CN114716867A - Filler dispersion liquid, ink and application of filler dispersion liquid and ink - Google Patents
Filler dispersion liquid, ink and application of filler dispersion liquid and ink Download PDFInfo
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- CN114716867A CN114716867A CN202210302705.3A CN202210302705A CN114716867A CN 114716867 A CN114716867 A CN 114716867A CN 202210302705 A CN202210302705 A CN 202210302705A CN 114716867 A CN114716867 A CN 114716867A
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- Prior art keywords
- ink
- butanone
- dispersion liquid
- filler dispersion
- silicon dioxide
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- 239000006185 dispersion Substances 0.000 title claims abstract description 50
- 239000000945 filler Substances 0.000 title claims abstract description 46
- 239000007788 liquid Substances 0.000 title claims abstract description 37
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims abstract description 63
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 60
- 238000000034 method Methods 0.000 claims abstract description 42
- 229920005989 resin Polymers 0.000 claims abstract description 38
- 239000011347 resin Substances 0.000 claims abstract description 38
- 230000008569 process Effects 0.000 claims abstract description 34
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 30
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 20
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 11
- 239000011342 resin composition Substances 0.000 claims abstract description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 38
- 238000002360 preparation method Methods 0.000 claims description 25
- 239000004593 Epoxy Substances 0.000 claims description 20
- 239000004925 Acrylic resin Substances 0.000 claims description 13
- 229920000178 Acrylic resin Polymers 0.000 claims description 13
- 239000012752 auxiliary agent Substances 0.000 claims description 10
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 9
- 125000000524 functional group Chemical group 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 8
- 229920006395 saturated elastomer Polymers 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 6
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 3
- 239000000194 fatty acid Substances 0.000 claims description 3
- 229930195729 fatty acid Natural products 0.000 claims description 3
- 150000004665 fatty acids Chemical class 0.000 claims description 3
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 2
- 150000001735 carboxylic acids Chemical class 0.000 claims 5
- 238000002156 mixing Methods 0.000 abstract description 17
- 238000011049 filling Methods 0.000 abstract description 9
- 238000007639 printing Methods 0.000 abstract description 6
- 239000000203 mixture Substances 0.000 abstract description 5
- 238000006243 chemical reaction Methods 0.000 abstract description 4
- WSGCRAOTEDLMFQ-UHFFFAOYSA-N nonan-5-one Chemical compound CCCCC(=O)CCCC WSGCRAOTEDLMFQ-UHFFFAOYSA-N 0.000 abstract description 2
- 239000000976 ink Substances 0.000 description 67
- 230000000694 effects Effects 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 14
- 238000001723 curing Methods 0.000 description 12
- 239000003822 epoxy resin Substances 0.000 description 10
- 229920000647 polyepoxide Polymers 0.000 description 10
- KQTIIICEAUMSDG-UHFFFAOYSA-N tricarballylic acid Chemical compound OC(=O)CC(C(O)=O)CC(O)=O KQTIIICEAUMSDG-UHFFFAOYSA-N 0.000 description 10
- 238000001035 drying Methods 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 229920001187 thermosetting polymer Polymers 0.000 description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 7
- VOOLKNUJNPZAHE-UHFFFAOYSA-N formaldehyde;2-methylphenol Chemical compound O=C.CC1=CC=CC=C1O VOOLKNUJNPZAHE-UHFFFAOYSA-N 0.000 description 7
- 238000011161 development Methods 0.000 description 6
- 125000003700 epoxy group Chemical group 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 229910000679 solder Inorganic materials 0.000 description 6
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 239000004848 polyfunctional curative Substances 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 238000001029 thermal curing Methods 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000003466 welding Methods 0.000 description 3
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 description 2
- 239000005750 Copper hydroxide Substances 0.000 description 2
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 239000002671 adjuvant Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229910001956 copper hydroxide Inorganic materials 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- MUXOBHXGJLMRAB-UHFFFAOYSA-N Dimethyl succinate Chemical compound COC(=O)CCC(=O)OC MUXOBHXGJLMRAB-UHFFFAOYSA-N 0.000 description 1
- -1 acrylic modified o-cresol formaldehyde Chemical class 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Inorganic materials [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
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- 238000007796 conventional method Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
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- 238000005516 engineering process Methods 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Chemical group CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000004850 liquid epoxy resins (LERs) Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000005476 soldering Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
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Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/0094—Filling or covering plated through-holes or blind plated vias, e.g. for masking or for mechanical reinforcement
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses filler dispersion liquid, ink and application thereof, wherein the filler dispersion liquid comprises spherical silicone butanone, and the spherical silicone butanone comprises butanone dispersion liquid of silicon dioxide. The silicon dioxide and the butanone are premixed and then added into the ink, and the mixture is added in a form of dispersion liquid, so that the silicon dioxide is well dispersed in the butanone, the silicon dioxide and the butanone are prevented from being added separately, the silicon dioxide is easy to aggregate in the ink, the mixing is uneven, the reaction is not thorough, and the ink hole filling is influenced; the silicon dioxide is high in hardness and good in heat conductivity, and after the silicon dioxide is prepared into the butyl ketone dispersion liquid, the dispersibility is better, the CTE and the stress of the printing ink can be well reduced, gaps in resin molecular chains in the printing ink are filled, the heat resistance of the resin composition is assisted to be improved, the contractibility of the printing ink is reduced in a high-temperature environment, and further cracks or peeling are not easy to generate in the hole plugging process.
