CN101776846B - Light-cured component for laser stereo lithography - Google Patents
Light-cured component for laser stereo lithography Download PDFInfo
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- CN101776846B CN101776846B CN2009100006810A CN200910000681A CN101776846B CN 101776846 B CN101776846 B CN 101776846B CN 2009100006810 A CN2009100006810 A CN 2009100006810A CN 200910000681 A CN200910000681 A CN 200910000681A CN 101776846 B CN101776846 B CN 101776846B
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- photosensitive resin
- acryloyl
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- ZRNCNTSXSYXHOW-UHFFFAOYSA-N butyl decanoate Chemical compound CCCCCCCCCC(=O)OCCCC ZRNCNTSXSYXHOW-UHFFFAOYSA-N 0.000 description 1
- UIZLQMLDSWKZGC-UHFFFAOYSA-N cadmium helium Chemical compound [He].[Cd] UIZLQMLDSWKZGC-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 150000007973 cyanuric acids Chemical class 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 1
- 230000004069 differentiation Effects 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 229940052303 ethers for general anesthesia Drugs 0.000 description 1
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- JBFHTYHTHYHCDJ-UHFFFAOYSA-N gamma-caprolactone Chemical compound CCC1CCC(=O)O1 JBFHTYHTHYHCDJ-UHFFFAOYSA-N 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 description 1
- 238000006897 homolysis reaction Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 238000000608 laser ablation Methods 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 239000002075 main ingredient Substances 0.000 description 1
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000035772 mutation Effects 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- AVBRYQRTMPHARE-UHFFFAOYSA-N octyl formate Chemical compound CCCCCCCCOC=O AVBRYQRTMPHARE-UHFFFAOYSA-N 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920001610 polycaprolactone Polymers 0.000 description 1
- 239000004632 polycaprolactone Substances 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- OVFMRFMJVFDSAA-UHFFFAOYSA-N propyl decanoate Chemical compound CCCCCCCCCC(=O)OCCC OVFMRFMJVFDSAA-UHFFFAOYSA-N 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000000284 resting effect Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 150000003413 spiro compounds Chemical class 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 125000003258 trimethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])[*:1] 0.000 description 1
Abstract
The invention relates to a liquid low-viscosity photosensitive resin formula system, which comprises a cation-cured substance, a free radical-cured substance, a cation type photoinitiator, a free radical type photoinitiator, a polyol, an amino resin cross linking agent, polyvinylether and the like. The light-cured component is applicable to laser stereo lithography (stereo optical imaging), in particular to acquisition of three-dimensional entities by using a laser stereo etching method, wherein the obtained three-dimensional entities have high heat resistance, strength, transparency and hydrolytic resistance.
Description
Technical field
The present invention relates to a kind of liquid low viscosity photosensitive resin prescription system; Be applicable to light chisel; Particularly be applicable to the material object that obtains three-dimensional picture with the method for the three-dimensional etching of laser, the three-dimensional material object of gained has good thermotolerance, intensity, the transparency and hydrolytic resistance.
Background technology
Photosensitive high polymer prescription system is generally used for comprising the planar etch imaging of printed-wiring board (PWB), yet specific photosensitive resin system can be used for obtaining with the method for the three-dimensional etching of laser the object of 3D shape.
The object that the method for the three-dimensional etching of employing laser is obtained the 3D shape with any labyrinth is a kind of known industrial technology, and two more than ten years appearred in this technology.Process with this technological three-dimensional imaging is to accomplish through the overlapping of two steps: (1) optionally makes the specific region to the liquid layer of the specific thicknesses on the surface of the responsive liquid resin material of Optical irradation receive light irradiation; Be meant the scanning and irradiation of the laser beam that receives computer control especially, sensitization and solidifying; (2), wait for that next amplitude is according to scanning at this this sensitive liquid resin that applies one deck predetermined thickness above cured layer again.Step (1) and (2) repeat, and just can produce three-dimensional object.The data of the three-dimensional body to be made that stereo-picture is just pre-designed come from the CAD figure shelves of a computer usually.This process is converted into material object to the CAD dummy object; Can continue to use the planar imaging term and be referred to as three-dimensional imaging; Also can be according to the characteristic of this technology at manufacture view; Be referred to as three-dimensional etching rapid shaping of laser or manufacturing fast, abbreviate stereolithography rapid shaping (Japanese is called the cubic light moulding) or quick the manufacturing as.
This three-dimensional imaging/rapid shaping comprises following two kinds of situations: change into the CAD virtual three-dimensional image of original design three-dimensional in kind; Perhaps existing three-dimensional material object is converted into three-dimensional data bag (being the anti-ball engineerings of so-called data) through means such as three-dimensional (solid) shootings, rectification is the CAD stereo-picture then, changes three-dimensional material object again into.Second kind of situation is so-called Xograph.
The performance of the solidfied material material that this three-dimensional imaging/quick molding method obtains comprises the performance of aspects such as mechanics, calorifics, electricity, and the chemistry that depends primarily on employed photosensitive resin system constitutes, and also partly receives the influence of illumination curing mode.And the processing usability of the liquid resin material in the three-dimensional imaging process, for example surface tension, viscosity, levelability and liquid film ductility etc. then are the composition decision of resin liquid fully.Therefore, comprehensive, the performance quality that the chemistry of specific photosensitive resin system constitutes the stereo shaped object plays decisive role.
This three-dimensional imaging/rapid shaping technique is diversified in the purposes aspect Design of Industrial Product and the exploitation, comprises the making of model of making and many special purposes goods of the model of general industry product.The special-purpose photosensitive resin prescription system of the three-dimensional etching of existing laser mostly is that the modelling that is directed against the general industry product requires to develop, and thermotolerance is bad, and temperature surpasses five or six ten degrees centigrade will the deliquescing distortion.But some special purposes requires the made model can anti-higher temperature; For example; Require product can tolerate the temperature of water vapour, thereby this type special-purpose require the object after the etching moulding to have the thermal change type temperature that is higher than 100 ℃, and excellent mechanical intensity.When needs are observed the flow state of internal flow, also require profiled member to possess good transparency.When needs contact with water or steam, must have satisfied hydrolytic resistance.
