CN111378080A - Nano micro needle and photosensitive material composition for micro needle array production and preparation method thereof - Google Patents
Nano micro needle and photosensitive material composition for micro needle array production and preparation method thereof Download PDFInfo
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- CN111378080A CN111378080A CN202010256463.XA CN202010256463A CN111378080A CN 111378080 A CN111378080 A CN 111378080A CN 202010256463 A CN202010256463 A CN 202010256463A CN 111378080 A CN111378080 A CN 111378080A
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- 239000000463 material Substances 0.000 title claims abstract description 41
- 239000000203 mixture Substances 0.000 title claims abstract description 40
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 238000003491 array Methods 0.000 claims abstract description 16
- 239000000178 monomer Substances 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 11
- 238000005516 engineering process Methods 0.000 claims abstract description 10
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 8
- 239000011347 resin Substances 0.000 claims abstract description 8
- 229920005989 resin Polymers 0.000 claims abstract description 8
- 238000000016 photochemical curing Methods 0.000 claims abstract description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 10
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 7
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 claims description 6
- GTELLNMUWNJXMQ-UHFFFAOYSA-N 2-ethyl-2-(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical class OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.CCC(CO)(CO)CO GTELLNMUWNJXMQ-UHFFFAOYSA-N 0.000 claims description 4
- 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 claims description 4
- 238000001723 curing Methods 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 239000012949 free radical photoinitiator Substances 0.000 claims description 4
- 239000012528 membrane Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 238000006116 polymerization reaction Methods 0.000 claims description 4
- 238000007789 sealing Methods 0.000 claims description 4
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 3
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 3
- 238000003828 vacuum filtration Methods 0.000 claims description 3
- MYWOJODOMFBVCB-UHFFFAOYSA-N 1,2,6-trimethylphenanthrene Chemical compound CC1=CC=C2C3=CC(C)=CC=C3C=CC2=C1C MYWOJODOMFBVCB-UHFFFAOYSA-N 0.000 claims description 2
- JZEXORLUKMQOFA-UHFFFAOYSA-N 2-(1-ethoxyethyl)-2-(hydroxymethyl)propane-1,3-diol prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.CCOC(C)C(CO)(CO)CO JZEXORLUKMQOFA-UHFFFAOYSA-N 0.000 claims description 2
- YIJYFLXQHDOQGW-UHFFFAOYSA-N 2-[2,4,6-trioxo-3,5-bis(2-prop-2-enoyloxyethyl)-1,3,5-triazinan-1-yl]ethyl prop-2-enoate Chemical compound C=CC(=O)OCCN1C(=O)N(CCOC(=O)C=C)C(=O)N(CCOC(=O)C=C)C1=O YIJYFLXQHDOQGW-UHFFFAOYSA-N 0.000 claims description 2
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 claims description 2
- HPGWAEIBNAULOL-UHFFFAOYSA-N C(C=C)(=O)OC(C(COC(C=C)=O)(COC(C=C)=O)COC(C=C)=O)OCC Chemical compound C(C=C)(=O)OC(C(COC(C=C)=O)(COC(C=C)=O)COC(C=C)=O)OCC HPGWAEIBNAULOL-UHFFFAOYSA-N 0.000 claims description 2
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 claims description 2
- XLXOGJYARRBRPZ-UHFFFAOYSA-N [2,3-di(prop-2-enoyloxy)-3-propoxypropyl] prop-2-enoate Chemical compound CCCOC(OC(=O)C=C)C(OC(=O)C=C)COC(=O)C=C XLXOGJYARRBRPZ-UHFFFAOYSA-N 0.000 claims description 2
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 claims description 2
- XRMBQHTWUBGQDN-UHFFFAOYSA-N [2-[2,2-bis(prop-2-enoyloxymethyl)butoxymethyl]-2-(prop-2-enoyloxymethyl)butyl] prop-2-enoate Chemical compound C=CC(=O)OCC(COC(=O)C=C)(CC)COCC(CC)(COC(=O)C=C)COC(=O)C=C XRMBQHTWUBGQDN-UHFFFAOYSA-N 0.000 claims description 2
- MPIAGWXWVAHQBB-UHFFFAOYSA-N [3-prop-2-enoyloxy-2-[[3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propoxy]methyl]-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C MPIAGWXWVAHQBB-UHFFFAOYSA-N 0.000 claims description 2
- 125000001931 aliphatic group Chemical group 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 238000005336 cracking Methods 0.000 claims description 2
- 238000006356 dehydrogenation reaction Methods 0.000 claims description 2
- 229920000728 polyester Polymers 0.000 claims description 2
- 239000004814 polyurethane Substances 0.000 claims description 2
- 229920002635 polyurethane Polymers 0.000 claims description 2
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 claims description 2
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 claims description 2
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 claims description 2