Description
Technical Field
The invention belongs to the technical field of PCBs, and particularly relates to filler dispersion liquid, ink and application thereof.
Background
The functional via hole developable resin plug hole has wide application in the manufacturing process of Printed Circuit Boards (PCBs), and the quality of the developable resin has important influence on the welding process of a client. With the rapid development of 5G communication, the integration level of PCB design is higher and higher, the circuit pattern is finer, the distance between the functional conducting through holes is smaller and smaller, the corresponding quality requirement on the hole plugging of the functional via hole developable resin is gradually improved, the problem of cracks is particularly not accepted, the poor cracks of the developable resin can cause the short circuit caused by tin balls hidden in the welding process, and the risk of open circuit caused by the corrosion of a conductor copper layer caused by residual liquid medicine in the hole is generated.
The hole plugging process of the developable resin comprises the following steps: normal flow → graphic production → developable resin hole plugging → solder resist → normal flow, wherein, the factors influencing the hole plugging quality mainly comprise hole plugging process, hole plugging ink, hole plugging and plate baking modes and the like. The hole plugging process mainly comprises two modes of solder-resisting aluminum sheet hole plugging and solder-resisting silk screen connection plugging and tape printing, wherein the solder-resisting aluminum sheet hole plugging process has a good effect through industrial verification and becomes a main hole plugging process in the manufacturing and processing process of the PCB. The hole plugging drying plate mode mostly adopts a sectional low-temperature drying plate program, and the corresponding manufacturing process and effect are basically the same, so the hole plugging drying plate has small influence on the hole plugging quality. The hole plugging ink mainly comprises developable resin, a solvent and an auxiliary agent, and the difference of hole plugging quality is large due to different types of the developable resin in the current market; therefore, the type of developable resin is one of the important factors affecting the quality of the via holes.
The conventional developable resin composition is mainly formed by mixing a main agent (connecting main material I) and a matched hardening agent (connecting main material II), wherein, because a local position needs to be developed and removed, the connecting main material I as the main agent must use a photosensitive developable acrylic resin. In the related art, the connection main body materials I and II for plugging holes or screen printing processing (a certain proportion of thinner is required to be added for viscosity adjustment) are usually mixed according to the mass ratio of 75:25, so that the good performance of resin plugging quality and easy development and cleaning can be realized. In view of the poor thermosetting property of the acrylic resin, the problem that cracks of different degrees are caused by curing stress occurs in 100% of resin plug holes after the resin plug holes are cured by hot baking, and no effective solution is provided in the industry at present.
In order to reduce the crack problem as much as possible and improve the reliability of the functional via hole, in the related art, a resin hole is usually plugged before the pattern is made, and thermosetting epoxy resin is used as a hardening agent for plugging, and the thermosetting resin hole plugging process: normal flow → resin plug hole → thermal bake curing → ceramic grinding plate → optical inspection → graphic making → solder mask → normal flow. Therefore, the process is complex and high in cost, and meanwhile, the resin plug holes can often cause the plug holes to be sunken or black holes due to bubbles/impurities in the holes, so that the open circuit problem is caused in the pattern manufacturing.
Based on the method, finding out a new improvement direction to realize the reduction of the crack problem and the improvement of the hole plugging quality has important significance.