Because this three-dimensional imaging/curing article of rapid shaping gained are widely used in the design and development of industrial products, thereby the utmost point is necessary in addition strict the confirming of the implication of the so-called heat resistance of solidfied material.At first, about the thermotolerance of thermoplastics and thermosetting plastics, the practical balancing method of in commercial Application, accepting extensively most is to measure its thermal change type temperature, secondly is softening temperature (for example vicat softening temperature etc.).The glass temperature that academia is often carried; Because transition temperature corresponding to the vitrifacation campaign of the free segment of macromolecular chain; For the polymeric system of crystalline thermoplastics and high Inorganic Fillers Filled; Often specific heat modification temperature is much lower, and as far as unbodied thermoplastics and thermosetting plastics, then often specific heat modification temperature exceeds 20-40 ℃; So it only has academic significance, should not use glass temperature as the stable on heating measurement index of plastic products in industry member.Secondly; Because present most of rapid shaping goods are the assemblings that are used for system; Requirement can not be heated the back again and solidified after illumination curing; Cause size to lose in order to avoid produce big out of contior contraction accurate, so just require resin material must accomplish only to rely on illumination curing just to have gratifying thermotolerance.Preliminary stage (before 2000) at the three-dimensional etching forming technique of laser; Because the power ratio performance lower and used photosensitive resin material of laser instrument is difficult to satisfy the assembling requirement; Resin all is to be used for making the Individual Items as purpose of model basically; The dealer usually can be after stereolithography machine the inside moulding takes out article to be placed on and continues the irradiation dozens of minutes in the ultraviolet baking box and make the surface curing that strengthened to several hours; Also often be placed on article further and under 120-160 ℃, toast several hours in the heated oven, thereby improve the thermotolerance and some mechanical propertys of material so that make material cured well-done.But this follow-up being heating and curing causes the bigger dimensional contraction that can not control in advance, but influences the assembleability of parts.After the novel photosensitive resin material that laser power improves and satisfied assembling purpose requires afterwards occurred, the dealer was heating and curing after can requiring any emerging resin kind not need to carry out usually again.Therefore, resin material just is asked to only to rely on (adding in the ultraviolet baking box in the stereolithography machine the inside) illumination curing promptly to have good heat endurance.
Except the above-mentioned performance requirement of the material of terminal use after to light chisel; Because this photosensitive component system mainly is on the stereolithography rapidform machine, to use; Also requiring such prescription system must be the not too high stable uniform liquid of viscosity; Because present stereolithography rapidform machine can't use the pastel photochromics of thickness.When the brookfield viscosity when 30 ℃ of resin surpasses 1500mPas, on present stereolithography machine, be difficult to use.
Commercial photosensitive resin system that is used for this kind three-dimensional imaging/flash mould purpose of selling and patent disclosed with the photosensitive resin system of applying for a patent open explanation, also have no a single product or prescription resin to satisfy these requirements simultaneously.The photosensitive resin product of the pure organic principle of the commercial so-called heat resistant type of selling is if only lean on photocuring at present, and thermal change type temperature all is no more than 80 ℃.It is that the merchant of Somos NanoTool sells resin and declares that thermal change type temperature can reach 225 ℃ after photocuring that a trade mark is arranged; But viscosity is up to 2500mPas; Also have the settlement issues of inorganic filler in organic media, common dealer is difficult to use, and solidfied material is opaque.The resin system that is not shown in commodity selling as yet that discloses in publication and the application publication at present; Also all can not accomplish to satisfy simultaneously requirement and the solidfied material that photocuring is heat-resisting more than 100 ℃, 30 ℃ of brookfield viscosities are no more than 1500mPas, resin must be for a long time uniform and stable has than high transparent and the better accessory claim of hydrolytic resistance; For example; Reveal the heat resistant type photosensitive resin system that does not contain inorganic filler in the U.S. Pat 6100007; It is higher to solidify the back transparency, but the thermal change type temperature behind the photocuring is no more than 80 ℃, and curing just can reach the thermal change type temperature more than 200 ℃ after 2 hours after must under 160 ℃, heating.U.S. Patent application prospectus US 6203966B1 reveals the thermal change type temperature that adopts behind the way raising light chisel that adds the micro-nano filler of aluminium oxide in the photosensitive resin system; After light chisel; Through heat, thermal change type temperature is brought up to more than 300 ℃ again.But this system not only viscosity is so high, and aluminium oxide very fast sedimentation in the resin medium, causes resin almost can't in the stereolithography machine, use at all.U.S. Patent application prospectus US 2006/0267252A1 reveals the softening temperature that adopts behind the way raising light chisel that adds nanoscale and micron order quartz filler in the photosensitive resin system, can make softening temperature bring up to 200 ℃.But this system has the too high problem with filling settlement of viscosity equally.U.S. Pat 6054250 has been reported the liquid low viscosity prescription system of using modified vinylic-ether; Has high glass transition (being higher than 100 ℃) behind the photocuring; It is so high that but thermal change type temperature does not but reach, and the resin system that is mixed with vinyl ether after curing, to be pitchy opaque.
Being necessary for present stereolithography technology provides a kind of low viscous photosensitive resin material of stable homogeneous; Have good stereolithography processing characteristics (30 ℃ brookfield viscosity be no more than 800mPas, resin must be uniform and stable for a long time), also accomplish not need to carry out again after the light chisel heat treated simultaneously and just reach thermal change type temperature and surpass 100 ℃ (preferably above 120 ℃), possess the favorable mechanical performance but also have the transparency and hydrolytic resistance preferably as far as possible.And this novelty that to be the present invention can accomplish is created.
