CN101776844A - Photocuring component used for three-dimensional imaging - Google Patents
Photocuring component used for three-dimensional imaging Download PDFInfo
- Publication number
- CN101776844A CN101776844A CN200910000682A CN200910000682A CN101776844A CN 101776844 A CN101776844 A CN 101776844A CN 200910000682 A CN200910000682 A CN 200910000682A CN 200910000682 A CN200910000682 A CN 200910000682A CN 101776844 A CN101776844 A CN 101776844A
- Authority
- CN
- China
- Prior art keywords
- segment
- poly
- methyl
- molecular weight
- glycol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Abstract
The invention relates to a liquid-state photosensitive resin prescription system which is suitable for three-dimensional imaging and is especially suitable for an entity obtaining a three-dimensional figure by a laser three-dimensional etching method. The obtained three-dimensional entity has favorable elasticity and transparence and is suitable for manufacturing a complicated technological physical model of a human body quickly.
Description
Technical field
The present invention relates to a kind of photosensitive resin prescription system of liquid state, be applicable to three-dimensional imaging, 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 the better elastic and the transparency.
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, promptly so-called three-dimensional imaging.
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 (being called the cubic light moulding in the Japanese) 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 three-dimensional in kind look means such as shooting by three and be converted into the three-dimensional data bag existing, rectification is the CAD stereo-picture then, changes into three-dimensional in kind again.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 medical research and medical aspect application also be known.The organ of human body complexity can be copied physical model in this way, be used for medical purpose, for example the discussion that participates in many ways of operation plan is determined.
Most medical applications require the object after the etching moulding to have good pliability (elasticity in other words) and transparency.Yet the photosensitive resin system that is used for this kind three-dimensional imaging/flash mould purpose that commercial aspect is used, U.S. Pat P5972563 for example, the resin prescription that USP6096796 and USP6379866 reveal, the mechanical property of the object of producing mostly is to make every effort to reach the magnitude of durable plastic material, seldom can satisfy the requirement of medical application to the elasticity and the transparency.Be necessary to develop and have the liquid photosensitive resin system that three-dimensional etching that the such favorable elasticity of silicon rubber has good transparency is simultaneously used after the imaging.
Though lack scientific strict difinition, this favorable elasticity that satisfies medical application should be corresponding to the elastomeric elasticity of ordinary rubber, that is to say shore a hardness in the 10-60 scope, elastic modulus is in the 0.1-10MPa magnitude, and elongation rate of tensile failure is more than 150%; The transparency should be near silastic product, and the light penetration of 1 cm thick flat board should surpass 50%.
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:
(A) at least a organic substance that can carry out cationic polymerization, from the material of following a few class oxygen heterocycle, select:
A) at least a aliphatic series (the comprising alicyclic) compound that contains at least two ring-type oxygen ethylene groups;
B) contain the aliphatic series or the aromatic compounds of at least two oxetane groups;
C) contain the aliphatic compounds of at least two glycidyl ether groups or contain the aromatic compounds of at least one glycidyl ether group, and this compounds that contains poly-alcoxyl support segment;
(B) at least a organic substance that can carry out free radical polymerization, from containing the compound of acryloyl-oxy or methacryloxy group, following several classes select:
A) contain the aliphatic compounds that at least one acryloyl-oxy or methacryloxy are rolled into a ball;
B) contain the aromatic compounds that at least one acryloyl-oxy or methacryloxy are rolled into a ball;
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) at least a aliphatics or aromatic series contain the material of at least two hydroxyls, perhaps contain the modified polyalcohol of poly-alkyl siloxane-poly-alkoxy block or random copolymers segment;
(F) can select to use one or more auxiliary agents (comprising surfactant, defoamer, levelling agent etc.) as required;
(G) can select to use one or more dyestuffs as required.
Another aspect of the present invention is to use this chemicals to carry out the process that three-dimensional imaging is also promptly made three-dimensional article, 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, but be not limited to, and adopts the mode of 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 favorable elasticity and transparency according to the three-dimensional imaging needs.When using the three-dimensional lithographic method of laser and this kind chemicals to make stereo article, the stereo article of gained has better elastic, and 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 good transparency, and 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; At least a organic substance that contains an above hydroxyl; And the auxiliary agent of selecting for use as required, dyestuff.
