CN101776846A - Light-cured component for laser stereo lithography - Google Patents
Light-cured component for laser stereo lithography Download PDFInfo
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- CN101776846A CN101776846A CN200910000681A CN200910000681A CN101776846A CN 101776846 A CN101776846 A CN 101776846A CN 200910000681 A CN200910000681 A CN 200910000681A CN 200910000681 A CN200910000681 A CN 200910000681A CN 101776846 A CN101776846 A CN 101776846A
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- bisphenol
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- UMWZLYTVXQBTTE-UHFFFAOYSA-N 2-pentylanthracene-9,10-dione Chemical compound C1=CC=C2C(=O)C3=CC(CCCCC)=CC=C3C(=O)C2=C1 UMWZLYTVXQBTTE-UHFFFAOYSA-N 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- 239000005632 Capric acid (CAS 334-48-5) Substances 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- BMRWNKZVCUKKSR-UHFFFAOYSA-N butane-1,2-diol Chemical compound CCC(O)CO BMRWNKZVCUKKSR-UHFFFAOYSA-N 0.000 description 1
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 1
- XUPYJHCZDLZNFP-UHFFFAOYSA-N butyl butanoate Chemical compound CCCCOC(=O)CCC XUPYJHCZDLZNFP-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
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 1
- 239000013530 defoamer Substances 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
- 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
- RGXWDWUGBIJHDO-UHFFFAOYSA-N ethyl decanoate Chemical compound CCCCCCCCCC(=O)OCC RGXWDWUGBIJHDO-UHFFFAOYSA-N 0.000 description 1
- SHZIWNPUGXLXDT-UHFFFAOYSA-N ethyl hexanoate Chemical compound CCCCCC(=O)OCC SHZIWNPUGXLXDT-UHFFFAOYSA-N 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
- 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
- 238000002156 mixing Methods 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- YLYBTZIQSIBWLI-UHFFFAOYSA-N octyl acetate Chemical compound CCCCCCCCOC(C)=O YLYBTZIQSIBWLI-UHFFFAOYSA-N 0.000 description 1
- AVBRYQRTMPHARE-UHFFFAOYSA-N octyl formate Chemical compound CCCCCCCCOC=O AVBRYQRTMPHARE-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- AHHWIHXENZJRFG-UHFFFAOYSA-N oxetane Chemical group C1COC1 AHHWIHXENZJRFG-UHFFFAOYSA-N 0.000 description 1
- RUOPINZRYMFPBF-UHFFFAOYSA-N pentane-1,3-diol Chemical compound CCC(O)CCO RUOPINZRYMFPBF-UHFFFAOYSA-N 0.000 description 1
- 208000021596 pentasomy X Diseases 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
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 230000035945 sensitivity Effects 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
- 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
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 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 technology three-dimensional imaging is to finish by the overlapping of two steps: (1) optionally makes the specific region to the liquid layer of the specific thicknesses on the surface of the liquid resin material of Optical irradation sensitivity be subjected to light irradiation, be meant the scanning and irradiation of the laser beam that is subjected to 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 feature 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 manufacturing fast 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) by 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 is subjected to 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 shaping 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 the model of the making of model of general industry product and many special purposes goods.The photosensitive resin prescription system of the three-dimensional etching special use of existing laser mostly is that the modelling at 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 class special-purpose require the object after 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 determining 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 accepting extensively most in commercial Application 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 for unbodied thermoplastics and thermosetting plastics, then often specific heat modification temperature exceeds 20-40 ℃, so it only has academic significance, should not be in industry member with glass temperature as the stable on heating measurement index of plastic products.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 be solidified after illumination curing, cause the size misalignment in order to avoid produce big out of contior contraction, 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 the Individual Items that are used for making 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 further article are placed on and under 120-160 ℃, toast several hours in the heated oven, thereby improve thermotolerance and some mechanical propertys of material so that make material cured well-done.But this follow-up being heating and curing causes bigger dimensional contraction that can not pre-control, 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 required 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 to use on the stereolithography rapidform machine, 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.