To general introduction of the present invention
Based on above-mentioned, one aspect of the present invention is to be applicable to the chemical system that is made up of following composition that obtains the material object of three-dimensional picture with the method for the three-dimensional etching of laser (light chisel):
(A) at least a organic substance that can carry out cationic polymerization, take from:
A) contain aliphatic series (the comprising alicyclic) compound of at least two ring-type oxygen ethylene groups; Or
B) contain the aromatic compounds of at least two oxetane groups; Or
C) contain aliphatic compounds, aromatic compounds or the heterogeneous ring compound of at least two glycidyl ether groups;
(B) at least a organic substance that can carry out free radical polymerization, take from:
A) contain the aliphatic compounds that at least one acryloyl-oxy or methacryloxy are rolled into a ball; Or
B) contain the aromatic compounds of not chain extension of at least two acryloyl-oxies or methacryloxy group; Or
C) contain (promptly passing through chain extension) aliphatic series or aromatic compounds that alcoxyl support segment, alkyl acyl-oxygen segment, alkyl urethano segment are contained again at least two acryloyl-oxies or methacryloxy group
(C) at least a cationic photoinitiator;
(D) at least a radical photoinitiator;
(E) can select to use aliphatics or aromatic polyol or amino resins polyvalent alcohol as required;
(F) can select to use the amino resin crosslinking agent that cross linking of epoxy resin is solidified as required;
(G) can select to use the polynary vinyl ether of aliphatics or aromatic series as required;
(H) can select to use auxiliary agent or dyestuff as required.
Another aspect of the present invention is to use this chemicals to make the process of three-dimensional article, and this process is made up of following concrete steps:
(1) at the liquid resin of this kind of surface applied one deck ability hardening with radiation;
(2) this coating is made public according to the imaging needs, realize planar imaging.The exposure area is to have confirmed according to the imaging needs in advance, can be the mode that adopts laser beams intersect scanning.So-called cross scan is meant this coating is carried out X-direction of principal axis and the scanning of Y-direction of principal axis respectively, perhaps along two enterprising line scannings of diagonally opposing corner direction.The intensity of exposure must be able to make liquid resin in a few tens of milliseconds, solidify to reach significant intensity, can support the weight of follow-up numerous coatings;
(3) on the coating that this has just made public, apply the liquid resin of this kind of one deck ability hardening with radiation again;
(4) this coating is made public according to the imaging needs, the intensity of exposure must be able to make liquid resin in a few tens of milliseconds, solidify the curing area that reaches significant intensity and last layer and form enough cohesive forces, and can support the weight of follow-up numerous coatings;
(5) repeat above-mentioned steps (3) and (4),, form the object of a three-dimensional up to accomplishing the predetermined number of plies.
The 3rd aspect of the present invention is to use this chemicals and this operation to produce various three-dimensional articles with very high thermotolerance, favorable mechanical performance, the transparency and hydrolytic resistance according to the needs of cubic light moulding.When using the three-dimensional lithographic method of laser to make stereo article with this kind chemicals; The stereo article of gained has good heat endurance; Only rely on photocuring and need not heat back curing, can accomplish to make thermal change type temperature to be higher than 100 ℃, this is a significant advantage of the present invention; When using the three-dimensional lithographic method of laser to make stereo article with this kind chemicals, the stereo article of gained has the favorable mechanical performance, and this is another significant advantage of the present invention; When using the three-dimensional lithographic method of laser to make stereo article with this kind chemicals, the stereo article of gained has the good transparency, and this is another significant advantage of the present invention; When using the three-dimensional lithographic method of laser to make stereo article with this kind chemicals, the stereo article of gained has good hydrolytic resistance, and this is another significant advantage of the present invention; When using the three-dimensional lithographic method of laser to make stereo article with this kind chemicals; The uniform low-viscosity (mobile) liquid chemicals of this non-Inorganic Fillers Filled provides the three-dimensional feasibility in kind and lasting shelf stability of making high precision; Also be good stereolithography processability, this is another significant advantage of the present invention.
Detailed presentations to invention
At first explanation, the liquid state that the present invention is alleged is meant under 5-60 ℃ of temperature, is rendered as aqueous.
On wide significance, understand, the alleged novel chemicals of the present invention is that various necessary chemical compositions are mixed according to a certain percentage and form: at least a organic substance that can cationic curing; At least a can radical-cured organic substance; At least a cationic initiator; At least a radical photoinitiator; The organic substance of selecting for use as required that contains an above hydroxyl; The amino resin crosslinking agent of selecting for use as required that cross linking of epoxy resin is solidified; The polynary vinyl ether of aliphatics of selecting for use as required or aromatic series; And auxiliary agent of selecting for use as required and dyestuff.
(A) can carry out the organic substance of cationic polymerization
The alleged chemical prescription system of the present invention contains a kind of or more kinds of have two or the compound of above ring-type oxygen ethylene group or two oxetane groups or the compound of two above glycidyl ether groups at least.The use amount that this type can carry out the material of cationic polymerization among the present invention accounts for the 10-80% of total photosensitive resin weight.
A) contain aliphatic series (the comprising alicyclic) compound of at least two ring-type oxygen ethylene groups
Aliphatic series (the comprising alicyclic) compound that contains at least two ring-type oxygen ethylene groups that the present invention is alleged is meant the compound of ring-type oxygen ethylene group as the part of alicyclic ring or backbone structure, and on average each molecule has at least two this ring-type oxygen ethylene groups.Such compound is that the dealer knows usually, and has commodity to sell.As an example, such compound has two (2,3-epoxide ring amyl group) ethers, and 1,2-two (2; The support of 3-epoxide ring amyl group oxygen) ethane, 3,4-7-oxa-bicyclo[4.1.0 carbonic acid 3,4-epoxycyclohexyl methyl ester, 3; 4-epoxy 6-methylcyclohexane carbonic acid 3,4-epoxy 6-methylcyclohexyl methyl ester, hexane diacid (3,4-epoxycyclohexyl methyl) diester, hexane diacid (3; 4-epoxy 6-methyl cyclohexane ylmethyl) diester, two (3, the 4-epoxycyclohexyl) carbonic esters of ethene, two (3, the 4-epoxycyclohexyl) glycol ether; The vinyl cyclohexane di-epoxide, the dicyclopentadiene di-epoxide, 2-(3,4-epoxycyclohexyl-5; 5-spiral shell-3, the 4-epoxy) cyclohexane-1, the 3-dioxan, epoxidised number-average molecular weight is not more than 2000 polybutadiene oligomer.The consumption of such compound accounts for the 0%-75% of overall prescription system weight.