(A) at least a organic substance that can carry out cationic polymerization
The alleged chemical prescription system of the present invention contains at least a the have compound of two or more ring-type oxygen ethylene groups or two oxetane groups or the compound of one or more glycidyl ether group.The use amount that this class can be carried out the material of cationic polymerization among the present invention accounts for the 30-60% of photosensitive resin prescription system general assembly (TW).
A) contain aliphatic series (the comprising alicyclic) compound of at least two ring-type oxygen ethylene groups
Aliphatic series that contains at least two ring-type oxygen ethylene groups that the present invention is alleged or alicyclic compound are 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.
B) contain the aliphatic series or the aromatics of at least two oxetane groups
Alicyclic or the aromatics that contains at least two oxetane groups that the present invention is alleged is meant the compound that has two or more oxetane groups in the molecule, represented as molecular formula (I), it is characterized in that two ends have shrink (1,1, the 1-trimethylolethane) ether structure:
R wherein
1Represent hydrogen, fluorine, alkyl and fluoro-alkyl (to have 1 to 6 carbon atom, for example methyl, ethyl, propyl group, butyl etc. with and perfluoro or the individuality of fluoro partially), aryl (having 6 to 18 carbon atoms, for example phenyl, naphthyl, furyl, thienyl) with and the fluoro thing; R
2Represent a linearity or have the carbochain segment or the siloxane segment of short-chain branch, in the middle of can contain ehter bond, ester bond, carbonic acid ester bond, amido link, ammonia ester bond, urine key, unsaturated double-bond, phenyl ring, bisphenol-A group, Bisphenol F group etc., perhaps not having the segment feature, directly is such group.As an example, such molecule is specifically represented just like molecular formula (II), (III), (IV), (V):
The compound that contains two or more oxetanes with siloxane structure feature except top just mentioned, also just like general molecular formula (VI) and (VII) represented such type, wherein R
3Representing carbon number is individual alkyl or trialkyl silica group such as trimethyl silicane group, triethyl silicon group, tripropyl silicon group or tributyl silicon group of 1-4:
C) the alleged fatty compound that contains at least two glycidyl ether groups of aromatics the present invention that contains the fatty compound of at least two glycidyl ether groups or contain at least one glycidyl ether group is meant and has that 4-chloro epoxypropane and aliphatic polyol remove hydrogen chloride and the compound of the such molecular structure of the etherate that generates.Here said aliphatic polyol has ethylene glycol, tirethylene glycol, multicondensed ethylene glycol, number-average molecular weight to be not more than 5000 polyglycol, 1,2-propylene glycol, number-average molecular weight are not more than 3000 polypropyleneoxide, 1,4-butylene glycol, number-average molecular weight are not more than 2000 PolyTHF, 2,2-dimethyl 1, ammediol, 1,6-hexanediol etc.The fatty compound that contains at least two glycidyl ether groups that the present invention is alleged also refers to contain this type of etherate of poly-alcoxyl support segment.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).
The aromatics that contains at least one glycidyl ether group 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 monohydroxy alcohol has phenol, methylphenol etc.; Such polyvalent alcohol 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.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).
(B) at least a organic substance that can carry out free radical polymerization
The alleged chemical prescription system of the present invention contains a kind of compound with or above 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 5-50% of photosensitive resin prescription system general assembly (TW).
A) contain the aliphatic compounds that at least one acryloyl-oxy or methacryloxy are rolled into a ball;
The aliphatic compounds that contain at least one acryloyl-oxy or methacryloxy group that the present invention is alleged are meant acrylic acid, methacrylic acid, (methyl) ethyl acrylate, (methyl) Isooctyl acrylate monomer, (methyl) hydroxy-ethyl acrylate, (methyl) hydroxypropyl acrylate, single functionality acrylate or methacrylate monomers such as (methyl) acrylic acid ethoxy ethyl ester, (methyl) esters of acrylic acid polyfunctionality monomer that (methyl) acrylic acid and aliphatic polyol generation esterification generate (methyl) esters of acrylic acid polyfunctionality monomer and synthesize with other approach with such chemical constitution.Such polyvalent alcohol has ethylene glycol, tirethylene glycol, multicondensed ethylene glycol, number-average molecular weight is not more than 5000 polyglycol, 1, the 2-propylene glycol, number-average molecular weight is not more than 3000 polypropyleneoxide, 1, the 4-butylene glycol, number-average molecular weight is not more than 2000 PolyTHF, 1, the 3-pentanediol, 1, the 6-hexanediol, 2,4,6-trihydroxy hexane, 1,4-methylol cyclohexane, 1,1, the 1-trimethylolpropane, 1,1, the 1-trimethylolethane, trihydroxy methyl or tetramethylol methane etc., and the intermolecular dehydration of the above polyvalent alcohol of these binary and the etherate polyvalent alcohol that generates.
