건조시킨 후 건조된 겔의 무게를 측정한 후 하기 식 1과 같이 겔화율을 계산하였으며, 그 결과는 하기 표 2에 나타내었다.In addition, in order to measure the gelation rate of the hydrogel in the present invention, the hydrogels of Examples 1 to 5 and Comparative Example 1 were cut to a certain size and then weighed. Then, the measured sample was placed in a 100 ml bottle containing purified water, operated in a shaking constant temperature water bath at 37 ° C and 60 rpm for 72 hours, then the sample was taken out and put in an oven at 75 ° C and dried until it reached a certain weight. After measuring the weight of the dried gel, the gelation rate was calculated as in Equation 1 below, and the results are shown in Table 2 below.
[식 1][Equation 1]
겔화율=(Wd/Wi)×100Gelation rate = (W d /W i ) × 100
식 1에서, Wi-는 최초 무게이고, Wd는 건조된 무게이다.In Equation 1, W i- is the initial weight and W d is the dry weight.
아울러, 본 발명에 있어 하이드로겔의 인장강도를 측정하기 위해서, 상기 실시예 1 내지 5 및 비교예 1의 하이드로겔을 2.5cm(폭)×10cm(길이)의 직사각형으로 잘라 샘플을 준비하고, 인장시험기에 적당한 표선거리(7~10cm)를 유지하며 위 아래 지그에 고정시킨 후 샘플을 300mm/min 속도로 잡아당겨 1분 동안의 최대 인장 하중을 측정하였고, 원하는 폭의 하중값으로 환산하여 결과값을 나타냈으며, 그 결과를 하기 표 2에 나타내었다.In addition, in order to measure the tensile strength of the hydrogel in the present invention, the hydrogel of Examples 1 to 5 and Comparative Example 1 was cut into a rectangle of 2.5 cm (width) × 10 cm (length) to prepare a sample, After fixing the upper and lower jigs while maintaining an appropriate gauge distance (7~10cm) in the testing machine, the sample was pulled at a speed of 300mm/min to measure the maximum tensile load for 1 minute, and the resulting value was converted into the load value of the desired width. , and the results are shown in Table 2 below.
실시예 1Example 1 실시예 2Example 2 실시예 3Example 3 실시예 4Example 4 비교예 1Comparative Example 1 비교예 2Comparative Example 2 비교예 3Comparative Example 3
전도성
(S/m)conductivity
(S/m) 		1.741.74 0.740.74 1.941.94 0.920.92 0.820.82 0.120.12 0.0220.022
점착력
(gf/in)adhesiveness
(gf/in) 		14801480 820820 10021002 16801680 15201520 488488 470470
겔화율(%)Gelation rate (%) 6565 7575 4242 5353 61.361.3 측정불가not measurable 측정불가not measurable
인장강도
(kPa)tensile strength
(kPa) 		252.3252.3 280.2280.2 200.2200.2 248.4248.4 245.2245.2 측정불가not measurable 측정불가not measurable
마지막으로, 아울러, 본 발명에 있어 하이드로겔의 늘어난 정도를 확인하기 위해서, 상기 실시예 1 내지 5 및 비교예 1의 하이드로겔을 잡아당겨 늘어난 정도를 확인하였으며, 그 결과를 하기 도 3에 나타내었다.표 2를 살펴보면, 실시예 1의 경우 우수한 점착력과 전도성의 특성을 보였다. 일반적으로 3M 점착제(비교예 3)의 경우 300 ~ 488 gf정도의 점착력을 가지는 것이 비해 전자빔 가교를 통해 제조된 점착 전도성 하이드로겔의 경우 그 제품 보다 더욱 우수한 점착력을 가지는 것을 확인하였다. 점착 부여제를 첨가한 실시예 4와 비교예 1의 경우 기본 조성 보다 더욱 우수한 점착 특성을 가지는 것을 확인하였다. 