B) contain the aromatics of at least two oxetane groups
The aromatics that contains at least two oxetane groups that the present invention is alleged is meant the aromatic compounds that has two or above oxetane groups in the molecule, and for example molecular formula (I) is represented, it is characterized in that two ends have oxetane groups:
The consumption of such compound accounts for the 0%-60% of overall prescription system weight.
C) contain fatty compound, aromatics or the heterogeneous ring compound of at least two glycidyl ether groups
The aliphatic compounds that contain at least two glycidyl ether groups that the present invention is alleged are meant to have that 4-chloro epoxypropane and aliphatic polyol remove hydrogen chloride and the compound of the such molecular structure of the etherate that generates, and such polyvalent alcohol has monoethylene glycol, tirethylene glycol, 1,2-propylene glycol, 2; 4,6-trihydroxy hexane, 1,4-methylol cyclohexane, 1; 1,1-trimethylolpropane, 1,1; 1-trimethylolethane, Pehanorm etc.; Require hydroxy functionality>=2, no ceiling, but to make the epoxide equivalent (EEW)≤300 of condensation gained compound.The representative configurations synoptic diagram of such glycidyl ether compound is following:
The aromatics that contains at least two glycidyl ether groups that the present invention is alleged is meant to have that 4-chloro epoxypropane and aromatics monohydroxy alcohol or polyvalent alcohol remove hydrogen chloride and the compound of the such molecular structure of the etherate that generates, and contains this type of etherate that gathers alcoxyl support segment.Such aromatic polyol has p-dihydroxy-benzene, catechol, resorcinol, methyl pyrocatechol, number-average molecular weight to be not more than 650 acid catalysis phenolics, bisphenol-A, Bisphenol F, bisphenol S etc.The structural formula of representative compound is following:
Elements such as that the heterogeneous ring compound that contains at least two glycidyl ether groups that the present invention is alleged is meant is nitrogenous, oxygen, sulphur be connected to five yuan of a plurality of terminal ethylene oxide groups, hexa-member heterocycle or assorted dicyclo, assorted spiro-compound, for example three isocyanuric acid esters (structural formula VIII) of the dehydration of three shown in figure below glycerine etherificate.
The consumption of the compound of such glycidyl ether accounts for the 0%-60% of overall prescription system weight.
(B) can carry out the organic substance of free radical polymerization
The alleged chemical prescription system of the present invention contains a kind of compound with at least one acryloyl-oxy or methacryloxy group at least.The use amount that this type can carry out the material of free radical polymerization among the present invention accounts for the 1-40% of total photosensitive resin weight.
A) contain the aliphatic compounds that at least one acryloyl-oxy or methacryloxy are rolled into a ball;
The aliphatic compounds that the present invention is alleged contains at least one acryloyl-oxy or methacryloxy group are meant ENB acrylate monomer, ENB methacrylate monomers, (methyl) acrylic acid and aliphatic polyol generation esterification and the esters of acrylic acid that generates or methyl acrylic ester polyfunctionality monomer and (methyl) esters of acrylic acid polyfunctionality monomer with such chemical constitution that synthesizes with other approach.Such polyvalent alcohol has monoethylene glycol, tirethylene glycol, multicondensed ethylene glycol, 1,2-propylene glycol, 1, and 4-butylene glycol, number-average molecular weight are not more than 600 PolyTHF, 1; 3-pentanediol, 1,6-hexanediol, 2,4; 6-trihydroxy hexane, 1,4-methylol cyclohexane, 1,1; 1-trimethylolpropane, 1,1,1-trimethylolethane, tetramethylol methane, two tetramethylol methane etc. that contracts.
The consumption of such compound accounts for the 0%-20% of overall prescription system weight.
B) contain the aromatic compounds of not chain extension of at least two acryloyl-oxies or methacryloxy group;
The aromatic ring compounds of group that the present invention is alleged contains the not chain extension of at least two acryloyl-oxies or methacryloxy group is meant esters of acrylic acid that (methyl) acrylic acid generates with aromatic polyol generation esterification or methyl acrylic ester monomer and (methyl) esters of acrylic acid polyfunctionality monomer with such chemical constitution that synthesizes with other approach.Such polyvalent alcohol has p-dihydroxy-benzene, catechol, resorcinol, methyl pyrocatechol, number-average molecular weight to be not more than 650 phenolics, bisphenol-A, Bisphenol F, bisphenol S etc.
The consumption of such compound accounts for the 0%-25% of overall prescription system weight, is more preferably to account for 0-20%.