- 239000002131 composite material Substances 0.000 claims 1
- 239000002184 metal Substances 0.000 abstract description 6
- 229910052751 metal Inorganic materials 0.000 abstract description 6
- 230000007547 defect Effects 0.000 abstract description 5
- 238000001259 photo etching Methods 0.000 abstract description 5
- 238000012545 processing Methods 0.000 abstract description 5
- 238000010923 batch production Methods 0.000 abstract description 4
- 239000011248 coating agent Substances 0.000 abstract description 2
- 238000000576 coating method Methods 0.000 abstract description 2
- 238000003756 stirring Methods 0.000 description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 239000002210 silicon-based material Substances 0.000 description 3
- -1 acyl phosphine oxide Chemical compound 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 210000003491 skin Anatomy 0.000 description 2
- VOELQEYVJLFZLS-UHFFFAOYSA-N 2-benzyl-2-(dimethylamino)-1-phenylbutan-1-one Chemical compound C=1C=CC=CC=1C(=O)C(CC)(N(C)C)CC1=CC=CC=C1 VOELQEYVJLFZLS-UHFFFAOYSA-N 0.000 description 1
- 241001391944 Commicarpus scandens Species 0.000 description 1
- YPCHGLDQZXOZFW-UHFFFAOYSA-N [2-[[4-methyl-3-[[3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propoxy]carbonylamino]phenyl]carbamoyloxymethyl]-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound CC1=CC=C(NC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C)C=C1NC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C YPCHGLDQZXOZFW-UHFFFAOYSA-N 0.000 description 1
- GUCYFKSBFREPBC-UHFFFAOYSA-N [phenyl-(2,4,6-trimethylbenzoyl)phosphoryl]-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C(=O)C1=C(C)C=C(C)C=C1C GUCYFKSBFREPBC-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 210000000434 stratum corneum Anatomy 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 230000037317 transdermal delivery Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/10—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers containing more than one epoxy radical per molecule
- C08F283/105—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers containing more than one epoxy radical per molecule on to unsaturated polymers containing more than one epoxy radical per molecule
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61M—DEVICES FOR INTRODUCING MEDIA INTO, OR ONTO, THE BODY; DEVICES FOR TRANSDUCING BODY MEDIA OR FOR TAKING MEDIA FROM THE BODY; DEVICES FOR PRODUCING OR ENDING SLEEP OR STUPOR
- A61M37/00—Other apparatus for introducing media into the body; Percutany, i.e. introducing medicines into the body by diffusion through the skin
- A61M37/0015—Other apparatus for introducing media into the body; Percutany, i.e. introducing medicines into the body by diffusion through the skin by using microneedles
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/006—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00
- C08F283/008—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00 on to unsaturated polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/01—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to unsaturated polyesters
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61M—DEVICES FOR INTRODUCING MEDIA INTO, OR ONTO, THE BODY; DEVICES FOR TRANSDUCING BODY MEDIA OR FOR TAKING MEDIA FROM THE BODY; DEVICES FOR PRODUCING OR ENDING SLEEP OR STUPOR
- A61M37/00—Other apparatus for introducing media into the body; Percutany, i.e. introducing medicines into the body by diffusion through the skin
- A61M37/0015—Other apparatus for introducing media into the body; Percutany, i.e. introducing medicines into the body by diffusion through the skin by using microneedles
- A61M2037/0053—Methods for producing microneedles
Abstract
The invention belongs to the technical field of photocuring materials, and particularly relates to a photosensitive material composition for manufacturing nano microneedles and microneedle arrays and a preparation method thereof. The coating consists of 75-90 parts by mass of light-cured monomer, 5-25 parts by mass of light-cured resin, 0.1-5.0 parts by mass of photoinitiator and 0.5-5.0 parts by mass of auxiliary agent. The photosensitive material composition for manufacturing the nano microneedle and the microneedle array has high processing precision and excellent performance, is suitable for manufacturing the nano microneedle and the microneedle array by using a laser direct writing technology, can realize batch production, overcomes the defects of the traditional metal microneedle or photoetching process, can be widely used for manufacturing the nano microneedle and the microneedle array with various sizes, and has wide industrial utilization value.