Photosensitive resin system commercial photosensitive resin system that is used for this kind three-dimensional imaging/flash mould purpose of selling and patent disclosure and that apply for a patent open explanation also satisfies these requirements simultaneously without any a single product or prescription resin.If the photosensitive resin product of the pure organic principle of the commercial so-called heat resistant type of selling is only by 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 does not see commodity selling as yet that discloses in present publication and the application publication, it is heat-resisting more than 100 ℃ also all can not to accomplish to satisfy photocuring simultaneously, 30 ℃ of brookfield viscosities are no more than 1500mPas, resin must be for a long time uniform and stable requirement and solidfied material have 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 must heating under 160 ℃ after 2 hours.U.S. Patent Application Publication instructions 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 the high temperature heating, 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 use in the stereolithography machine at all.U.S. Patent Application Publication instructions 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 problem of the too high and 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 to be pitchy after curing 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 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 of following concrete steps:
(1) at the liquid resin of this kind of surface applied one deck energy hardening with radiation;
(2) this coating is exposed according to the imaging needs, realize planar imaging.The exposure area is to have determined 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 solidify in a few tens of milliseconds to reach significant intensity, can support the weight of follow-up numerous coatings;
(3) on the coating that this has just exposed, apply the liquid resin of this kind of one deck energy hardening with radiation again;
(4) this coating is exposed according to the imaging needs, the intensity of exposure must be able to make liquid resin solidify the curing area that reaches significant intensity and last layer in a few tens of milliseconds 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 finishing 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 and this kind chemicals to make stereo article, 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 and this kind chemicals to make stereo article, 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 and this kind chemicals to make stereo article, 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 and this kind chemicals to make stereo article, 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 and this kind chemicals to make stereo article, the uniform low-viscosity (mobile) liquid chemicals of this non-Inorganic Fillers Filled provides the three-dimensional feasibility in kind and the 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.
Understand on wide significance, 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 one or more kinds at least and has the compound of two or more ring-type oxygen ethylene groups or two oxetane groups or the compound of two above glycidyl ether groups.The use amount that this class can be carried 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, 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) ethylene glycol diether, the 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.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 more 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, such polyvalent alcohol has ethylene 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 exemplary configuration synoptic diagram of such glycidyl ether compound is as follows:
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 this type of etherate that contains poly-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 compounds is as follows:
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 class can be carried 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 norborene acrylate monomer, norborene 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 ethylene glycol, tirethylene glycol, multicondensed ethylene glycol, 1,2-propylene glycol, 1,4-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 contains at least two acryloyl-oxies or methacryloxy group and contains (promptly the passing through chain extension) aliphatic series of alcoxyl support segment, alkyl acyl-oxygen segment, alkyl urethano segment or aromatic compounds again and be meant above-mentioned (B) a) and (B) b) two kinds of compounds that situation is alleged are inlaid with poly-alcoxyl support segment, alkyl acyl-oxygen segment or alkyl urethano segment in its molecule.Alleged poly-alcoxyl support segment is meant polyoxyethylene segment (for example polyglycol segment or polyethylene oxide segment), polyoxy trimethylene segment (polypropyleneoxide segment for example, poly-1,2-propylene glycol segment or poly-positive propylene glycol segment), poly tetramethylene oxide segment (PolyTHF segment for example, gather 1,2-butylene glycol segment or poly-positive butylene glycol segment) or polyoxy hexamethylene segment (for example poly-positive hexanediol segment).Alleged alkyl acyloxy segment is meant poly-butyl hexanoate segment, polycaprolactone segment, poly-ethyl hexanoate