C) contain (promptly passing through chain extension) aliphatic series or aromatic compounds that alcoxyl support segment, alkyl acyl-oxygen segment, alkyl urethano segment are contained again at least two acryloyl-oxies or methacryloxy group
The present invention is alleged contain at least two acryloyl-oxies or methacryloxy group contain again (promptly passing through chain extension) aliphatic series or the aromatic compounds of alcoxyl support segment, alkyl acyl-oxygen segment, alkyl urethano segment be meant above-mentioned (B) a) with (B) b) two kinds of compounds that situation is alleged are inlaid with in its molecule and gather alcoxyl support segment, alkyl acyl-oxygen segment or alkyl urethano segment.The alleged alcoxyl support segment that gathers is meant polyoxyethylene segment (for example polyglycol segment or polyethylene oxide segment), polyoxy trimethylene segment (polypropyleneoxide segment for example; Gather 1; 2-propylene glycol segment or gather positive propylene glycol segment), poly tetramethylene oxide segment (PolyTHF segment for example; Gather 1,2-butylene glycol segment perhaps gathers positive butylene glycol segment) or polyoxy hexamethylene segment (for example gathering positive hexanediol segment).Alleged alkyl acyloxy segment be meant gather butyl hexanoate segment, polycaprolactone segment, gather the ethyl hexanoate segment, gather capric acid butyl ester segment, gather capric acid propyl ester segment, gather the ethyl caprate segment, gather the n-hexyl butyrate segment, gather the n-hexyl butyrate segment, gather the butyl butyrate segment, gather the ethyl butyrate segment, gather the ethyl acetate segment, gather the butyl acetate segment, gather the capryl acetate segment, gather the octyl acetate segment, polyphenyl hexyl formate segment, polyphenyl octyl formate segment etc.Alleged alkyl urethano segment is meant by the characteristic segment of diisocyanate (like toluene diisocyanate, '-diphenylmethane diisocyanate, hexamethylene diisocyanate, IPDI etc.) with the chain polymerization product of line style dibasic alcohol (like butylene glycol, hexanediol, polyglycol, polypropylene glycol, polytetramethylene glycol, polytetrahydrofuran diol etc.).
The consumption of such compound accounts for the 0%-25% of overall prescription system weight.
(C) at least a cationic initiator
The cation light initiator that uses in the alleged chemical prescription system of the present invention causes oxirane or the oxetane groups generation ring-opening polymerization in the epoxy compound molecule and solidifies thereby can produce kation behind irradiation.As the known knowledge of a kind of professional, this cationoid type light trigger has phenyl sulfosalt, phenyl salt compounded of iodine, boron trifluoride, ferrocene etc., it is characterized in that negative ion (hexafluoroantimonic anion, hexafluoroarsenate root, hexafluoro-phosphate radical etc.) has very weak nucleophilicity.Example has European patent application EP 153904,35969,44274,54509,0164314 and United States Patent (USP) U.S.Patent No.3708296,5002856,5972563 etc. to be disclosed.
The cation light initiator that uses in the alleged chemical prescription system of the present invention can be one or both these photoinitiators, and total consumption accounts for 0.1% to 9.0% weight portion of total photosensitive resin, and the most frequently used is 0.5% to 5% weight portion.
(D) at least a radical photoinitiator
The homolysis of molecule can take place in the radical photoinitiator that uses in the alleged chemical prescription system of the present invention behind irradiation; Generation has the not group of sharing electron, and initiation contains the compound generation free radical polymerization of acryloyl-oxy or methacryloxy group and solidifies.As the known knowledge of a kind of professional; This type free fundamental mode light trigger has styrax compounds (like styrax), benzoin ether (like benzoin methyl ether, ethyl benzoin ether, isopropyl benzoin ether, the phenyl scented rice of resting in peace), styrax acetate, acetophenones (acetophenone, 2; 2-dimethoxy-acetophenone, 1; The 1-dichloroacetophenone), phenyl ketal class (like phenyl dimethyl ketal, diethylamino phenyl base ketal), anthraquinone class (like 2-methylanthraquinone, 2-EAQ, 2-tert-butyl group anthraquinone, 1-chloroanthraquinone, 2-amyl anthraquinone) and phenyl phosphorus oxygen and phenyl phosphinylidyne oxygen class (shown in structural formula IX and the X), xylene ketone are (like diformazan benzophenone, 4; 4 '-two (N, N '-dimethyl amine) phenyl ketone), thioxanthene ketone, xanthone etc.The radical photoinitiator that is adapted at most using under the laser ablation wavelength (being 325nm, 351nm, 355nm, 364nm wavelength) has acetophenones and phenyl ketal class.
The radical photoinitiator that uses in the alleged chemical prescription system of the present invention can be one or more these photoinitiators, and total consumption accounts for 0.1% to 6.0% weight portion of total photosensitive resin, and the most frequently used is 1.5% to 3.5% weight portion.
(E) select aliphatics or aromatic polyol or amino resins polyvalent alcohol as required for use
The material of the aliphatics hydroxyl that the present invention is alleged is meant the aliphatic compounds that contain two or more hydroxyls with line style, star-like or comb type host molecule structure of oligomer type, and hydroxyl is in the end, and segment is polyethers, polyester or polycarbonate structure.As an example, have glyceryl alcohol or trimethylolpropane as initiator through the alkoxy chain extension and trihydroxy alcohol, gather X acid Y ester binary or polyvalent alcohol (wherein X and Y are second, third, fourth, own etc.), gather (6-caprolactone) trihydroxy alcohol (for example shown in the structural formula XI) etc.
The material of the aromatic series hydroxyl that the present invention is alleged is meant aryl polyvalent alcohol such as p-dihydroxy-benzene, catechol, resorcinol, methyl pyrocatechol, 2; 6-two (the hydroxyl tert-butyl group) phenol, bisphenol-A, Bisphenol F, bisphenol S, modified bisphenol A or Bisphenol F (shown in structural formula XIII and XIV), and inlaying the mutation (shown in structural formula XII) that gathers alkoxy segment (like polyethoxy, propoxyl group, butoxy segment) in its molecular skeleton.
The alleged amino resins polyvalent alcohol of the present invention is three, four, five or hexamethylol melamine resin and their potpourri.
The consumption of this type of polyvalent alcohol material accounts for 0% to 50% weight portion of total photosensitive resin in the alleged chemical prescription system of the present invention.