Description
Technical Field
The invention belongs to the technical field of photocuring materials, and particularly relates to a photosensitive material composition for manufacturing nano microneedles and microneedle arrays and a preparation method thereof.
Background
The micro-needle administration is a novel transdermal administration mode, and provides a painless and minimally invasive method for administration, namely, a tiny needle of the micro-needle is utilized to pierce the outermost layer, namely stratum corneum, of the skin, then the medicine enters the body to play a role, and the micro-needle is widely applied to the field of transdermal administration with the advantages of effectiveness, safety, no pain and the like. Solid microneedles are typically made of materials with relatively high hardness, such as silicon, metals, polymers, etc. Among them, the silicon material is relatively mature in the processing technology of the MEMS, and is the material which is used for manufacturing the microneedle for the first time and is used for researching the transdermal delivery of the drug, however, the processing cost of the silicon material using the MEMS is high, and the defect that the silicon material is easy to break in the using process is gradually eliminated. The traditional photoetching process for preparing the nano micro-needle and the micro-needle array needs the processes of plating a metal seed coating, spin coating, pre-baking, exposure, development and the like, and meanwhile, the high-precision micro-needle array has high requirements on a mask, so that the manufacturing cost is increased.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: providing a photosensitive material composition for manufacturing nano micro-needles and micro-needle arrays; the composition has high processing precision and excellent performance, is suitable for manufacturing nano micro needles and micro needle arrays by a laser direct writing technology, and can realize batch production; the invention also provides a preparation method thereof.
The photosensitive material composition for preparing the nano micro-needle and the micro-needle array comprises the following raw materials in parts by mass:
wherein:
the light-cured monomer is one or more of acrylate, acrylate modified organosilicon monomer or acrylate modified organosilicon oligomer, wherein the light-cured group n is more than or equal to 2, preferably more than or equal to 3, and the viscosity is 50-1500 centipoises.
The light curing monomer is one or more of (methyl) acrylate, a (methyl) acrylate modified organic silicon monomer or a (methyl) acrylate modified organic silicon oligomer.
Preferably, the photocurable monomer is trimethylolpropane trimethacrylate, trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate, 3 (ethoxy) trimethylolpropane triacrylate, ethoxylated (6) trimethylolpropane triacrylate, (9) ethoxylated trimethylolpropane triacrylate, ethoxylated (15) trimethylolpropane triacrylate, ethoxylated (20) trimethylolpropane triacrylate, one or more of pentaerythritol triacrylate, 3 (propoxy) glycerol triacrylate, tris (2-hydroxyethyl) isocyanurate triacrylate, ditrimethylolpropane tetraacrylate, pentaerythritol tetraacrylate, 4 (ethoxy) pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, or Ormocomp (manufacturer micro resistance technology company).
The light-cured resin is any one or more of bisphenol A epoxy acrylate, polyurethane acrylate or polyester acrylate.
The urethane acrylate is one or two of aliphatic urethane acrylate (preferably UT53956 in Australia chemical engineering) or aromatic urethane acrylate (preferably EBECRYL 220 in America).
The photoinitiator is a free radical photoinitiator, the free radical photoinitiator is one of a cracking type (I type) photoinitiator or a hydrogen abstraction type (II type) photoinitiator, preferably acyl phosphine oxide Irgcure819 (phenyl bis (2,4, 6-trimethylbenzoyl) phosphine oxide) or α -amine alkyl aryl ketone Irgcure369 (BDMB: 1-p-morpholine phenyl-2-dimethylamino-2-benzyl-1-butanone), more preferably the acyl phosphine oxide Irgcure819 is 1.0 part by mass, and the α -amine alkyl aryl ketone Irgcure369 is 2.0 parts by mass.
The auxiliary agent is one or more of gamma-glycidoxypropyltrimethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, gamma-methacryloxypropyltrimethoxysilane or polymethyl methacrylate, preferably polymethyl methacrylate.