segment, poly-capric acid butyl ester segment, poly-capric acid propyl ester segment, poly-ethyl caprate segment, poly-n-hexyl butyrate segment, poly-n-hexyl butyrate segment, poly-butyl butyrate segment, poly-ethyl butyrate segment, poly-ethyl acetate segment, poly-butyl acetate segment, poly-capryl acetate segment, poly-octyl acetate segment, polyphenyl hexyl formate segment, polyphenyl octyl formate segment etc.Alleged alkyl urethano segment is meant by the feature segment of diisocyanate (as toluene diisocyanate, '-diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate etc.) with the chain polymerization product of line style dibasic alcohol (as 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 in the epoxy compound molecule or oxetane groups generation ring-opening polymerization 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. 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 (as styrax), benzoin ether is (as benzoin methyl ether, the ethyl benzoin ether, the isopropyl benzoin ether, the phenyl scented rice of resting in peace), the styrax acetate, acetophenones (acetophenone, 2, the 2-dimethoxy-acetophenone, 1, the 1-dichloroacetophenone), phenyl ketal class is (as the phenyl dimethyl ketal, diethylamino phenyl base ketal), the anthraquinone class is (as 2-methylanthraquinone, the 2-EAQ, 2-tert-butyl group anthraquinone, the 1-chloroanthraquinone, the 2-amyl anthraquinone), and phenyl phosphorus oxygen and phenyl phosphinylidyne oxygen class (shown in structural formula IX and the X), the dimethylbenzene ketone is (as the diformazan benzophenone, 4,4 '-two (N, N '-dimethyl amine) phenyl ketone), the 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, poly-X acid Y ester binary or polyvalent alcohol (wherein X and Y be second, third, fourth, oneself 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 in the mutation (shown in the structural formula XII) of having inlayed poly-alkoxy segment (as 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 as required to use, the alleged amino resin crosslinking agent of amino resin crosslinking agent the present invention that cross linking of epoxy resin is solidified is meant many melamine methylols resin of methyl etherified or butyl etherificate, the most importantly 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 defoamer, levelling agent, homogenize agent, antioxidant, sensitizer and dyestuff in the alleged chemical prescription system of the present invention.Only otherwise can be to the usability generation ill-effect that will reach, the consumption of auxiliary agent or adjuvant be 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.By 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 selected light trigger, 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 of following concrete steps: (1) is at the liquid resin of this kind of surface applied one deck energy hardening with radiation; (2) this coating is exposed according to the imaging needs, realize planar imaging.The exposure area is to have determined 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 solidify in a few tens of milliseconds to reach significant intensity, can support the weight of follow-up numerous coatings; (3) on the coating that this has just exposed, apply the liquid resin of this kind of one deck energy hardening with radiation again; (4) this coating is exposed according to the imaging needs, the intensity of exposure must be able to make liquid resin solidify the curing area that reaches significant intensity and last layer in a few tens of milliseconds 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 finishing the predetermined number of plies.
Generally speaking, the object that obtains by above technological process does not reach stable mechanical strength toward contact when just finishing 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 needs so to do.
Application example
This invention can access detailed embodiment by following concrete application example.Before introducing example, 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 that the SLA-350 type produced in U.S. three dimension system company and the three-dimensional etching machine of SLA-7000 type (adopting the Solid State Laser light source, the 355nm wavelength) are gone up and made, 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 ASTMD648.The notched izod impact strength is carried out according to ASTMD256.Crooked test carries out according to ASTMD790.The material transmittance adopts the flat board of 1 cm thick to test its transmittance in 500 nanometers with common visible spectrophotometer.The chemical prescription system that describes below all is the uniform fluent meterial that forms through being mixed.
Table one: example 1 is to example 10 (amounts of components that provides in each example 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 product, Main Ingredients and Appearance is 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 sees table two:
Table two
The cubic light moulding that above-mentioned example provides except example 1, has all obtained very high thermal change type temperature with chemical prescription system, also mostly has penetrability (except the example 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 is subjected to the restriction of embodiment though the example 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 describes in detail to the greatest extent of category.