Statements in this background are not admitted to be prior art to the present disclosure.
Disclosure of Invention
The present invention is directed to solving at least one of the problems of the prior art described above. Therefore, the invention provides the application of the filler dispersion liquid in the preparation of the ink of the hole plugging process, which can effectively reduce the incidence rate of resin hole plugging cracks.
The invention also provides the application of the filler dispersion liquid.
According to one aspect of the present invention, there is provided the use of a filler dispersion comprising a dispersion of sphero-silicone butanone comprising silica in the preparation of a via-fill process ink.
According to a preferred embodiment of the present invention, at least the following advantages are provided: the silicon dioxide and the butanone are premixed and then added into the ink, and the mixture is added in a form of dispersion liquid, so that the silicon dioxide is well dispersed in the butanone, the silicon dioxide and the butanone are prevented from being added separately, the silicon dioxide is easy to aggregate in the ink, the mixing is uneven, the reaction is not thorough, and the ink hole filling is influenced; the silicon dioxide is high in hardness and good in heat conductivity, and after the silicon dioxide is prepared into the butyl ketone dispersion liquid, the dispersibility is better, the Coefficient of Thermal Expansion (CTE) and curing shrinkage stress of the ink can be better reduced, gaps in resin molecular chains in the ink are filled, the heat resistance of the resin composition is assisted to be improved, the ink shrinkage is reduced in a high-temperature environment, and further cracks or peeling are not easy to generate in the hole plugging process.
In some preferred embodiments of the invention, the silica has a particle size of less than 5 microns.
In some preferred embodiments of the invention, the silica has a particle size of from 0.1 micron to 2 microns.
In some more preferred embodiments of the invention, the silica has an average particle size of from 0.4 microns to 0.6 microns.
In some more preferred embodiments of the invention, the silica has an average particle size of about 0.5 microns.
In some embodiments of the invention, the silica is spherical.
In some embodiments of the present invention, the filler dispersion is ball silicone butanone, and the butanone accounts for 8% to 15% of the weight of the filler dispersion.
In some preferred embodiments of the invention, the butanone is present in the filler dispersion at a weight ratio of about 10%.
In some preferred embodiments of the present invention, the above filler dispersion is prepared by a method comprising the steps of:
dispersing and mixing the silicon dioxide and butanone to obtain the silicon dioxide/butanone composite material.
In some embodiments of the invention, the dispersive mixing is stirred mixing.
In some embodiments of the invention, the dispersive mixing is ultrasonic mixing.
In some embodiments of the invention, the time of dispersive mixing is 8 hours or more.
In some preferred embodiments of the invention, the time of dispersive mixing is 8 hours to 12 hours.
In some preferred embodiments of the invention, the time of dispersive mixing is 9.5 hours to 10.5 hours.
In some preferred embodiments of the invention, the time for dispersive mixing is about 10 hours.
According to another aspect of the present invention, an ink is prepared from a developable resin composition, a solvent, and an auxiliary agent, the auxiliary agent comprising a filler dispersion, the filler dispersion comprising a sphero-silicone butanone comprising a butanone dispersion of silica.
According to a preferred embodiment of the present invention, at least the following advantages are provided: adding spherical silicone butanone into the ink to assist in improving the heat resistance of the composition; by adopting the ink provided by the invention, the crack degree of the resin can be obviously reduced, and the incidence rate of the resin hole plugging cracks is effectively reduced. The ink adopting the scheme of the invention only generates slight cracks, the cracks can not penetrate through the hole diameter to the hole wall position, no influence or little influence on the performance is caused, and the use requirement is basically met, while the traditional ink generates 19.6-100% of cracks, the cracks are serious, generally penetrate through the whole hole diameter size, the cracks extend to the hole wall, the performance is greatly influenced, and the use requirement can not be met.
In some embodiments of the present invention, the developable resin composition is composed of a main agent and a hardener, the main agent is selected from modified photosensitive resins selected from carboxylic acid-modified epoxy acrylic resins, and the molar ratio of carboxyl functional groups to epoxy functional groups in the carboxylic acid-modified epoxy acrylic resins is 1.9 ± 0.1. The quantity of-COOH functional groups is increased, and solder resist cracks can be effectively reduced; in addition, the mole ratio of the carboxyl functional group of-COOH to the functional group of epoxy group is increased from the conventional range of 1.4 +/-0.2 to the range of 1.9 +/-0.1, so that the developing performance is better. The hardening agent needs to meet the requirements of developing and heat resistance, and after the proportion of the hardening agent is increased, the developing performance is influenced to a certain extent.