(F) can select to use the amino resin crosslinking agent that cross linking of epoxy resin is solidified as required
The alleged amino resin crosslinking agent of the present invention is meant many melamine methylols resin of methyl etherified or butyl etherificate, most importantly the hexamethylol melamine resin of hexamethyl or six butyl etherificates (HMMM or HBMM).Though HMMM or HBMM are not the polyvalent alcohols of dominance, under sour environment, be easy to take place pure exchange reaction and and cross linking of epoxy resin.
The consumption of this type of amino resin crosslinking agent accounts for 0% to 35% weight portion of total photosensitive resin in the alleged chemical prescription system of the present invention.
(G) can select to use the polynary vinyl ether of aliphatics or aromatic series as required
The polynary vinyl ether of aliphatics that the present invention is alleged or aromatic series is meant the aliphatics or the aromatics of the oligomer shape of containing at least two vinyl ether terminal functionality; For example cyclohexyl is to dimethanol divinyl ether and terephthaldehyde's acid diethylene glycol divinyl ether, it is characterized in that containing in the molecule penylene or the hydrogenation of benzene support structure unit important component part as molecular structure.
The consumption of this type of amino resin crosslinking agent accounts for 0% to 40% weight portion of total photosensitive resin in the alleged chemical prescription system of the present invention.
(H) select auxiliary agent or dyestuff as required for use
As required, can also add adjuvants such as auxiliary agents such as foam-breaking agent, levelling agent, homogenize agent, antioxidant, sensitizer and dyestuff in the alleged chemical prescription system of the present invention.Only otherwise the usability generation ill-effect that can will reach institute, the consumption of auxiliary agent or adjuvant is unrestricted.
The process of three-dimensional imaging (making the process of three-dimensional body)
The chemical prescription system that the present invention is alleged can be solidified under the effect of electron beam, X-light, ultraviolet light, visible light.Through controlled curing, can form the three dimensional practicality image.The wavelength of effect light source is preferably in the 280-650nm scope, especially, preferably uses LASER Light Source that three-dimensional lithographic technique developed use for example helium cadmium (HeCd) laser, argon laser and Solid State Laser (NdYAG).Skill practician in this industry knows that the frequency of selected light source must adapt with the kind of the light trigger of being selected for use, and initiating agent produces maximum absorption when making irradiation, and makes the thickness of the curing that single pass causes big as far as possible.
The present invention thereby relate to alleged chemical prescription system and solidify to form three-dimensional body through irradiation particularly makes the process of three dimensional practicality with the method for the three-dimensional etching of laser.This process is made up of following concrete steps: (1) is at the liquid resin of this kind of surface applied one deck ability hardening with radiation; (2) this coating is made public according to the imaging needs, realize planar imaging.The exposure area is to have confirmed according to the imaging needs in advance, can be the mode that adopts laser beams intersect scanning.So-called cross scan is meant this coating is carried out X-direction of principal axis and the scanning of Y-direction of principal axis respectively, perhaps along two enterprising line scannings of diagonally opposing corner direction.The intensity of exposure must be able to make liquid resin in a few tens of milliseconds, solidify to reach significant intensity, can support the weight of follow-up numerous coatings; (3) on the coating that this has just made public, apply the liquid resin of this kind of one deck ability hardening with radiation again; (4) this coating is made public according to the imaging needs, the intensity of exposure must be able to make liquid resin in a few tens of milliseconds, solidify the curing area that reaches significant intensity and last layer and form enough cohesive forces, and can support the weight of follow-up numerous coatings; (5) repeat above-mentioned steps (3) and (4),, form the object of a three-dimensional up to accomplishing the predetermined number of plies.
Generally speaking, the object that obtains through above technological process does not reach stable mechanical strength toward contact when just accomplishing making.The common practice of dealer is that it was positioned in the ultraviolet baking box of a wide spectrum further irradiation 0-200 minute, even heats the back again and solidify, so that intensity is fully set up.But this depends on the characteristic of used photosensitive resin system, and not all photosensitive resin system all need so be done.
Application example
This invention can access detailed embodiment through following concrete application example.Before introducing instance, earlier relevant test event is done the introduction an of necessity.Each prescription resin mixes material under 30 ℃-80 ℃ and forms in common stirring mixer.After the mixing, with the viscosity of 30 ℃ of Brookfield viscometer measurements.The sample that mechanical meaurement is used is to go up making in the SLA-350 type that U.S. three dimension system company produces with the three-dimensional etching machine of SLA-7000 type (adopting the Solid State Laser light source, the 355nm wavelength), and in wide spectrum ultraviolet baking box irradiation 2 hours.All samples all do not heat the back and solidify.The material extending test is carried out according to American society of test material standards ASTM D638.Hardness test is carried out according to ASTM D1415.Thermal change type temperature test carries out according to ASTM D648.The notched izod impact strength is carried out according to ASTM D256.Crooked test carries out according to ASTMD790.The material transmittance adopts the flat board of 1 cm thick with common its transmittance in 500 nanometers of visible spectrophotometer test.
The chemical prescription system that describes below all is the uniform fluent meterial that forms through being mixed.
Table one: instance 1 to instance 10 (amounts of components that provides in each instance is a percentage by weight)
Annotate: (a) UVA1500 is Belgian UCB. S.A. (BE) Bruxelles Belgium product, and principal ingredient is 3,4-7-oxa-bicyclo[4.1.0 carbonic acid 3,4-epoxycyclohexyl methyl ester; (b) Switzerland's vapour Bagong department product, the phenolics of the catechol base of epoxy-functional; (c) U.S. Allied Signal Company products, Main Ingredients and Appearance are that cyclohexyl is to the dimethyl divinyl ether; (d) abbreviation of Hexamethoxymethylmelamine (hexamethoxy methyl cyanuramide resin); (e) viscosity 25 ℃ the time is 500-900PaS; (f) sample that provides of Belgian Surface Specialties company; (g)-(j) Switzerland's vapour Bagong department (Ciba SC) product, light trigger.