이는 점착 부여제 내 하이드록실기의 첨가로 인하여 점착 특성이 상승되는 원인되는 것을 알 수 있다.Finally, in addition, in order to confirm the degree of elongation of the hydrogel in the present invention, the degree of elongation was confirmed by pulling the hydrogels of Examples 1 to 5 and Comparative Example 1, and the results are shown in FIG. 3 Looking at Table 2, Example 1 showed excellent adhesive strength and conductivity. In general, compared to 3M adhesive (Comparative Example 3) having adhesive strength of about 300 to 488 gf, it was confirmed that the adhesive conductive hydrogel prepared through electron beam crosslinking had better adhesive strength than that product. In the case of Example 4 and Comparative Example 1 in which the tackifier was added, it was confirmed that they had better adhesive properties than the basic composition. It can be seen that this is the cause of the increase in adhesive properties due to the addition of a hydroxyl group in the tackifier.
그러나 도 3을 살펴보면, 비교예 1과 같이 3-(3,4-dihydroxyphenyl)-L-alanine(DOPA)을 포함하는 경우 시간이 지나면 겔 내에서 산화되어 색상이 변색되는 문제점이 발생하여 투명 하이드로겔은 적절하지 않은 것을 확인하였다. 이에, 투명한 전도성 하이드로겔로는 소량의 HEA를 첨가한 실시예 4가 가장 적절한 것을 알 수 있다.However, looking at Figure 3, in the case of containing 3- (3,4-dihydroxyphenyl) -L-alanine (DOPA) as in Comparative Example 1, there is a problem that the color is discolored due to oxidation in the gel over time, resulting in a transparent hydrogel. was found to be inappropriate. Accordingly, it can be seen that Example 4 in which a small amount of HEA was added is most suitable as a transparent conductive hydrogel.
또한, 실시예 1 내지 4의 점착 전도성 하이드로겔은 별도의 기재(부직포) 없이도 200.2kPa 내지 280.2kPa의 인장강도를 나타내여 우수한 기계적 강도를 나타내는 반면, 비교예 2(세키스이 하이드로겔)의 경우 별도의 기재 없이는 형상이 유지되지 않아 하이드로겔만의 인장강도 및 겔화율을 측정하기 어려우며, 비교예 3(3M 사 제품)의 경우 별도의 기재가 부착되어 있어 하이드로겔만의 인장강도 및 겔화율을 측정할 수 없다.In addition, the adhesive conductive hydrogels of Examples 1 to 4 exhibit excellent mechanical strength by exhibiting tensile strength of 200.2 kPa to 280.2 kPa without a separate substrate (nonwoven fabric), whereas Comparative Example 2 (Sekisui hydrogel) Without the substrate, the shape is not maintained, making it difficult to measure the tensile strength and gelation rate of the hydrogel alone. does not exist.
더불어, 가교제의 투입에 따라 겔화율이 증가되는 것으로 볼 때 가교율이 높아 기계적 강도가 우수한 하이드로겔을 제조할 수 있으나, 반대로 점착 특성이 저하되는 것을 확인하였다. 이를 통해, 가교율이 높아짐에 따라 하이드로겔 주쇄간의 화학결합(cohesive)이 저하되어 점착 특성이 낮아지는 것을 확인하였다.In addition, considering that the gelation rate is increased according to the addition of the crosslinking agent, it is possible to prepare a hydrogel having excellent mechanical strength due to the high crosslinking rate, but it is confirmed that the adhesive property is reduced. Through this, it was confirmed that as the crosslinking rate increased, the chemical bonding (cohesive) between the hydrogel backbones was lowered and the adhesive properties were lowered.
이를 살펴보면, 본 발명에 따른 점착 전도성 하이드로겔은 전도성 및 점착력이 우수할 뿐만 아니라 별도의 기재 없이도 기계적 강도가 향상됨을 알 수 있다.Looking at this, it can be seen that the adhesive conductive hydrogel according to the present invention not only has excellent conductivity and adhesive strength, but also improves mechanical strength without a separate substrate.