In some preferred embodiments of the present invention, the carboxylic acid modified epoxy acrylic resin is prepared from a saturated carboxylic acid and an epoxy acrylic resin, wherein the epoxy acrylic resin may be a photosensitive epoxy acrylic resin commonly used in the art.
In some more preferred embodiments of the present invention, the saturated carboxylic acid is selected from at least one of a fatty acid or an aromatic acid.
In some more preferred embodiments of the present invention, the saturated carboxylic acid is selected from at least one of a mono-acid, a di-acid, or a poly-acid.
In some more preferred embodiments of the invention, the saturated carboxylic acid is selected from polybasic fatty acids. The polycarboxylic acid is adopted to provide a plurality of carboxyl groups, so that the hydrophilic solubility of reactants can be better improved after the main agent reacts with the hardening agent.
In some preferred embodiments of the present invention, the hardener is selected from thermosetting epoxy resins. Hardeners conventional in the art may be used.
In some preferred embodiments of the present invention, the mass ratio of the hardener to the main agent is x: 1, the value of x satisfies the following relation: 1< x < 2. If the ratio is more than 2, the problem of incomplete development is likely to occur, while if the ratio is less than 1, cracks are likely to occur relatively seriously, which has a certain influence on the performance.
In some embodiments of the present invention, the value of x satisfies the following relationship: 1.5< x < 1.8. Compared with the traditional developable resin composition, the specific gravity of the hardening agent relative to the main agent is improved, the thermosetting property of the developable resin is further improved, the composition with the proportion has better heat resistance, the problem of resin cracks can be further improved, and the cracks are avoided. When the mass ratio of the hardening agent to the main agent is controlled within the range of 1.5< x <1.8, the generation of cracks can be synergistically reduced, and meanwhile, the developing effect can be well ensured. When the value of x is 1.5 or more, slight cracks (less than 5%) are likely to occur, and when it is 1.8 or less, development failure occurs.
In some embodiments of the invention, the coagent further comprises a photoinitiator and a thermal curing agent. The scheme of the invention adopts the conventional photoinitiator and thermal curing agent.
In some embodiments of the invention, the adjuvant further comprises a pigment. Pigments may be added as desired.
In some embodiments of the invention, the adjuvant further comprises a filler. The filler can be added according to the requirement, and the filler can be the conventional filler in the field. In addition, other auxiliary agents, such as defoaming agents and other functional auxiliary agents commonly used in the same type of ink can be added.
In some embodiments of the present invention, the raw materials for preparing the ink comprise the following components by mass: 45-50% of a developable resin composition, 25-30% of a solvent and 25% of an auxiliary agent, wherein the filler dispersion liquid accounts for 5-10% of the weight of the ink preparation raw materials.
In some preferred embodiments of the present invention, the filler dispersion liquid accounts for 5% by mass of the ink preparation raw material.
In some embodiments of the invention, the ink is an ink used in a PCB hole plugging process.
In some embodiments of the invention, the ink is a flexible ink.
In another aspect of the invention, the application of the ink in the preparation of the PCB is also provided.
The application according to a preferred embodiment of the invention has at least the following advantageous effects: the ink of the scheme of the invention can be used for the developable resin PCB which is prepared by filling the hole with the aluminum solder mask sheet and has the plate thickness of less than 3.0mm (such as 1.0 mm) and the hole filling aperture of less than 0.40mm (such as 0.275 mm), the alkali liquor is well developed after the solder mask green oil is normally coated, the problem of hole filling crack is only slightly or even not blocked after reflow soldering at 260 ℃, and the crack rate is usually 19.6-100% by adopting the traditional ink.
In some embodiments of the invention, the application is an application in a PCB jack process.
The invention also provides a PCB, and the preparation raw materials of the PCB comprise the printing ink.
The PCB according to a preferred embodiment of the invention has at least the following beneficial effects: the printing ink has good developability, low resin crack generation and no resin crack generation, and can effectively reduce the risks of short circuit caused by tin ball hiding in the welding process and open circuit caused by corrosion of a conductor copper layer caused by residual liquid medicine in a hole.