Claims (15)
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 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, 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;
2. (A) is two (2 a) in the claim 1,3-epoxide ring amyl group) ether, 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) ethylene glycol diether, the vinyl cyclohexane di-epoxide, the dicyclopentadiene di-epoxide, 2-(3,4-epoxycyclohexyl-5,5-spiral shell-3, the 4-epoxy) cyclohexane-1,3-dioxan, epoxidised number-average molecular weight are not more than aliphatic series (the comprising alicyclic) compound that polybutadiene oligomer of 2000 etc. contains at least two ring-type oxygen ethylene groups, and the consumption of its combination in any accounts for the 0%-75% of overall prescription system weight;
3. be the aromatic compounds that has two or more oxetane groups in the molecule (A) b in the claim 1), its consumption accounts for the 0%-60% of overall prescription system weight.Reasonable is to two (the 4-methyl 4-methylol oxetanes) diether of benzene methylene glycol;
4. be 4-chloro epoxypropane and 2 (A) c in the claim 1), 4,6-trihydroxy hexane, 1,4-methylol cyclohexane, 1,1, the 1-trimethylolpropane, 1,1, the 1-trimethylolethane, Pehanorms etc. (require hydroxy functionality 〉=2, no ceiling) aliphatic polyol removes hydrogen chloride and etherate that generates and the etherate with such chemical constitution (requiring epoxide equivalent (EEW)≤300) that synthesizes with other approach, 4-chloro epoxypropane and p-dihydroxy-benzene, catechol, resorcinol, methyl pyrocatechol, number-average molecular weight is not more than 650 acid catalysis phenolics, bisphenol-A, Bisphenol F, aromatic polyols such as bisphenol S remove chlorination oxygen and etherate that generates and the etherate with such chemical constitution that synthesizes with other approach, perhaps epoxide equivalent is the three functionalized isocyanuric acid ester resins of glycidol ether of 135-180 gram, and the consumption of its combination in any accounts for the 0%-60% of overall prescription system weight;
5. three 10%-80% that add up to consumption to account for overall prescription system weight in the claim 2,3,4;
6. (B) is the norborene acrylate monomer a) in the claim 1, the norborene methacrylate monomers, (methyl) acrylic acid and 1,4-methylol cyclohexane, 1,1, the 1-trimethylolpropane, 1,1, the 1-trimethylolethane, tetramethylol methane, two contract aliphatic polyol generation esterification such as tetramethylol methane and the esters of acrylic acid that generates or methyl acrylic ester polyfunctionality monomer and with synthetic (methyl) esters of acrylic acid polyfunctionality monomer with such chemical constitution of other approach, and the consumption of its combination in any accounts for the 0%-20% of overall prescription system weight.Reasonable is norborene methacrylate monomers and the many acrylate of dipentaerythrityl ether;
7. be that (methyl) acrylic acid and p-dihydroxy-benzene, catechol, resorcinol, methyl pyrocatechol, number-average molecular weight are not more than not the aromatic polyol generation esterification of chain extension and the esters of acrylic acid that generates or methyl acrylic ester monomer and (methyl) esters of acrylic acid polyfunctionality monomer with such chemical constitution that synthesizes with other approach such as 650 phenolics, bisphenol-A, Bisphenol F, bisphenol S (B) b in the claim 1), the consumption of its combination in any accounts for the 0%-25% of overall prescription system weight.Reasonable is Bisphenol F type or bisphenol type epoxy two (methyl) acrylate (average Mw=300-800), and consumption accounts for the 0%-20% of overall prescription system weight;
8. (B) c in the claim 1) item is meant a) or (B) b at (B)) be inlaid with alcoxyl support segment, alkyl acyl-oxygen segment or alkyl urethano segment in described polynary (methyl) acrylate molecule.Alleged alcoxyl support segment is meant polyglycol segment, polypropyleneoxide segment or PolyTHF segment.Reasonable segment is the polyurethane segment that polyphenyl hexyl formate segment, toluene diisocyanate or '-diphenylmethane diisocyanate and ethylene glycol form, and the consumption of its combination in any accounts for the 0%-25% of overall prescription system weight;