본 발명에 있어 하이드로겔의 세포 독성을 평가하기 위해서, 상기 실시예 1의 하이드로겔을 대상으로 1×1 cm2의 사각형으로 절단한 샘플을 5.0mL의 세포 배양 배지에서 37℃의 온도에서 각각 24시간, 48시간 및 72시간 동안 가볍게 흔들면서 배양시켰고, 배양 배지는 HaCaT 세포 또는 SK-MEL-28 세포를 4x104 cells/500 μl으로 씨딩(seeding)한 것이다. 대조군(control)으로서 CCK-8 시약만 처리한 샘플도 동시에 실험을 진행하였으며 그 결과를 하기 도 4 및 도 5에 나타내었다.In order to evaluate the cytotoxicity of the hydrogel in the present invention, samples cut into 1 × 1 cm 2 squares from the hydrogel of Example 1 were incubated in 5.0 mL of cell culture medium at a temperature of 37 ° C. It was cultured for 48 hours and 72 hours with gentle shaking, and the culture medium was seeded HaCaT cells or SK-MEL-28 cells at 4x10 4 cells/500 μl. As a control, samples treated with only the CCK-8 reagent were simultaneously tested, and the results are shown in FIGS. 4 and 5 below.
도 4는 HaCaT 세포와 SK-MEL-28 세포를 대상으로 세포 독성 실험을 진행 후 세포의 형태를 촬영한 주사전자현미경 이미지이다. 도 4를 살펴보면, (a)는 HaCaT 세포를 대상으로 실험한 결과이고, (b)는 SK-MEL-28 세포를 대상으로 실험한 결과이다. 구체적으로, 본 발명에 따른 하이드로겔을 처리한 경우는 대조군과 비교하여 큰 변화가 없는 것을 알 수 있다.Figure 4 is a scanning electron microscope image of the cell morphology after performing a cytotoxicity test on HaCaT cells and SK-MEL-28 cells. Referring to Figure 4, (a) is the result of the experiment on HaCaT cells, (b) is the result of the experiment on SK-MEL-28 cells. Specifically, it can be seen that when the hydrogel according to the present invention is treated, there is no significant change compared to the control group.
도 5는 HaCaT 세포와 SK-MEL-28 세포를 대상으로 세포 독성 실험을 진행 후의 세포 비율을 측정한 그래프이다. 도 5를 살펴보면, (a)는 HaCaT 세포를 대상으로 실험한 결과이고, (b)는 SK-MEL-28 세포를 대상으로 실험한 결과이다. 구체적으로, 본 발명에 따른 하이드로겔을 처리한 경우는 HaCaT 세포는 대조군과 비교하여 큰 변화가 없고, SK-MEL-28 세포는 대조군과 비교하여 90% 이상의 세포 생존율을 나타내는 것을 알 수 있다.Figure 5 is a graph measuring the cell ratio after conducting a cytotoxicity test on HaCaT cells and SK-MEL-28 cells. Referring to Figure 5, (a) is the result of the experiment on HaCaT cells, (b) is the result of the experiment on SK-MEL-28 cells. Specifically, when the hydrogel according to the present invention was treated, it can be seen that HaCaT cells showed no significant change compared to the control group, and SK-MEL-28 cells showed a cell viability of 90% or more compared to the control group.
이를 통해 본 발명에 따른 점착 전도성 하이드로겔은 인체에 적용시에도 무해한 것을 알 수 있다.Through this, it can be seen that the adhesive conductive hydrogel according to the present invention is harmless even when applied to the human body.
이상에서 설명한 실시예는 본 발명의 바람직한 실시예를 설명한 것에 불과하고 이러한 실시예에 극히 한정되는 것은 아니며, 본 발명의 기술적 사상과 청구범위 내에서 이 기술분야의 당해업자에 의하여 다양한 수정과 변형 또는 단계의 치환 등이 이루어질 수 있다 할 것이며, 이는 본 발명의 기술적 범위에 속한다 할 것이다.The embodiments described above are merely those of preferred embodiments of the present invention and are not extremely limited to these embodiments, and various modifications and variations or modifications by those skilled in the art within the scope of the technical spirit and claims of the present invention. It will be said that the substitution of steps can be made, and it will be said that it belongs to the technical scope of the present invention.