The invention also provides a PCB hole plugging method, which comprises the following steps: and filling the ink into the through hole, pre-baking, exposing and developing, and then thermally baking and curing. Wherein the pre-drying temperature is 65-80 ℃, and the pre-drying time is 10-20 min.
The PCB hole plugging method according to a preferred embodiment of the invention has at least the following beneficial effects: the pore plugging plate after thermosetting and prebaking of the hardener in the prebaking process has good developability and no residue, and can better reduce the occurrence degree of cracks by further thermosetting through heat baking so as to improve the reliability of functional via holes.
In some preferred embodiments of the present invention, the pre-drying temperature is 65 ℃ to 80 ℃, and the pre-drying time is 10min to 20 min.
In some preferred embodiments of the present invention, the pre-drying temperature is 70 ℃ to 75 ℃, and the pre-drying time is 10min to 15 min.
In some more preferred embodiments of the present invention, the pre-baking temperature is 73 ℃ and the pre-baking time is 15 min.
In some embodiments of the present invention, the baking temperature is 80-150 ℃ and the baking time is 200-500 min. After pre-baking, carrying out exposure and development, then carrying out thermal baking curing, gradually curing from low temperature to high temperature, reducing resin curing stress, and enabling the resin to slowly carry out resin thermal curing polymerization reaction completely. The hole plugging method provided by the scheme of the invention is simple and convenient to operate and high in hole plugging quality.
Drawings
The invention is further described with reference to the following figures and examples, in which:
FIG. 1 is a schematic view showing the operation flow of via filling of a solder resist aluminum sheet in examples 1 to 6 and comparative examples 1 to 3 of the present invention;
FIG. 2 is a diagram illustrating the plugging effect of embodiment 1 of the present invention;
FIG. 3 is a diagram illustrating the hole plugging effect of embodiment 2 of the present invention;
FIG. 4 is a diagram illustrating the hole plugging effect of embodiment 6 of the present invention;
FIG. 5 is a graph showing the hole plugging effect of comparative example 1 according to the present invention;
FIG. 6 is a graph showing the hole plugging effect of comparative example 2 according to the present invention;
fig. 7 is a reaction mechanism diagram of the ink curing process.
Detailed Description
The concept and technical effects of the present invention will be clearly and completely described below in conjunction with the embodiments to fully understand the objects, features and effects of the present invention. It is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments, and those skilled in the art can obtain other embodiments without inventive effort based on the embodiments of the present invention, and all embodiments are within the protection scope of the present invention. The test methods used in the examples are all conventional methods unless otherwise specified; the materials, reagents and the like used are commercially available reagents and materials unless otherwise specified.
In the description of the present invention, reference to the description of the terms "one embodiment," "some embodiments," "an illustrative embodiment," "an example," "a specific example," or "some examples," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
In the description of the present invention, the meaning of "about" means plus or minus 2%, unless otherwise specified.
Example 1
The present example provides the use of a filler dispersion in the preparation of a via fill process ink. The filler dispersion is silicon ball butanone, and the silicon ball butanone is a dispersion of silicon dioxide. The preparation process comprises the following steps: mixing silicon dioxide (spherical, with an average particle size of 0.5 micron) and butanone according to a mass ratio of 90: 10 and stirring for 10 hours.
And mixing the filler dispersion liquid with other auxiliary agents, a main agent, a hardening agent and a solvent to prepare the hole plugging process ink.
Wherein, the mass percentage of the filler dispersion liquid in the ink is 5 percent, the mass percentage of the main agent in the ink is 19 percent, the mass percentage of the hardening agent in the ink is 31 percent, the other auxiliary agents (containing photoinitiator (2,4, 6-trimethyl benzoyl-diphenyl phosphine oxide) is 3.5 percent, the thermal curing agent (triethylamine) is 5 percent, and the filling material is 11.5 percent (TiO) (2And BaSO4The mass ratio of the two is 1:1)) is 20 percent, and the balance is solvent (dimethyl succinate).
The main agent is modified epoxy acrylic resin, is synthesized by tricarballylic acid and o-cresol formaldehyde epoxy acrylic photosensitive resin, and the molar ratio of the carboxyl functional group to the epoxy group functional group is 1.9.