B) contain the aromatic compounds that at least one acryloyl-oxy or methacryloxy are rolled into a ball;
The aromatic ring compounds of group that contains at least one acryloyl-oxy or methacryloxy group that the present invention is alleged is meant (methyl) esters of acrylic acid polyfunctionality monomer with such chemical constitution that (methyl) acrylic acid phenol oxygen ester monomer, (methyl) acrylic acid and aromatic polyol generation esterification generate (methyl) esters of acrylic acid polyfunctionality monomer and synthesize 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, bisphenol A type epoxy resin, bisphenol f type epoxy resin etc.
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
The present invention is alleged contains at least two acryloyl-oxies or methacryloxy group and contains the 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.).
(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% of photosensitive resin prescription system general assembly (TW), and the most frequently used is 0.3% to 3% 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 benzoin ether), 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 (as the product Lucirin TPO of Ciba company), 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 the laser of 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 5.0% of photosensitive resin prescription system general assembly (TW), and the most frequently used is 1.5% to 3.5% weight portion.
(E) at least a aliphatics or aromatic series contain the material of at least two hydroxyls or contain the modified polyalcohol of poly-alkylsiloxane-poly-alkoxy block or random copolymers segment
The material of the aliphatics hydroxyl that the present invention is alleged is meant the compound that contains two or more hydroxyls with line style, star-like, comb type host molecule structure of oligomer type, and hydroxyl is in the segment end, and the main chain section is polyethers, polyester or polycarbonate structure.As an example, have polyglycol, polypropylene glycol, polytetramethylene glycol (polytetrahydrofuran diol), with 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 can be respectively second, third, fourth, oneself etc.), gather (6-caprolactone) trihydroxy alcohol etc.The present invention is that molecular weight is higher than 100 but softening point is not higher than 60 ℃ to the request for utilization of this compounds.
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, and 6-two (the hydroxyl tert-butyl group) phenol, bisphenol-A, Bisphenol F, bisphenol S etc. have been inlayed poly-alkoxy segment (as polyethoxy, poly-propoxyl group, poly-butoxy segment).The present invention is that molecular weight is higher than 100 but softening point is not higher than 60 ℃ to the request for utilization of this compounds.
The modified polyalcohol that contains poly-alkyl siloxane-poly-alkoxy block or random copolymers segment that the present invention is alleged is meant the block or the random copolymers of polymethyl siloxane or PSI and polyglycol, polypropylene glycol or polytetramethylene glycol, contain at least two terminal hydroxy groups, mean molecular weight is not higher than 1500, and the shared massfraction of polyglycol is between 30%-70%; Or with other approach synthetic but have the poly-alkylsiloxane-poly-alkoxy block of this chemical constitution or the modified polyalcohol of random copolymers segment.
The consumption of this type of polyvalent alcohol material accounts for 1% to 50% of photosensitive resin prescription system general assembly (TW) in the alleged chemical prescription system of the present invention.
(F) auxiliary agent
As required, can also add the table auxiliary agents such as agent, defoamer, levelling agent, homogenize agent, antioxidant, sensitizer of living in the alleged chemical prescription system of the present invention.Only otherwise can be to the usability generation ill-effect that will reach, the use of auxiliary agent be unrestricted.
(G) dyestuff
The alleged chemical prescription system of the present invention is when being used for the medical imaging purpose, and the very important point is that employed material must have different colors.For this reason, can add in the alleged chemical prescription system of the present invention and can make photosensitive resin present dyes in different colors, as dyestuffs such as redness, blueness, white, yellow, consumption is decided as required.