The test result of these ten prescription systems is shown in table two:
Table two
The cubic light moulding that above-mentioned instance provides except instance 1, has all obtained very high thermal change type temperature with chemical prescription system, also mostly has penetrability (except the instance 7-10) and favorable mechanical performance preferably.The brookfield viscosity of the prescription system that each embodiment provides in the time of 30 ℃ be all far below 800mPas, thereby have good stereolithography processability.The prescription system that each embodiment provides has all obtained very high bending modulus after the three-dimensional etching of laser is solidified, the modulus fall all is no more than 5% after one week of immersion in water, shows that they have possessed good hydrolytic resistance.
The initiative thinking that the present invention discloses obtains detailed embodiment via these instantiations.Yet,, and do not mean that claim of the present invention receives the restriction of embodiment though the instance quantity that provides is limited.Under the initiative thinking that the present invention discloses is guided, to example change easily or the differentiation that discloses here.Correspondingly, claim proposed by the invention is intended to contain and can not jumps out the set pattern that the present invention reveals and the possible embodiment that details to the greatest extent of category.
Claims (11)
1. the chemical prescription system of a liquid photosensitive resin, this system contains:
(A) at least a organic substance that can carry out cationic polymerization, take from:
A) contain the aliphatic compounds of at least two ring-type oxygen ethylene groups; Or
B) contain the aromatic compounds of at least two oxetane groups; Or
C) contain aliphatic compounds, aromatic compounds or the heterogeneous ring compound of at least two glycidyl ether groups;
(B) at least a organic substance that can carry out free radical polymerization, take from:
A) contain the aliphatic compounds that at least one acryloyl-oxy or methacryloxy are rolled into a ball; Or
B) contain the aromatic compounds of not chain extension of at least two acryloyl-oxies or methacryloxy group; Or
C) contain aliphatic series or the aromatic compounds that alcoxyl support segment, alkyl acyl-oxygen segment, alkyl urethano segment are contained again at least two acryloyl-oxies or methacryloxy group;
(C) at least a cationic photoinitiator;
(D) at least a radical photoinitiator;
(E) can select to use aliphatics or aromatic polyol, perhaps amino resins polyvalent alcohol as required;
(F) can select to use the amino resin crosslinking agent that cross linking of epoxy resin is solidified as required;
(G) can select to use the polynary vinyl ether of aliphatics or aromatic series as required;
Said (A) contains the aliphatic compounds of at least two ring-type oxygen ethylene groups in a), is selected from a kind of of following material or surpasses a kind of combination in any: two (2,3-epoxide ring amyl group) ether, and 1,2-two (2; The support of 3-epoxide ring amyl group oxygen) ethane, 3,4-7-oxa-bicyclo[4.1.0 carbonic acid 3,4-epoxycyclohexyl methyl ester; 3,4-epoxy 6-methylcyclohexane carbonic acid 3,4-epoxy 6-methylcyclohexyl methyl ester, hexane diacid (3; 4-epoxycyclohexyl methyl) diester, hexane diacid (3,4-epoxy 6-methyl cyclohexane ylmethyl) diester, ethene two (3; The 4-epoxycyclohexyl) carbonic ester, two (3, the 4-epoxycyclohexyl) monoethylene glycol diether, vinyl cyclohexane di-epoxide; The dicyclopentadiene di-epoxide, and 2-(3,4-epoxycyclohexyl-5,5-spiral shell-3; The 4-epoxy) cyclohexane-1, the 3-dioxan, epoxidised number-average molecular weight is not more than 2000 polybutadiene oligomer, and its consumption accounts for the 0%-75% of overall prescription system weight;
Said (A) b) contain the aromatic compounds of at least two oxetane groups in, its consumption accounts for the 0%-60% of overall prescription system weight;
Said (A) c) the aliphatic compounds, aromatic compounds or the heterogeneous ring compound that contain at least two glycidyl ether groups in; Be selected from a kind of of following material or surpass a kind of combination in any: 4-chloro epoxypropane and 2; 4; 6-trihydroxy hexane, 1,4-methylol cyclohexane, 1,1; 1-trimethylolpropane, 1; 1,1-trimethylolethane, Pehanorm, aliphatic polyol remove hydrogen chloride and the etherate that generates, and the aromatic polyol that 4-chloro epoxypropane and p-dihydroxy-benzene, catechol, resorcinol, methyl pyrocatechol, number-average molecular weight are not more than 650 acid catalysis phenolics, bisphenol-A, Bisphenol F, bisphenol S removes hydrogen chloride and the etherate that generates; Perhaps epoxide equivalent is the three functionalized isocyanuric acid ester resins of glycidol ether of 135-180 gram, and its consumption accounts for the 0%-60% of overall prescription system weight;
Said (A) contains the aliphatic compounds of at least two ring-type oxygen ethylene groups, said (A) b in a)) in contain aromatic compounds and said (A) c of at least two oxetane groups) in contain aliphatic compounds, aromatic compounds or the heterogeneous ring compound of at least two glycidyl ether groups, three 10%-80% that add up to consumptions to account for overall prescription system weight.
2. the chemical prescription system of liquid photosensitive resin according to claim 1; Wherein, Said (B) contains the aliphatic compounds of at least one acryloyl-oxy or methacryloxy group in a); Be selected from a kind of of following material or surpass a kind of combination in any: ENB acrylate monomer, ENB methacrylate monomers, (methyl) acrylic acid and 1,4-methylol cyclohexane, 1,1; 1-trimethylolpropane, 1; 1,1-trimethylolethane, tetramethylol methane, two contract aliphatic polyol generation esterification and the esters of acrylic acid or the methyl acrylic ester polyfunctionality monomer that generate of tetramethylol methane, its consumption accounts for the 0%-20% of overall prescription system weight.