The o-cresol formaldehyde epoxy acrylic photosensitive resin can be prepared by referring to the related technology, and the preparation process of the acrylic modified o-cresol formaldehyde epoxy resin used in the embodiment is as follows: taking o-cresol formaldehyde epoxy resin (the type of which is CY-DCN-200 in the tomine petrochemical production, the epoxy value is 0.48-0.51, and the epoxy equivalent is 195-210 g/eq), mixing the o-cresol formaldehyde epoxy resin with acrylic acid according to the proportion of the mole number of acrylic acid to the mole number of epoxy groups of 0.3:1, adding 1 wt% of N, N-dimethylaniline (accounting for 1 wt% of the total mass of the o-cresol formaldehyde epoxy resin and the acrylic acid), uniformly stirring, and heating (95 ℃) to react for 3 hours.
And mixing the mixture and the tricarballylic acid according to the mol number of carboxyl in the tricarballylic acid and the mol number of the residual epoxy group in the o-cresol formaldehyde epoxy acrylic acid photosensitive resin in a ratio of 1.9:1, uniformly stirring, and heating (100 ℃) to react for 8 hours.
Hardening agent: bisphenol A type liquid epoxy resin 128(cas number: 61788-97-4, epoxy equivalent 180-.
Example 2
The preparation of the embodiment provides application of the filler dispersion liquid in preparation of the hole plugging process ink. The differences from example 1 are: in the prepared ink, the main agent and the hardening agent are sequentially in percentage by mass: 20% and 30%, the corresponding mass% changes being filled by the solvent.
Example 3
The preparation of the embodiment provides application of the filler dispersion liquid in preparation of the hole plugging process ink. The differences from example 1 are: in the prepared ink, the main agent and the hardening agent are sequentially in percentage by mass: 17% and 28%, the corresponding mass percentage changes being filled by the solvent.
Example 4
The preparation of the embodiment provides application of the filler dispersion liquid in preparation of the hole plugging process ink. The differences from example 1 are: the mixing ratio (mass ratio) of the silicon dioxide and the butanone in the preparation process of the filler dispersion liquid is as follows: 85: 15, respectively.
Example 5
The preparation of the embodiment provides application of the filler dispersion liquid in preparation of the hole plugging process ink. The differences from example 1 are: in the prepared ink, the mass ratio of the filler dispersion liquid is 10%, and the corresponding mass percentage change is leveled up by reducing the mass ratio of the filler.
Example 6
The comparative example provides the application of the filler dispersion liquid in the preparation of the hole plugging process ink. The differences from example 1 are: in the prepared ink, the mass ratio of the main agent to the hardening agent is respectively 17.85%: 32.15 percent.
Comparative example 1
This example preparation provides a via plugging process ink which differs from example 2 by: in the preparation process of the main agent, the mole number of carboxyl in the tricarballylic acid of the tricarballylic acid and the mole number of the residual epoxy group in the o-cresol formaldehyde epoxy acrylic acid photosensitive resin are mixed according to the proportion of 1.4, and the filler dispersion liquid is not added, and the corresponding mass ratio of the filler dispersion liquid is increased to the mass ratio of the filler.
Comparative example 2
This comparative example preparation provides an ink which differs from comparative example 1 in that: in the ink, the mass ratio of the main agent to the hardening agent is 19% and 31%, respectively.
Comparative example 3
This comparative example provides an ink that differs from example 1 by: in the ink, the silica was not added in the form of a filler dispersion, but was directly added separately in the same mass as in example 1 as silica and methyl ethyl ketone.
Test examples
This test example tested the plugging effect of the inks prepared in the examples and comparative examples. Plugging treatment was performed using a conventional aluminum-sheet-solder-resist plugging technique (pressure: 10 kg/cm) as shown in FIG. 12(5-20kg/cm2All can be used); opening size of the aluminum sheet: d +6mil (D is the diameter of the plug hole via, 0.1mm, 0.25mm, 0.1mm is selected in this embodiment).
The hole plugging process is as follows:
the ink is subjected to thermosetting (prebaking at 73 ℃ for about 15min, cooling for 20min, exposing by using an exposure machine (taking a high-pressure mercury lamp as a light source), developing by using a developing machine after exposure and cooling (2 wt% of sodium carbonate aqueous solution, the developing temperature is 35 ℃), baking for 300min at 100 ℃ (80-150 ℃), detecting the crack condition (using a ten-fold mirror and a hundred-fold mirror for visual inspection, and analyzing the crack size of a vertical slice by a metallographic microscope), and the detection results are as follows:
the ink of example 1 showed the plugging effect as shown in fig. 2, and it can be seen that no cracks were generated after plugging.