The process of three-dimensional imaging (making the process of three-dimensional body)
The novel chemical prescription system that the present invention is alleged can be solidified under the effect of electron beam, X-light, ultraviolet light, visible light or daylight.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 the three-dimensional lithographic technique of laser 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.
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 the final state stationary value of 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 the application target after the imaging, 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 description an of necessity.Each prescription resin is to mix and form via the common material technology that is mixed under 30 ℃-80 ℃.After the mixing, with the viscosity of 30 ℃ of Brookfield viscometer measurements.The sample that mechanical meaurement is used is to make on the three-dimensional etching former of the SLA-350 laser that U.S. three dimension system company produces, and in the general ultraviolet baking box irradiation 1 hour.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.Testing material hardness carries out according to American society of test material standards ASTMD1415.The material glass transition temperature test carries out with DMA dynamic mechanical analysis method.The material transmittance adopts the flat board of 1 cm thick to test its transmitance in wavelength 500 nanometers with common visible spectrophotometer.
Example one is to example six
The chemical prescription system that describes below all is the uniform fluent meterial that forms through being mixed.The amounts of components that provides in each example is a percentage by weight.
Annotate: (EO) 20 represent 20 of ethoxy support repetitive sum average out to; CD-1720 is a French Atofina company product, polypropyleneglycol diacrylate; The quality of polyalkylene glycol moiety accounts for 40% in polymethyl siloxane-polyethyleneglycol block copolymer (average Mw=1500).
The test result of the solidfied material that obtains through the three-dimensional etching moulding of laser of these six prescription systems sees table one:
Table one
Example as auxiliary agent and dyestuff use has: can in above-mentioned example six, add defoamer Surfynol 420 to 0.1% weight shares, and phenol red 100ppm, prepared three-dimensional material object is pink.
These instantiations show that chemical prescription system of the present invention has good light transmittance and with the elastic modulus that rubber phase is worked as, satisfies the requirement of medical model articles for use.
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 (11)
1. the photosensitive resin of liquid state chemistry prescription system, this system contains:
(A) at least a organic substance that can carry out cationic polymerization, from the material of following a few class oxygen heterocycle, select:
A) at least a aliphatic series (the comprising alicyclic) compound that contains at least two ring-type oxygen ethylene groups;
B) contain the aliphatic series or the aromatic compounds of at least two oxetane groups;
C) contain the aliphatic compounds of at least two glycidyl ether groups or contain the aromatic compounds of at least one glycidyl ether group, and this compounds that contains poly-alcoxyl support segment;
(B) at least a organic substance that can carry out free radical polymerization, from containing the compound of acryloyl-oxy or methacryloxy group, following several classes select:
A) contain the aliphatic compounds that at least one acryloyl-oxy or methacryloxy are rolled into a ball;
B) contain the aromatic compounds that at least one acryloyl-oxy or methacryloxy are rolled into a ball;
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) at least a aliphatics or aromatic series contain the material of at least two hydroxyls or contain the modified polyalcohol that gathers alkyl siloxane-poly-alkoxy block or random copolymers segment;
(F) can select to use one or more auxiliary agents as required;
(G) can select to use one or more dyestuffs 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 15%-60% of overall prescription system weight;
3. be the compound that contains at least two oxetane groups of the oxetane-functionalization of structural formula in the text (I), (II), (V), (VI), (VII) representative (A) b in the claim 1), its consumption accounts for the 0%-40% of overall prescription system weight.Reasonable be 4-methyl 4-methylol oxetanes ether, to two (the 4-methyl 4-methylol oxetanes) diether, four of benzene methylene glycol-(dimethyl (2-oxetanes propyl group oxygen propyl group) silica) silane, the consumption of its combination in any accounts for the 0%-40% of overall prescription system weight;