Claims (15)

  1. 이온성 모노머; 증류수 및 pH 조절제를 혼합하는 예비하이드로겔 조성물 제조단계; 및ionic monomers; Preparing a pre-hydrogel composition by mixing distilled water and a pH adjusting agent; and
    제조된 상기 예비하이드로겔 조성물을 도포한 후 1 내지 20 MeV 크기의 에너지를 갖는 전자빔을 5 kGy 내지 50 kGy의 흡수선량으로 조사하여 가교시키는 전자빔 조사단계;를 포함하고,After applying the prepared prehydrogel composition, an electron beam irradiation step of crosslinking by irradiating an electron beam having an energy of 1 to 20 MeV with an absorbed dose of 5 kGy to 50 kGy; Including,
    상기 이온성 모노머는 2-아크릴아미도-2-메틸프로판술폰산(AMPS), 2-하이드록시에틸아크릴레이드(2-hydroxylethyl acrylate), 아크릴산(acrylic acid) 및 3-(3,4-디하이드록시페닐)-L-알라닌(3-(3,4-Dihydroxyphenyl)-L-alanine) 중 어느 하나 이상을 포함하고,The ionic monomers are 2-acrylamido-2-methylpropanesulfonic acid (AMPS), 2-hydroxylethyl acrylate, acrylic acid and 3-(3,4-dihydroxy). Phenyl) -L-alanine (3- (3,4-Dihydroxyphenyl) -L-alanine) containing any one or more,
    상기 pH 조절제는 수산화나트륨, 수산화칼륨, 수산화 리튬, 염화나트륨, 및 염화칼륨 중 어느 하나 이상을 포함하고, The pH adjusting agent includes at least one of sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium chloride, and potassium chloride,
    전도성은 0.5 내지 5 S/m이며, 점착력은 600 내지 2000 gf/in인 것인, 점착 전도성 하이드로겔의 제조방법.The conductivity is 0.5 to 5 S / m, and the adhesive strength is 600 to 2000 gf / in, a method for producing an adhesive conductive hydrogel.
  2. 제1항에 있어서,According to claim 1,
    상기 하이드로겔 조성물 제조단계는 상기 예비하이드로겔 조성물 100중량부에 대해서 이온성 모노머 40 내지 70중량부; 증류수 30 내지 60 중량부; 및 pH 조절제 10 내지 30 중량부로 혼합하는 것을 특징으로 하는 점착 전도성 하이드로겔의 제조방법.The step of preparing the hydrogel composition may include 40 to 70 parts by weight of an ionic monomer based on 100 parts by weight of the prehydrogel composition; 30 to 60 parts by weight of distilled water; and 10 to 30 parts by weight of a pH adjusting agent.
  3. 제1항에 있어서,According to claim 1,
    상기 예비하이드로겔 조성물 제조단계에서,In the step of preparing the preliminary hydrogel composition,
    상기 예비하이드로겔 조성물은 2-아크릴아미도-2-메틸프로판술폰산(AMPS), 증류수 및 수산화나트륨만으로 이루어져 있고,The preliminary hydrogel composition consists of only 2-acrylamido-2-methylpropanesulfonic acid (AMPS), distilled water and sodium hydroxide,
    상기 예비하이드로겔 조성물 제조단계는 별도의 광중합 개시제 및 UV중합 개시제를 첨가하지 않는 것을 특징으로 하는 점착 전도성 하이드로겔의 제조방법.The preliminary hydrogel composition preparation step is a method for producing an adhesive conductive hydrogel, characterized in that a separate photopolymerization initiator and UV polymerization initiator are not added.
  4. 제1항에 있어서,According to claim 1,
    상기 예비하이드로겔 조성물 제조단계는 The preliminary hydrogel composition preparation step is
    이온성 모노머; 증류수 및 pH 조절제를 혼합한 후, 가교제를 첨가하는 것을 더 포함하고,ionic monomers; Further comprising adding a crosslinking agent after mixing the distilled water and the pH adjusting agent,