The effect of plugging the pores of the ink of example 2 is shown in fig. 3, from which it can be seen that slight cracks (less than 5%) are generated after plugging the pores.
The plugging effects of examples 3 to 5 are similar to those of example 1, and are not shown one by one to avoid redundancy.
The plug-in effect of example 6 was similar to that of example 1, but slight development failure occurred (as shown in fig. 4).
The plugging effect of the ink of comparative example 1 is shown in fig. 5, and it can be seen that severe cracks were generated after plugging.
The plugging effect of the ink of comparative example 2 is shown in fig. 6, and it can be seen that severe cracks were generated after plugging.
The ink of comparative example 3 has poor silica dispersibility and is liable to aggregate, the CTE of the ink is not uniform due to non-uniform filling and distribution in molecular framework of the developable resin, severe cracks occur depending on stress at different positions after the via holes of the ink are cured, and the workability of the drilling process and the like is impaired.
The resin reaction mechanism is shown in fig. 7, and it can be seen from the figure that when the epoxy resin is used for plugging the pores, intermolecular adsorption (i.e., curing stress) exists between the strong polar groups such as hydroxyl groups and ether bonds in the epoxy resin and the adjacent interface, and meanwhile, both epoxy groups and hydroxyl groups react with free bonds on the surface of the medium (the surface of metal such as copper on the pore wall) to form chemical bonds (e.g., hydroxyl copper bonding force) and form extremely strong adhesive tension; when the copper hydroxide is not stripped from the hole wall, the bonding force of the copper hydroxide is basically equivalent to the curing stress; when the ink is baked and cured and stripped from the hole wall, as the baking and curing process of the ink is a process of heating from the hole wall to the hole to form a polymer three-dimensional cured object, the volume shrinkage of the epoxy resin causes the generation of shrinkage stress which is separated from a bonding interface, the more the volume shrinkage, the larger the acting force is, and the ink cracks appear when the molecular bonding force after the epoxy resin is cured is exceeded; the middle position of the hole wall is a region with the largest volume deformation and a region with the weakest ink macromolecule bonds, so that cracks usually appear in the middle region of the hole wall. In the embodiments of the invention, the shrinkage stress in the ink baking process is controlled and synergistically reduced by using the filler dispersion liquid or the ink containing the filler dispersion liquid in the scheme of the invention in combination with the processes of low-temperature pre-baking and high-temperature baking curing, so that the crack occurrence rate is effectively reduced.
The embodiments of the present invention have been described in detail with reference to the accompanying drawings, but the present invention is not limited to the above embodiments, and various changes can be made within the knowledge of those skilled in the art without departing from the gist of the present invention. Furthermore, the embodiments of the present invention and the features of the embodiments may be combined with each other without conflict.
Claims (11)
1. The application of the filler dispersion liquid in the preparation of the hole plugging process ink is characterized in that: the filler dispersion comprises ball silicone butanone, and the ball silicone butanone comprises a butanone dispersion of silicon dioxide.
2. Use according to claim 1, characterized in that: the filler dispersion liquid is spherical silicone butanone, and the mass ratio of the butanone in the filler dispersion liquid is 8-15%.
3. An ink, characterized by: the preparation raw materials of the ink comprise a developable resin composition, a solvent and an auxiliary agent, wherein the auxiliary agent comprises a filler dispersion liquid, the filler dispersion liquid comprises spherical silicone butanone, and the spherical silicone butanone comprises butanone dispersion liquid of silicon dioxide.
4. An ink according to claim 3, wherein: the developable resin composition is composed of a main agent and a hardening agent, wherein the main agent is selected from modified photosensitive resin, the modified photosensitive resin is selected from carboxylic acid modified epoxy acrylic resin, and the carboxylic acid modified epoxy acrylic resin is prepared from saturated carboxylic acid and epoxy acrylic resin.
5. The ink according to claim 4, characterized in that: the molar ratio of the carboxyl functional group in the saturated carboxylic acid to the epoxy functional group in the epoxy acrylic resin is 1.9 +/-0.1.
6. The ink of claim 4, wherein: the saturated carboxylic acid is selected from at least one of fatty acid or aromatic acid.