4. be to have 4-chloro epoxypropane and ethylene glycol (A) c in the claim 1), tirethylene glycol, multicondensed ethylene glycol, number-average molecular weight is not more than 5000 polyglycol, 1, the 2-propylene glycol, number-average molecular weight is not more than 3000 polypropyleneoxide, 1, the 4-butylene glycol, number-average molecular weight is not more than 2000 PolyTHF, 1, the 3-pentanediol, 1, aliphatic polyols such as 6-hexanediol remove hydrogen chloride and the compound of the such molecular structure of the etherate that generates and have such chemical constitution but by the synthetic compound of other approach, has 4-chloro epoxypropane and phenol, aromatics monohydroxy alcohol or p-dihydroxy-benzene such as methylphenol, 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 hydrogen chloride and the compound of the such molecular structure of the etherate that generates and have such chemical constitution but by the synthetic compound of other approach, and contain the polyoxyethylene segment, polyoxy trimethylene segment, this two classes etherate of poly tetramethylene oxide segment or polyoxy hexamethylene segment, the consumption of its combination in any accounts for the 0%-20% of overall prescription system weight;
5. (B) is (methyl) ethyl acrylate a) in the claim 1, (methyl) Isooctyl acrylate monomer, (methyl) hydroxy-ethyl acrylate, (methyl) hydroxypropyl acrylate, single functionality aliphatic acrylate or methacrylate monomers such as (methyl) acrylic acid ethoxy ethyl ester, perhaps (methyl) acrylic acid and ethylene glycol, tirethylene glycol, multicondensed ethylene glycol, number-average molecular weight is not more than 5000 polyglycol, 1, the 2-propylene glycol, number-average molecular weight is not more than 3000 polypropyleneoxide, 1, the 4-butylene glycol, number-average molecular weight is not more than 2000 PolyTHF, 2,2-dimethyl 1, ammediol, 1, the 6-hexanediol, 2,4,6-trihydroxy hexane, 1,4-methylol cyclohexane, 1,1, the 1-trimethylolpropane, 1,1, the 1-trimethylolethane, trihydroxy methyl or tetramethylol methane etc., and the intermolecular dehydration of the above polyvalent alcohol of these binary and the aliphatic polyol generation esterifications such as etherate polyvalent alcohol that generate generate (methyl) esters of acrylic acid polyfunctionality monomer and with synthetic (methyl) esters of acrylic acid polyfunctionality monomer with such chemical constitution of other approach, the consumption of its combination in any accounts for the 0.5%-40% of overall prescription system weight.Reasonable is trimethylolpropane triacrylate, the glycerol tri-acrylate of ethoxylation, the polyethyleneglycol diacrylate (average Mw=300-1500), poly-1 of ethoxylation, 2-propylene glycol diacrylate (average Mw=500-1500), the consumption of its combination in any accounts for the 0.5%-35% of overall prescription system weight;
6. be (methyl) acrylic acid phenol oxygen ester monomer (B) b in the claim 1), perhaps (methyl) acrylic acid and p-dihydroxy-benzene, catechol, resorcinol, methyl pyrocatechol, number-average molecular weight is not more than 650 phenolics, bisphenol-A, Bisphenol F, bisphenol S, bisphenol A type epoxy resin, aromatic polyol generation esterifications such as bisphenol f type epoxy resin generate (methyl) esters of acrylic acid polyfunctionality monomer and with synthetic (methyl) esters of acrylic acid polyfunctionality monomer with such chemical constitution of other approach, the consumption of its combination in any accounts for the 0.5%-30% of overall prescription system weight.Reasonable is (methyl) acrylic acid phenol oxygen ester, Bisphenol F type or bisphenol type epoxy diacrylate or diacrylate methyl esters (average Mw=300-800), and the consumption of its combination in any accounts for the 0.5%-25% of overall prescription system weight;
7. be to 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 (B) c in the claim 1), promptly above-mentioned (B) be b a) and (B)) two kinds of compounds that situation is alleged are inlaid with alcoxyl support segment, alkyl acyl-oxygen segment or alkyl urethano segment in its molecule.Alleged poly-alcoxyl support segment is meant polyoxyethylene segment, polyoxy trimethylene segment, poly tetramethylene oxide segment or polyoxy hexamethylene 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 this type of component combination in any accounts for the 0%-20% of overall prescription system weight.Reasonable is the dimethylacrylate (average Mw=500-800) of hexane diisocyanate and chain expansion of succinic acid, and its consumption accounts for the 0%-15% of overall prescription system weight;