9. three 1%-40% that add up to consumption to account for overall prescription system weight in the claim 6,7,8;
10. (C) item is phenyl sulphur hexafluoro antimonate, phenyl sulphur hexafluoro arsenate, phenyl sulphur hexafluorophosphate, phenyl-iodide hexafluorophosphate in the claim 1, and the consumption of its combination in any accounts for the 0.1%-9% of overall prescription system weight;
11. (D) item is the styrax class in the claim 1, benzoin ether is (as benzoin methyl ether, the ethyl benzoin ether, the isopropyl benzoin ether, the phenyl scented rice of resting in peace), the styrax acetate, acetophenones (acetophenone, 2, the 2-dimethoxy-acetophenone, 1, the 1-dichloroacetophenone), phenyl ketal class is (as the phenyl dimethyl ketal, diethylamino phenyl base ketal), and phenyl phosphorus oxygen and phenyl phosphinylidyne oxygen class, the dimethylbenzene ketone is (as the diformazan benzophenone, 4,4 '-two (N, phenyl ketone N '-dimethyl amine)) radical photoinitiator such as, the consumption of its combination in any accounts for the 0.1%-10% of overall prescription system weight.Reasonable is 2,2-dimethoxy-2 phenyl acetophenone, 1-hydroxy-cyclohexyl benzophenone and triphenylphosphine acyl-oxygen, and the consumption of its combination in any accounts for the 0.1%-6% of overall prescription system weight;
12. (E) is aryl polyvalent alcohol such as p-dihydroxy-benzene, catechol, resorcinol, methyl pyrocatechol, 2 in the claim 1,6-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 in the medium mutation of having inlayed poly-alkoxy segment (as polyethoxy, propoxyl group, butoxy segment) of its molecular skeleton, or amino resins polyvalent alcohol.Reasonable is the chemical structural formula in the literary composition (XIII) or (XIV) bisphenol-A of represented chemical modification, perhaps melamine methyl alcohol resin, and the consumption of its combination in any accounts for the 0%-50% of overall prescription system weight;
13. (F) item is the amino resin crosslinking agent that cross linking of epoxy resin is solidified in the claim 1, most importantly the amino resins polyvalent alcohol of alkyl-blockedization, reasonable is the melamine formaldehyde resin of hexamethyl or six butyl etherificates, and consumption accounts for the 0%-35% of overall prescription system weight;
14. (G) is aliphatics or the aromatics that contains the oligomer shape of at least two vinyl ether terminal functionality in the claim 1, it is characterized in that containing in the molecule penylene or the hydrogenation of benzene support structure unit important component part as molecular structure.Reasonable be cyclohexyl to dimethyl divinyl ether and terephthaldehyde's acid diethylene glycol divinyl ether, the consumption of its combination in any accounts for the 0%-40% of overall prescription system weight;
15. a technological process of using the chemical prescription system of this kind through the three-dimensional etching making of laser three dimensional practicality, may further comprise the steps: (1) is at the liquid resin of this kind of surface applied one deck energy hardening with radiation; (2) this coating is exposed according to the imaging needs, to realize the planar imaging of this layer.The exposure area is to have determined 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 solidify in a few tens of milliseconds to reach significant intensity, can support the weight of follow-up numerous coatings; (3) on the coating that this has just exposed, apply the liquid resin of this kind of one deck energy hardening with radiation again; (4) this coating is exposed according to the imaging needs, the intensity of exposure must be able to make liquid resin solidify the curing area that reaches significant intensity and last layer in a few tens of milliseconds and form enough cohesive forces, and can support the weight of follow-up numerous coatings; (5) overlapping above-mentioned steps (3) and (4) up to finishing the predetermined number of plies, form the object of a three-dimensional.The resin of the energy hardening with radiation that uses in this process is the chemical prescription system of describing in the claim 1.
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