The preparation method of the photosensitive material composition for manufacturing the nano-micro-needle and the micro-needle array comprises the steps of mixing the photo-curing monomer, the photo-curing resin, the photoinitiator and the auxiliary agent at normal temperature, filtering by using a vacuum filtration replaceable membrane filter, and sealing and storing under the condition of keeping out of the sun or yellow light to obtain the photosensitive material composition.
Preferably, the preparation method of the light-sensitive material composition for manufacturing the nano-micro-needle and the micro-needle array comprises the steps of adding the light-cured monomer and the light-cured resin into a double-planet stirrer in proportion, stirring for 25-35 minutes, preferably 30 minutes, fully mixing uniformly, adding the photoinitiator and the auxiliary agent in proportion under the condition of light shielding or yellow light, stirring for 1-3 hours, preferably 2 hours, filtering by using a vacuum filtration replaceable membrane filter, and injecting into a brown bottle for sealing and storing.
The application of the photosensitive material composition provided by the invention adopts one of curing modes such as a laser direct writing technology, near-infrared femtosecond laser two-photon polymerization or multi-photon polymerization and the like, and realizes the direct manufacture of complex three-dimensional nano micro-needles and micro-needle arrays without masks or molds on the photosensitive material composition.
Preferably, the invention uses the laser direct writing technology, and utilizes the ultrashort laser pulse to expose the predefined three-dimensional micro-nano structure to realize the direct manufacture of the complex three-dimensional nano microneedle and the microneedle array without a mask or a mold on the photosensitive material.
Compared with the prior art, the invention has the following beneficial effects:
(1) the prepared nano microneedle and the photosensitive material composition for manufacturing the microneedle array are suitable for a laser direct writing technology on one hand, and the complex three-dimensional nano microneedle and the microneedle array which do not need a mask or a die are directly manufactured on a photosensitive material by exposing a predefined three-dimensional micro-nano structure through ultrashort laser pulses; on the other hand, according to the requirements of an application end, the excellent performances of the nano micro-needle and the micro-needle array in extensibility, impact resistance, skin penetrability, high peeling strength, tearing strength and the like can be realized, the defects of the traditional metal micro-needle or photoetching process are overcome, and the nano micro-needle and the micro-needle array with various sizes can be widely used for manufacturing.
(2) The photosensitive material composition for manufacturing the nano microneedle and the microneedle array has high processing precision and excellent performance, is suitable for manufacturing the nano microneedle and the microneedle array by using a laser direct writing technology, can realize batch production, overcomes the defects of the traditional metal microneedle or photoetching process, can be widely used for manufacturing the nano microneedle and the microneedle array with various sizes, and has wide industrial utilization value.
Detailed Description
The present invention is further described below with reference to examples.
Examples 1 to 5
The light-sensitive material composition for fabricating the nano-micro-needles and the micro-needle arrays described in example 1 comprises the raw materials of the light-curable monomer, the light-curable resin, the photoinitiator and the auxiliary agent, the raw materials of examples 2 to 5 are the same as those of example 1, and the specific raw material compositions of the light-sensitive compositions of examples 1 to 5 are shown in table 1.
The preparation method of the light-sensitive material composition for manufacturing the nano-micro-needles and the micro-needle array described in the embodiment 1 comprises the steps of adding a light-cured monomer and a light-cured resin into a double-planet stirrer in proportion, stirring for 30 minutes, fully mixing uniformly, adding a photoinitiator and an auxiliary agent in proportion under the condition of keeping out of the sun or yellow light, stirring for 2 hours, filtering by using a vacuum suction filtration replaceable membrane filter, and injecting into a brown bottle for sealing and storing; examples 2-5 were prepared in the same manner as in example 1.
The photosensitive material compositions prepared in examples 1 to 5 were applied to the preparation of three-dimensional nano microneedles and microneedle arrays:
by adopting a laser direct writing technology, the direct manufacture of the complex three-dimensional nano microneedle and the microneedle array without a mask or a mold is realized on the photosensitive material composition prepared in the embodiment 1-5 by using the ultrashort laser pulse exposure predefined three-dimensional micro-nano structure, and the performance detection is carried out on the microneedle forming shape and the bonding property of the microneedle to the glass substrate, and the results are shown in table 1.