7. The ink according to claim 4, characterized in that: the mass ratio of the hardening agent to the main agent is x: 1, the value of x satisfies the following relation: 1< x < 2.
8. The ink of claim 7, wherein: the value of x satisfies the following relationship: 1.5< x < 1.8.
9. Use of an ink according to any one of claims 4 to 8 in the preparation of a PCB.
10. A PCB, characterized by: the PCB is prepared from a raw material comprising the ink as set forth in any one of claims 4 to 8.
11. A PCB hole plugging method is characterized in that: the method comprises the following steps: inserting the ink according to any one of claims 4 to 8 into the through-hole, pre-baking, exposing, developing, and then curing by heat baking.
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| CN202210302705.3A CN114716867B (en) | 2022-03-25 | 2022-03-25 | Filler dispersion liquid, printing ink and application thereof |
| PCT/CN2022/099822 WO2023178850A1 (en) | 2022-03-25 | 2022-06-20 | Filler dispersion liquid, ink and use thereof |
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| CN202210302705.3A CN114716867B (en) | 2022-03-25 | 2022-03-25 | Filler dispersion liquid, printing ink and application thereof |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6238840B1 (en) * | 1997-11-12 | 2001-05-29 | Hitachi Chemical Company, Ltd. | Photosensitive resin composition |
| JP2005250004A (en) * | 2004-03-03 | 2005-09-15 | Tamura Kaken Co Ltd | Photosensitive resin composition, composition for solder resist, photosensitive dry film and printed wiring board |
| JP2006036916A (en) * | 2004-07-27 | 2006-02-09 | Admatechs Co Ltd | Slurry composition, varnish composition, and insulating film and prepreg using the same |
| JP2009280726A (en) * | 2008-05-23 | 2009-12-03 | Goo Chemical Co Ltd | Carboxyl group-containing resin and its cured product |
| CN105086604A (en) * | 2015-07-13 | 2015-11-25 | 深圳市容大感光科技股份有限公司 | Printing ink composition, application thereof and printed circuit board |
| CN110079128A (en) * | 2019-04-29 | 2019-08-02 | 江苏辉迈粉体科技有限公司 | A kind of Submicron spherical silica micropowder organic dispersions and preparation method thereof |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI346111B (en) * | 2004-02-09 | 2011-08-01 | Nippon Kayaku Kk | Photosensitive resin composition and products of cured product thereof |
| EP2292678B1 (en) * | 2008-06-09 | 2012-02-15 | Goo Chemical Co., Ltd. | Carboxyl group-containing resin, curable composition containing carboxyl group-containing resin, and cured product of the composition |
| CN105086603A (en) * | 2015-07-13 | 2015-11-25 | 惠州市容大油墨有限公司 | Photo-curing thermo-curing composition ink, application of photo-curing thermo-curing composition ink and circuit board containing photo-curing thermo-curing composition ink |
| CN106700132B (en) * | 2016-12-20 | 2019-04-30 | 广东生益科技股份有限公司 | A kind of silica slurry feed composition and its preparation method and application |
| CN110402029A (en) * | 2019-07-19 | 2019-11-01 | 华芯电子(天津)有限责任公司 | A kind of processing technology of PCB substrate ink plugging |
-
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6238840B1 (en) * | 1997-11-12 | 2001-05-29 | Hitachi Chemical Company, Ltd. | Photosensitive resin composition |
| JP2005250004A (en) * | 2004-03-03 | 2005-09-15 | Tamura Kaken Co Ltd | Photosensitive resin composition, composition for solder resist, photosensitive dry film and printed wiring board |
| JP2006036916A (en) * | 2004-07-27 | 2006-02-09 | Admatechs Co Ltd | Slurry composition, varnish composition, and insulating film and prepreg using the same |
| JP2009280726A (en) * | 2008-05-23 | 2009-12-03 | Goo Chemical Co Ltd | Carboxyl group-containing resin and its cured product |
| CN105086604A (en) * | 2015-07-13 | 2015-11-25 | 深圳市容大感光科技股份有限公司 | Printing ink composition, application thereof and printed circuit board |
| CN110079128A (en) * | 2019-04-29 | 2019-08-02 | 江苏辉迈粉体科技有限公司 | A kind of Submicron spherical silica micropowder organic dispersions and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 李子东等, 新时代出版社 * |
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| CN114716867B (en) | 2023-06-27 |
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