8. (C) item is one of phenyl sulphur hexafluoro antimonate, phenyl sulphur hexafluoro arsenate, phenyl sulphur hexafluorophosphate, phenyl-iodide hexafluorophosphate or whole in the claim 1, and the consumption of its combination in any accounts for the 0.1%-9% of overall prescription system weight;
9. (D) is styrax compounds, benzoin ether (as benzoin methyl ether, ethyl benzoin ether, isopropyl benzoin ether, phenyl benzoin ether), styrax acetate, acetophenones, phenyl ketal class and phenyl phosphorus oxygen and phenyl phosphinylidyne oxygen class, dimethylbenzene ketone radical photoinitiator in the claim 1, and the consumption of its combination in any accounts for the 0.1%-9% of overall prescription system weight.Reasonable is 2,2-dimethoxy-2 phenyl acetophenone, 1-hydroxy-cyclohexyl benzophenone, triphenylphosphine acyl-oxygen, and the consumption of its combination in any accounts for the 0.1%-5% of overall prescription system weight;
10. (E) item is the line style that has of oligomer type in the claim 1, star-like, the compound that contains two or more hydroxyls of comb type host molecule structure, hydroxyl is in the end, segment is a polyethers, polyester or polycarbonate structure, molecular weight is higher than 100 but softening point is not higher than 60 ℃ aliphatic polyol (reasonable polyglycol is arranged, polypropylene glycol, polytetramethylene glycol (polytetrahydrofuran diol), with glyceryl alcohol or trimethylolpropane as initiator through the alkoxy chain extension and trihydroxy alcohol, (wherein X and Y can be respectively second for poly-X acid Y ester binary or polyvalent alcohol, third, fourth, oneself etc.), poly-(6-caprolactone) trihydroxy alcohol etc.); The molecular weight of having inlayed poly-alkoxy segment (as polyethoxy, propoxyl group, butoxy segment) is higher than 100 but softening point is not higher than 60 ℃ aromatic polyol (as p-dihydroxy-benzene, catechol, resorcinol, methyl pyrocatechol, 2,6-two (the hydroxyl tert-butyl group) phenol, bisphenol-A, Bisphenol F, bisphenol S etc.); Or the block of polymethyl siloxane or PSI and polyglycol, polypropylene glycol or polytetramethylene glycol or random copolymers (wherein gathering the shared massfraction of alkoxy portion between 30%-70%), contain at least two terminal hydroxy groups, mean molecular weight is not higher than 1500.This compounds is reasonable to have mean molecular weight to gather 1 at polyglycol, the mean molecular weight of 200-1500 200-1000's, (mean molecular weight is between 600-1500 at polytetramethylene glycol, the polymethyl siloxane-polyethyleneglycol block copolymer of 200-800 for 2-propylene glycol, mean molecular weight, the shared massfraction of polyglycol is between 30%-70%), the consumption of its combination in any accounts for the 1%-50% of overall prescription system weight;
11. 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.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910000682A CN101776844A (en) | 2009-01-14 | 2009-01-14 | Photocuring component used for three-dimensional imaging |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910000682A CN101776844A (en) | 2009-01-14 | 2009-01-14 | Photocuring component used for three-dimensional imaging |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101776844A true CN101776844A (en) | 2010-07-14 |
Family
ID=42513334
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200910000682A Pending CN101776844A (en) | 2009-01-14 | 2009-01-14 | Photocuring component used for three-dimensional imaging |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101776844A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013067947A1 (en) * | 2011-11-08 | 2013-05-16 | Henkel (China) Company Limited | Dual-curable adhesive composition, use thereof, and process for bonding substrates |
| CN103282388A (en) * | 2010-10-19 | 2013-09-04 | 马克斯·普朗克科学促进学会 | Ultra fast process for the preparation of polymer nanoparticles |
| CN103298840A (en) * | 2010-10-19 | 2013-09-11 | 马克斯·普朗克科学促进学会 | Process for the modification of polymers, in particular polymer nanoparticles |
| CN108475011A (en) * | 2016-01-28 | 2018-08-31 | Dws有限公司 | For the photo curable resin combination of Stereo Lithography moulding manufacture, with the three-dimensional article and relative manufacturing process of the composition production |