Comparative examples 1 to 2
The raw material composition of the photosensitive material composition for the fabrication of the nano-micro needles and the micro-needle array described in comparative examples 1-2 is shown in table 1; the preparation method of the photosensitive material composition is the same as that of example 1, and the method of applying the photosensitive material composition to the preparation of the nano-micro needles and the micro-needle array is the same as that of example 1.
TABLE 1 photosensitive material composition raw material composition and performance test results of nano-micro-needle and micro-needle array prepared from the photosensitive material composition
Therefore, the high-precision photosensitive material composition for manufacturing the nano micro-needle and the micro-needle array, which is suitable for batch production, and the preparation method thereof, provided by the invention, overcome the defects of the traditional metal micro-needle or photoetching process, can be widely used for manufacturing nano micro-needles and micro-needle arrays with various sizes, and have wide industrial utilization value.
The above examples are merely illustrative of the principles of preparation and use of the present invention and are not intended to limit the invention. Modifications and variations can be made to the above-described synthetic examples and embodiments by those skilled in the art without departing from the spirit and scope of the present invention. Accordingly, it is intended that all equivalent modifications or changes which can be made by those skilled in the art without departing from the spirit and technical spirit of the present invention be covered by the claims of the present invention.
Claims (9)
1. A photosensitive material composition for manufacturing nano micro needles and micro needle arrays is characterized in that: the composite material consists of the following raw materials in parts by mass:
2. the photosensitive material composition for the fabrication of nano-microneedles and microneedle arrays according to claim 1, wherein: the light-cured monomer is one or more of acrylate, acrylate modified organosilicon monomer or acrylate modified organosilicon oligomer, wherein the light-cured group n is more than or equal to 2, and the viscosity is 50-1500 centipoises.
3. The photosensitive material composition for the fabrication of nano-microneedles and microneedle arrays according to claim 1, wherein: the light-curing monomer is one or more of trimethylolpropane trimethacrylate, trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate, 3 (ethoxy) trimethylolpropane triacrylate, ethoxylated (6) trimethylolpropane triacrylate, (9) ethoxylated trimethylolpropane triacrylate, ethoxylated (15) trimethylolpropane triacrylate, ethoxylated (20) trimethylolpropane triacrylate, pentaerythritol triacrylate, 3 (propoxy) glycerol triacrylate, tris (2-hydroxyethyl) isocyanurate triacrylate, ditrimethylolpropane tetraacrylate, pentaerythritol tetraacrylate, 4 (ethoxy) pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, or Ormocomp.
4. The photosensitive material composition for the fabrication of nano-microneedles and microneedle arrays according to claim 1, wherein: the light-cured resin is any one or more of bisphenol A epoxy acrylate, polyurethane acrylate or polyester acrylate.
5. The photosensitive material composition for the fabrication of nano-microneedles and microneedle arrays according to claim 4, wherein: the urethane acrylate is one or two of aliphatic urethane acrylate or aromatic urethane acrylate.
6. The photosensitive material composition for the fabrication of nano-microneedles and microneedle arrays according to claim 1, wherein: the photoinitiator is a free radical photoinitiator, and the free radical photoinitiator is one of a cracking photoinitiator or a hydrogen abstraction photoinitiator.
7. The photosensitive material composition for the fabrication of nano-microneedles and microneedle arrays according to claim 1, wherein: the auxiliary agent is one or more of gamma-glycidoxypropyltrimethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, gamma-methacryloxypropyltrimethoxysilane or polymethyl methacrylate.
8. The use of the photosensitive material composition for the preparation of nano-microneedles and microneedle arrays according to claim 1, wherein: the method adopts one of a laser direct writing technology and a near infrared femtosecond laser two-photon polymerization or multi-photon polymerization curing mode to realize the direct manufacture of the complex three-dimensional nano microneedle and the microneedle array without a mask or a mould on the photosensitive material composition.
9. A method for preparing the nano-micro-needle and the photosensitive material composition for micro-needle array fabrication according to claim 1, wherein the method comprises the following steps: mixing the photo-curing monomer, the photo-curing resin, the photoinitiator and the auxiliary agent at normal temperature, filtering by using a vacuum filtration replaceable membrane filter, and sealing and storing under the condition of keeping out of the sun or yellow light to obtain the photosensitive material composition.
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| CN114456334A (en) * | 2021-09-30 | 2022-05-10 | 浙江大学 | Preparation method of porous microneedle, porous microneedle micro-needle and needle array drug delivery system |
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