    상기 가교제는 폴리에틸렌글리콜 디아크릴레이트(poly(ethylene glycol) diacrylate, PEG-DA), 2-하이드록시에틸아크릴레이드(2-hydroxylethyl acrylate), 아크릴산(acrylic acid) 및 3-(3,4-디하이드록시페닐)-L-알라닌(3-(3,4-Dihydroxyphenyl)-L-alanine) 중 어느 하나 이상을 포함하고,The crosslinking agent is poly(ethylene glycol) diacrylate (PEG-DA), 2-hydroxylethyl acrylate, acrylic acid and 3-(3,4-dihydride). Contains any one or more of hydroxyphenyl) -L-alanine (3- (3,4-Dihydroxyphenyl) -L-alanine),
    상기 가교제는 상기 예비하이드로겔 조성물 100중량부에 대해서 0.01 내지 0.08 중량부로 혼합하는 것을 특징으로 하는 점착 전도성 하이드로겔의 제조방법.The method of producing an adhesive conductive hydrogel, characterized in that the crosslinking agent is mixed in 0.01 to 0.08 parts by weight based on 100 parts by weight of the prehydrogel composition.
  5. 제1항에 있어서,According to claim 1,
    상기 예비하이드로겔 조성물 제조단계는 pH 조절제를 혼합하여 예비하이드로겔 조성물의 pH를 5 내지 6으로 조절하는 것을 특징으로 하는 점착 전도성 하이드로겔의 제조방법.The prehydrogel composition preparation step is a method for producing an adhesive conductive hydrogel, characterized in that by mixing a pH adjusting agent to adjust the pH of the prehydrogel composition to 5 to 6.
  6. 제1항에 있어서, 상기 전자빔 조사단계에서, 예비하이드로겔 조성물이 5 내지 50 kGy의 전자빔 조사 선량을 흡수하는 것을 특징으로 하는 점착 전도성 하이드로겔의 제조방법.The method of claim 1, wherein in the electron beam irradiation step, the prehydrogel composition absorbs an electron beam irradiation dose of 5 to 50 kGy.
  7. 제1항에 있어서,According to claim 1,
    상기 전자빔 조사단계는 상기 제조한 하이드로겔 조성물을 0.5 내지 10 mm의 두께로 도포하는 것을 특징으로 하는 점착 전도성 하이드로겔의 제조방법.The electron beam irradiation step is a method for producing an adhesive conductive hydrogel, characterized in that for applying the prepared hydrogel composition to a thickness of 0.5 to 10 mm.
  8. 제1항에 있어서,According to claim 1,
    상기 전자빔 조사단계는 부직포 상에 상기 예비하이드로겔 조성물을 도포한 후 전자빔을 조사하는 것을 특징으로 하는 점착 전도성 하이드로겔의 제조방법.The electron beam irradiation step is a method for producing an adhesive conductive hydrogel, characterized in that the electron beam is irradiated after applying the prehydrogel composition on the nonwoven fabric.
  9. 제1항에 있어서,According to claim 1,
    상기 전자빔 조사단계를 거쳐 제조된 점착 전도성 하이드로겔 내의 이온성 모노머의 가교도는 50% 내지 80%인 것을 특징으로 하는 점착 전도성 하이드로겔의 제조방법.The method of producing an adhesive conductive hydrogel, characterized in that the degree of crosslinking of the ionic monomer in the adhesive conductive hydrogel prepared through the electron beam irradiation step is 50% to 80%.
  10. 2-아크릴아미도-2-메틸프로판술폰산(AMPS), 2-하이드록시에틸아크릴레이드(2-hydroxylethyl acrylate), 아크릴산(acrylic acid) 및 3-(3,4-디하이드록시페닐)-L-알라닌(3-(3,4-Dihydroxyphenyl)-L-alanine) 중 어느 하나의 이온성 모노머를 포함하는 예비하이드로겔 조성물에 전자빔 조사하여 가교시켜 구비되고,2-acrylamido-2-methylpropanesulfonic acid (AMPS), 2-hydroxylethyl acrylate, acrylic acid and 3-(3,4-dihydroxyphenyl)-L- It is provided by crosslinking a prehydrogel composition containing any one ionic monomer of alanine (3-(3,4-Dihydroxyphenyl)-L-alanine) by electron beam irradiation,