| CN109343309A (en) * | 2018-12-03 | 2019-02-15 | 深圳市华星光电技术有限公司 | Negative photoresist and its application |
| CN110140086A (en) * | 2016-12-23 | 2019-08-16 | 3M创新有限公司 | Printable composition, product including polymer and polymerizable components and the method that product is prepared by it |
| WO2024070348A1 (en) * | 2022-09-26 | 2024-04-04 | 東レ株式会社 | Resin composition, cured product, scintillator panel, and inductor |
-
2009
- 2009-01-14 CN CN200910000682A patent/CN101776844A/en active Pending
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103282388A (en) * | 2010-10-19 | 2013-09-04 | 马克斯·普朗克科学促进学会 | Ultra fast process for the preparation of polymer nanoparticles |
| CN103298840A (en) * | 2010-10-19 | 2013-09-11 | 马克斯·普朗克科学促进学会 | Process for the modification of polymers, in particular polymer nanoparticles |
| WO2013067947A1 (en) * | 2011-11-08 | 2013-05-16 | Henkel (China) Company Limited | Dual-curable adhesive composition, use thereof, and process for bonding substrates |
| CN103917619A (en) * | 2011-11-08 | 2014-07-09 | 汉高股份有限公司 | Dual-curable adhesive composition, use thereof, and process for bonding substrates |
| CN103917619B (en) * | 2011-11-08 | 2016-08-17 | 汉高股份有限及两合公司 | Dual-curing adhesive composition and application thereof and the method for bonded substrate |
| TWI572692B (en) * | 2011-11-08 | 2017-03-01 | 漢高股份有限公司 | Dual-curable adhesive composition, use thereof, and process for bonding substrates |
| CN108475011A (en) * | 2016-01-28 | 2018-08-31 | Dws有限公司 | For the photo curable resin combination of Stereo Lithography moulding manufacture, with the three-dimensional article and relative manufacturing process of the composition production |
| CN110140086A (en) * | 2016-12-23 | 2019-08-16 | 3M创新有限公司 | Printable composition, product including polymer and polymerizable components and the method that product is prepared by it |
| US11602412B2 (en) | 2016-12-23 | 2023-03-14 | 3M Innovative Properties Company | Printable compositions including polymeric and polymerizable components, articles, and methods of making articles therefrom |
| CN109343309A (en) * | 2018-12-03 | 2019-02-15 | 深圳市华星光电技术有限公司 | Negative photoresist and its 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 |
| WO2024070348A1 (en) * | 2022-09-26 | 2024-04-04 | 東レ株式会社 | Resin composition, cured product, scintillator panel, and inductor |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101776846B (en) | Light-cured component for laser stereo lithography | |
| CN1322371C (en) | Solid imaging compsns. for preparing polypropylene-like articles | |
| CN101776844A (en) | Photocuring component used for three-dimensional imaging | |
| CN101466767B (en) | resin composition for stereolithography | |
| KR101341081B1 (en) | Resin composition for optical three-dimensional molded object | |
| CN101178539A (en) | Photo-curable resin composition | |
| WO2017177795A1 (en) | Free radical-cation hybrid photocuring system and applications thereof | |
| JP4969137B2 (en) | Optical three-dimensional resin composition | |
| JP5210645B2 (en) | Optical three-dimensional resin composition | |
| JP4516019B2 (en) | Three-dimensional structure and manufacturing method thereof | |
| JP5266131B2 (en) | Optical three-dimensional resin composition | |
| JP5280610B2 (en) | Active energy ray-curable resin composition for optical three-dimensional modeling with improved stability | |
| JP5111774B2 (en) | Optical three-dimensional resin composition | |
| EP0833205B2 (en) | Three-dimensional object by optical stereography and resin composition for producing the same | |
| JP6091342B2 (en) | Optical three-dimensional resin composition | |
| WO2009145167A1 (en) | Resin composition for optical three-dimensional molding | |
| JP5393239B2 (en) | Processing method for optical three-dimensional object | |
| WO2015068820A1 (en) | Resin composition for optical three-dimensional molding | |
| JP3974336B2 (en) | Active energy ray-curable resin composition for optical three-dimensional modeling | |
| JPH11240939A (en) | Photocuring liquid resin composition | |
| JP5738367B2 (en) | Optical three-dimensional model with low yellowness | |
| JP5205018B2 (en) | Optical three-dimensional resin composition | |
| JP2009203306A (en) | Resin composition for optical three-dimensional shaping | |
| JP5302022B2 (en) | Optical three-dimensional resin composition | |
| EP3429833A1 (en) | Radiation curable compositions for additive fabrication with improved toughness and high temperature resistance |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Open date: 20100714 |