3. the chemical prescription system of liquid photosensitive resin according to claim 1; Wherein, Said (B) contains the aliphatic compounds of at least one acryloyl-oxy or methacryloxy group in a); Be selected from a kind of of following material or surpass a kind of combination in any: ENB methacrylate monomers, the many acrylic ester of dipentaerythrityl ether.
4. the chemical prescription system of liquid photosensitive resin according to claim 1; Wherein, Said (B) b) the aromatic compounds that contains the not chain extension of at least two acryloyl-oxies or methacryloxy group in; Be selected from a kind of of following material or surpass a kind of combination in any: (methyl) acrylic acid and p-dihydroxy-benzene, catechol, resorcinol, methyl pyrocatechol, number-average molecular weight are not more than aromatic polyol generation esterification and the esters of acrylic acid or the methyl acrylic ester monomer that generate of the not chain extension of 650 phenolics, bisphenol-A, Bisphenol F, bisphenol S, and its consumption accounts for the 0%-25% of overall prescription system weight.
5. the chemical prescription system of liquid photosensitive resin according to claim 1; Wherein, Said (B) c) contain aliphatic series or the aromatic compounds that alcoxyl support segment, alkyl acyl-oxygen segment, alkyl urethano segment are contained again at least two acryloyl-oxies or methacryloxy group in the item, its consumption accounts for the 0%-25% of overall prescription system weight.
6. the chemical prescription system of liquid photosensitive resin according to claim 1; Wherein, Said (B) contains aliphatic compounds, said (B) b of at least one acryloyl-oxy or methacryloxy group in a)) in contain aromatic compounds and said (B) c of the not chain extension of at least two acryloyl-oxies or methacryloxy group) in contain aliphatic series or the aromatic compounds that alcoxyl support segment, alkyl acyl-oxygen segment, alkyl urethano segment are contained again at least two acryloyl-oxies or methacryloxy group, three 1%-40% that add up to consumptions to account for overall prescription system weight;
7. the chemical prescription system of liquid photosensitive resin according to claim 1; Wherein, Cationic photoinitiator in said (C) item; Be selected from a kind of of following material or surpass a kind of combination in any: phenyl sulphur hexafluoro antimonate, phenyl sulphur hexafluoro arsenate, phenyl sulphur hexafluorophosphate, phenyl-iodide hexafluorophosphate, its consumption accounts for the 0.1%-9% of overall prescription system weight.
8. the chemical prescription system of liquid photosensitive resin according to claim 1; Wherein, Radical photoinitiator in said (D) item; Be selected from a kind of of following material or surpass a kind of combination in any: styrax class, benzoin ether, styrax acetate, acetophenones, phenyl ketal class and phenyl phosphorus oxygen and phenyl phosphinylidyne oxygen class, xylene ketone, its consumption accounts for the 0.1%-10% of overall prescription system weight.
9. the chemical prescription system of liquid photosensitive resin according to claim 1, wherein, aliphatics or aromatic polyol in said (E), perhaps amino resins polyvalent alcohol, its consumption accounts for the 0%-50% of overall prescription system weight.
10. the chemical prescription system of liquid photosensitive resin according to claim 1; Wherein, The amino resin crosslinking agent that in said (F) item cross linking of epoxy resin is solidified; Be selected from following material: the amino resins polyvalent alcohol of alkyl-blockedization, the melamine formaldehyde resin of hexamethyl or six butyl etherificates, consumption accounts for the 0%-35% of overall prescription system weight.
11. the chemical prescription system of liquid photosensitive resin according to claim 1; Wherein, Aliphatics or the polynary vinyl ether of aromatic series in said (G) item; Be selected from a kind of of following material or surpass a kind of combination in any: cyclohexyl is to dimethyl divinyl ether and terephthaldehyde's acid diethylene glycol divinyl ether, and its consumption accounts for the 0%-40% of overall prescription system weight.
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| WO2013028281A1 (en) * | 2011-08-22 | 2013-02-28 | Dow Global Technologies Llc | Toughener and toughened epoxy adhesive |
| CN102432840A (en) * | 2011-10-25 | 2012-05-02 | 南昌大学 | Stereolithography rapid protoyping photosensitive resin prepared by using polypropylene glycol diglycidyl ether diacrylate as prepolymer, and preparation method for stereolithography rapid protoyping photosensitive resin |
| BR112016029766A2 (en) | 2014-06-23 | 2017-08-22 | Carbon Inc | methods of producing three-dimensional polyurethane objects from materials having multiple hardening mechanisms |
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| JP6883020B2 (en) * | 2016-03-31 | 2021-06-02 | 株式会社Adeka | Curable composition, method for producing cured product, and cured product thereof |
| CN107621752B (en) | 2016-07-13 | 2019-11-12 | 常州强力先端电子材料有限公司 | One specific admixture type photosensitive resin and preparation method thereof |
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| CN106583710B (en) * | 2016-12-29 | 2019-01-22 | 西安铂力特增材技术股份有限公司 | A kind of manufacturing process of magnesium and magnesium alloy complex component based on photocuring technology |
| US10316213B1 (en) | 2017-05-01 | 2019-06-11 | Formlabs, Inc. | Dual-cure resins and related methods |
| CN110016271B (en) * | 2018-01-10 | 2021-04-27 | 常州强力电子新材料股份有限公司 | Cyclic carbonate epoxy compound, cationically polymerizable composition and use thereof |
| CN110845680A (en) * | 2018-08-21 | 2020-02-28 | 常州强力电子新材料股份有限公司 | Energy-curable epoxy graft-modified amino resin, energy-curable composition containing same, and application |
| CN109343309B (en) * | 2018-12-03 | 2020-07-10 | 深圳市华星光电技术有限公司 | Negative photoresist and application thereof |
| CN111849394B (en) * | 2019-04-29 | 2021-12-28 | 常州强力电子新材料股份有限公司 | Photocurable adhesive composition, photocurable adhesive, polarizing plate, and optical device |
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