    전도성은 0.5 내지 5 S/m이며, 점착력은 600 내지 2000 gf/in인 것을 특징으로 하는 점착 전도성 하이드로겔.An adhesive conductive hydrogel, characterized in that the conductivity is 0.5 to 5 S / m, and the adhesive force is 600 to 2000 gf / in.
  11. 제10항에 있어서,According to claim 10,
    상기 점착 전도성 하이드로겔은 5 내지 50 kGy의 전자빔을 조사하여 5 내지 15 kGy의 전자빔을 흡수하는 것을 특징으로 하는 점착 전도성 하이드로겔.The adhesive conductive hydrogel is characterized by absorbing an electron beam of 5 to 15 kGy by irradiating an electron beam of 5 to 50 kGy.
  12. 제10항에 있어서,According to claim 10,
    상기 점착 전도성 하이드로겔층의 두께는 0.5 내지 10 mm인 것을 특징으로 하는 점착 전도성 하이드로겔.The adhesive conductive hydrogel, characterized in that the thickness of the adhesive conductive hydrogel layer is 0.5 to 10 mm.
  13. 제10항에 있어서,According to claim 10,
    상기 점착 전도성 하이드로겔층 내 이온성 모노머의 가교도는 50% 내지 80%인 것을 특징으로 하는 점착 전도성 하이드로겔.The adhesive conductive hydrogel, characterized in that the degree of crosslinking of the ionic monomer in the adhesive conductive hydrogel layer is 50% to 80%.
  14. 제10항에 있어서,According to claim 10,
    상기 점착 전도성 하이드로겔은 인장강도가 200 kPa 내지 300 kPa인 것을 특징으로 하는 점착 전도성 하이드로겔.The adhesive conductive hydrogel has a tensile strength of 200 kPa to 300 kPa.
  15. 2-아크릴아미도-2-메틸프로판술폰산(AMPS), 2-하이드록시에틸아크릴레이드(2-hydroxylethyl acrylate), 아크릴산(acrylic acid) 및 3-(3,4-디하이드록시페닐)-L-알라닌(3-(3,4-Dihydroxyphenyl)-L-alanine) 중 어느 하나의 이온성 모노머를 포함하는 예비하이드로겔 조성물과, 시트형태로 구비되는 부직포층을 포함하고,2-acrylamido-2-methylpropanesulfonic acid (AMPS), 2-hydroxylethyl acrylate, acrylic acid and 3-(3,4-dihydroxyphenyl)-L- A prehydrogel composition containing any one ionic monomer of alanine (3-(3,4-Dihydroxyphenyl)-L-alanine), and a nonwoven fabric layer provided in the form of a sheet,
    상기 예비하이드로겔 조성물은 상기 부직포층의 적어도 일면에 도포된 후 전자빔 조사에 의하여 가교되어 점착 전도성 하이드로겔로 제조되며,The prehydrogel composition is applied to at least one surface of the nonwoven fabric layer and then crosslinked by electron beam irradiation to form an adhesive conductive hydrogel,
    상기 부직포층은 상기 점착 전도성 하이드로겔과 그라프팅(grafting)되어 결합되는 것을 특징으로 하는 점착 전도성 하이드로겔 시트.The adhesive conductive hydrogel sheet, characterized in that the non-woven fabric layer is bonded to the adhesive conductive hydrogel by grafting.
PCT/KR2021/019808 2021-12-24 2021-12-24 Adhesive conductive hydrogel using radiation crosslinking method, method for preparing same, and adhesive conductive hydrogel sheet using same WO2023120782A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PCT/KR2021/019808 WO2023120782A1 (en) 2021-12-24 2021-12-24 Adhesive conductive hydrogel using radiation crosslinking method, method for preparing same, and adhesive conductive hydrogel sheet using same

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/KR2021/019808 WO2023120782A1 (en) 2021-12-24 2021-12-24 Adhesive conductive hydrogel using radiation crosslinking method, method for preparing same, and adhesive conductive hydrogel sheet using same

Publications (1)

Publication Number Publication Date
WO2023120782A1 true WO2023120782A1 (en) 2023-06-29

Family

ID=86903023

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/KR2021/019808 WO2023120782A1 (en) 2021-12-24 2021-12-24 Adhesive conductive hydrogel using radiation crosslinking method, method for preparing same, and adhesive conductive hydrogel sheet using same

Country Status (1)

Country Link
WO (1) WO2023120782A1 (en)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20110042860A (en) * 2009-10-20 2011-04-27 주식회사 바이오프로테크 Conductive hydrogel and preparation method of the same
CN109503757A (en) * 2018-02-06 2019-03-22 青岛大学 The preparation of novel double-net network hydrogel and obtained double-network hydrogel and application
KR20190058125A (en) * 2017-11-21 2019-05-29 주식회사 영우 Manufacturing method of hydrogel
KR20200050552A (en) * 2018-11-02 2020-05-12 충남대학교산학협력단 Temperature Responsive Soft Actuator and Method for Manufacturing the Same
KR20220036999A (en) * 2020-09-16 2022-03-24 서울방사선서비스주식회사 Adhesive conductive hydrogel using radiation crosslinking method, manufacturing method thereof and sheet of adhesive conductive hydrogel using the same

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20110042860A (en) * 2009-10-20 2011-04-27 주식회사 바이오프로테크 Conductive hydrogel and preparation method of the same
KR20190058125A (en) * 2017-11-21 2019-05-29 주식회사 영우 Manufacturing method of hydrogel
CN109503757A (en) * 2018-02-06 2019-03-22 青岛大学 The preparation of novel double-net network hydrogel and obtained double-network hydrogel and application
KR20200050552A (en) * 2018-11-02 2020-05-12 충남대학교산학협력단 Temperature Responsive Soft Actuator and Method for Manufacturing the Same
KR20220036999A (en) * 2020-09-16 2022-03-24 서울방사선서비스주식회사 Adhesive conductive hydrogel using radiation crosslinking method, manufacturing method thereof and sheet of adhesive conductive hydrogel using the same

Similar Documents

Publication Publication Date Title
JP4331261B2 (en) Hydrophilic polyoxyethylene pressure sensitive adhesive
EP0542201B1 (en) Heat-resistant vibration-damping pressure-sensitive adhesive composition, process for producing the same and vibration-damping adhesive tape or sheet using the composition
US7999023B2 (en) Process for making pressure sensitive adhesive hydrogels
EP0289852B1 (en) Radiation curable pressure sensitive adhesive composition
US5124076A (en) Rapid, curing, electrically conductive adhesive
KR102571383B1 (en) Adhesive conductive hydrogel using radiation crosslinking method, manufacturing method thereof and sheet of adhesive conductive hydrogel using the same
WO1982002559A1 (en) Pressure-sensitive adhesive copolymers of acrylic acid ester and n-vinyl pyrrolidone
WO2015041403A1 (en) Acrylic emulsion adhesive, and production method for same
CA1237229A (en) Method for making conductive member for skin contact electrode containing sulfonated polymer material
EP0349232A2 (en) Acrylic copolymers and method of making the same
US20070281029A1 (en) Method for preparing high absorbent hydrocolloid
CN110157364B (en) Medical conductive pressure-sensitive adhesive, preparation method thereof and electrode slice prepared from same
WO2023120782A1 (en) Adhesive conductive hydrogel using radiation crosslinking method, method for preparing same, and adhesive conductive hydrogel sheet using same
CN113621100A (en) Polymerizable eutectic solvent, dry-type ion conductor prepared from polymerizable eutectic solvent and preparation method of dry-type ion conductor
EP0161048B1 (en) Radiation curable adhesive composition for surface protective film
US5183599A (en) Rapid curing, electrically conductive adhesive
EP0869977A1 (en) Use of pendant photoreactive moieties on polymer precursors to prepare hydrophilic pressure sensitive adhesives
WO2016043521A1 (en) Adhesive composition, optical adhesive film and touch screen panel
WO2013154261A1 (en) Eva sheet for solar cell sealing material and method for manufacturing same
WO2013065981A1 (en) Adhesive film having good machinability for protecting the surface of a semiconductor wafer
WO2016043518A1 (en) Adhesive composition for touch screen panel, adhesive film and touch screen panel
WO2013165067A1 (en) Adhesive composition having outstanding barrier characteristics
CN114891447B (en) Acrylate/polyisobutylene rubber hybrid pressure-sensitive adhesive composition
JP4353721B2 (en) Medical adhesive sheet
WO2023068455A1 (en) Method for forming hydrophilic electrodeposited coat film on surface of heat exchanger and heat exchanger fabricated thereby

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 21969146

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE