JPH0511449A - Solid lithographic method depositing three-dimensional article and curing composition - Google Patents

Abstract

PURPOSE: To make it possible to impart toughness and non-embrittlement post- curing characteristic and to maintain a high curing rate by using a thiol-nene compd. of a photosetting resin system having low shrinkability in place of acrylate having high shrinkability. CONSTITUTION: This method consists of a stage for curing the curable liquid resin compd. until articles are completely deposited by each subsequent layer pattern of the bath of this compd., then removing the articles from the liquid resin bath and subjecting the articles to post-curing. The compding of the liquid resin consists of (a) a first compd. having plural thiol groups thereon, (b) a second compd. having the plural thiol groups therein and (c) a free group photoinitiator and the total functionality of the compounding is >=4.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a solid lithographic printing method for depositing a three-dimensional article and a hardening composition.

[0002]

BACKGROUND OF THE INVENTION The term "stenorography" refers to the compound solid three-dimensional by the action of patterned photo-curing of the liquid surface, which cures successive thin layers of a photo-curable liquid composition using a computer controlled laser. It means the method of production of an object. This technology is based on Murphy's "Radiation Curing", February 1989, 5
“Reduced. Destortion.” On pages 3 to 7 of the monthly issue.
Inn. optical. free. Form. Fabrications. With. UV laser (Reduced De)
storage in Optical Free
Form Fabrications with UV
Lasers "and" Chemical Week (Chem
No. 24, September 9, 1987
25 to 25 and US Pat. Nos. 4,575,330, 4,
801,447, 4,929,402 and 4,75
2,498, all of which are incorporated herein by reference.

To date, various acrylic acid ester monomers have been commonly used as photocurable liquids in three-dimensional lithographic printing due to their fast UV response time and lack of curability outside the irradiation boundaries. Came. However, acrylic esters also have a very high shrinkage upon curing which, even in stereolithography, severely limits the practical use effect.
As successive layers are deposited, the composite object is susceptible to deformation due to the difference in contraction between parts of the object.

[0004]

Whilst low shrinkage photocurable resin systems, such as photocurable epoxy system formulations, are well known, such systems do not allow continuous curing outside the irradiation boundaries. Lower UV than acrylic monomer for
It is generally considered to have corresponding or / and large potential. Therefore, such systems have hitherto not been accepted as unfavorable for three-dimensional lithographic printing applications.

US Pat. No. 4,808,638 describes a photocurable thiolene composition comprising a norbornene functional resin, a polythiol and a free radical photoinitiator. A further explanation of this system can be found in 1989, "Science.
and. Engineering "Volume 60, 211-2
See "Proceedings of ACS Division." By Jacobine et al.
Ov. Polymeric. Materials (Proceedi
ngs of ACS Division ofPol
ymeric Materials) ”.

The present invention is a thiol-ene resin system (hereinafter "thiol-nene") based on a conventional acrylic resin based on a curable norbornene of the type disclosed in US Pat. No. 4,808,638. It aims to provide a new method of three-dimensional lithographic printing that replaces

[0007]

SUMMARY OF THE INVENTION The present invention is a three-dimensional lithographic printing method for depositing a three-dimensional article, wherein successive layers of a curable liquid resin formulation bath are cured in a pattern until the article is completely deposited. Further improving the three-dimensional lithographic printing process comprising the steps of removing the article from the liquid resin bath and post-curing the article, wherein the liquid resin comprises (a) a first compound having a plurality of norbornene groups thereon, b) a thiol-nene blend comprising a second compound having a plurality of thiol groups therein, and (c) a free radical photoinitiator, characterized in that the total functionality of the blend is 4 or more. .

We have found that the significant advantages of thiol-nene formulations over acrylic formulations in three-dimensional lithographic applications provide faster curability, lower shrinkage and sufficient dimensional stability after post cure. I found that it is given by doing. The formulation also has very low toxicity. Particularly preferably, the resin system is a norbornene carboxylic acid ester of an alkane polyol, an alkoxylated bisphenol-
It is based on A diols or mixtures thereof and polyesters of α- or β-mercapto acids. Such materials can impart a wide variety of mechanical and Tg properties to the post-cured product. For example, acrylic formulations industrially compounded for three-dimensional lithographic printing prior to the present invention produced highly brittle post-cure products, which were very susceptible to breakage during the manufacture of thin walled articles. However, as described below, the thiol-nene blends of the present invention are readily compoundable, while imparting tough, non-brittle post-curing properties, while curing faster than the brittle acrylic resins previously described. Hold the speed.

[0009]

The typical three-dimensional lithographic printing process to which the present invention pertains involves the step of depositing a three-dimensional object in a liquid resin bath by patternwise curing successive thin layer portions of said object.

In most conventional methods, a sequential UV laser traces at the surface of the curable liquid on the submersible platform, depositing each layer and then incrementally lowering to deposit the object. As the platform is lowered, liquid resin flows over the previous layer and the laser imparts a smooth liquid surface that traces the next layer. When the article is complete, it is removed from the bath and drained or washed, but the resin in the object is only partially cured. This is called the "green" stage. Stabilization and strengthening of the article usually involves post-cure. Post-curing is usually accomplished by subjecting the entire object to prolonged exposure to UV floodlight, but other techniques such as oven curing are also described in the literature.
Industrial equipment for carrying out such a three-dimensional lithographic printing method is available, for example, from 3D Systems.

The plurality of norbornene functional compounds useful in the present invention are those well known in US Pat. No. 4,808,638, which was recently published in 1990 by the American Chemical Society ( American
Chemical Society ACS Symposium Series # 417, "Radiation. Curing of Polymeric Materials (Radia).
tion Curingof Polymeric M
13), Jacobin (Ja
Cobine) et al., “Photoinitiated Crosslinking of Norbornene Resins with Multifunctional Functional Thiols”.
king of Norbornene Resins
with Multifunctional Thiol
s), which is also incorporated herein by reference. Further examples of suitable norbornene functional resins are provided in the general examples 1-19 below. Particularly preferred norbornene compounds are norbornene carboxylate esters of polyols such as 1,6-hexanediol, trimethylolpropane, ethoxylated bisphenol A, and mixtures thereof.

The polythiol component of this inventive composition can be any compound having more than one thiol group per molecule. A suitable polythiol is
U.S. Pat. No. 3,661,744, column 8, line 76 to column 9, line 46, and U.S. Pat. No. 4,119,617.
No. 7, col. 40-57, U.S. Pat.
45,419 and U.S. Pat. No. 4,289,867.
No. Particularly preferred polythiols are those obtained by esterification of polyols with α- or β-mercaptocarboxylic acids such as thioglycolic acid or β-mercaptopropionate. Particularly preferred polythiols are pentaerythritol tetramercaptoacetate, and pentaerythriol tetrakis-β-.
Mercaptopropionate (PETMR).

The ratio of polyene to polythiol component can be varied over a wide range. Generally, the thiol ene (en
It is preferred that the ratio to group e) is 0.7: 1 to 1.3: 1, but ratios outside this range can be usefully used in some cases without departing from this invention.

The curable composition using the norbornene functional compound of the present invention may contain both a bifunctional norbornenyl compound and a bifunctional thiol compound, but at least one of these components and at least one of these components may be included. 1 in part
It is necessary to include more than one functional group per molecule to form a crosslinked product upon curing. In other words, the sum of the average number of norbornene groups per molecule of norbornene functional compound and the average number of co-reactive thiol groups per molecule of thiol functional compound is 4 when a crosslinked cured product is desired. It must be above. This sum is referred to as the "total reactive functionality" of the composition.

The initiators used in the curable thiolene formulations are those suitable for free radical photoinitiators. Examples of free radical photoinitiators include benzoin and substituted benzoin compounds, such as those described in US Pat. Nos. 4,616,826 and 4,604,295, benzophenones, Mitchler's ketones, dialkoxybenzophenones, and dibenzophenones. Includes alkoxy acetophenone and peroxy ester. The photoinitiator is in an amount effective to initiate cure of the formulation, typically 0.
5 to 5% is used.

The formulation also preferably includes a stabilizer. Preferred stabilizers are described in U.S. patent application Ser. No. 07 / 612,759, filed Nov. 13, 1989, in Irish Application No. 3638/89, which is incorporated herein by reference. There is. Said stabilizer is a non-acidic nitroso compound, in particular N-nitrosohydroxylamine and its salts. Suitable of said compounds are the aluminum salts of N-nitrosophenylhydroxylamine, which can be usefully used at levels of about 100 ppm to 2%, preferably 500 to 10,000 ppm.

Although stabilized, thiol-nene formulations are extremely sensitive to fluorescent light and therefore need to be kept in the dark for at least several days to stabilize. If storage is required for several months or more, it is necessary to separate the nene and the thiol compound into a two-part formulation.

Triiodide and other polyiodides are thiol
It has been found to be useful as a shelf life stabilizer for Nene formulations. No studies have been conducted to date on the use of said stabilizers in three-dimensional lithographic printing. It is highly preferred to include them in the thiol nenes used in the present invention if they can be easily determined by those skilled in the art, i.e. stabilizers do not significantly reduce the UV response. Suitable polyiodide stabilizers are k
l / l ₂ (1: 2 by weight) of 10 to 2,000 pp
ml ₂ , preferably at a level of giving 30 to 800 ppml ₂ . kl / where the concentration of l ₂ is 1N
solution of l ₂ is suitable as the solution. Compatible solvents such as lower alcohols can also be used to incorporate the polyiodide stabilizer into the formulation. The kl / l ₂ solution is appropriately added to either norbornene resin or thiol resin and then mixed.

The usefulness of thiol-nene for use in three-dimensional lithographic printing is surprising from the standpoint of the difference in curing function between both acrylic and thiol-nene systems. The thiol-nene mechanism is a step-growth chain transfer mechanism, which is considered to be very sensitive to the growth of polymerization reaction beyond the irradiation boundary. Therefore, the line reso
It is believed that this occurs when the resin is irradiated with a UV laser. Polymer growth reactions outside the laser passage, which sometimes lead to severe partial line contamination or growth of polymer "nodules" beyond the laser passage, are observed in the thiol-nene system at cure depths of 4 mm and above. However, it has a typical incremental cure depth of about 5 to 20.
A mil, most typically 10-12 mils, is not a significant issue.

[0020]

Example 1 End, synthesis of exo-norborn-2-ene-5-carbonyl chloride, I Magnetic stirrer, effective condenser, constant pressure addition funnel, and "Thermowatch ^(TM) " thermostatic controller In a 1000 ml, 4-neck, round bottom flask equipped with a thermometer, acryloyl chloride (271.8 g, 3.00 mol) was stirred under a nitrogen atmosphere. Fresh decomposition Distilled cyclopentadiene monomer (1
98.2 g, 3.00 mol) was added at such a rate that the reaction temperature did not exceed 80 to 90 ° C. at any time during the addition. Upon completion of addition, the reaction was stirred for an additional 3 hours. Residual starting material was removed using a water aspirator, then the crude reaction mixture was distilled in vacuo to give the purified product (4
Boiling point 66 to 70 ° C. in mmHg). Example 2 End, Synthesis of Exo-Norborn-5-ene-5-Carbonyl Chloride, II Magnetic Stirrer, Effective Condenser, Constant Pressure Funnel and Thermometer Connected to "Thermowatch ^(TM) " Constant Temperature Controller 1
Freshly distilled methacryloyl chloride (250 g, 2.391 mol, Aldrich Chemical Co.) was stirred in a nitrogen atmosphere in a 000 ml, 4-neck, round bottom flask. Fresh decomposition Distilled cyclopentadiene monomer (173.62g,
2.63 mol) at any time during the reaction temperature addition of 80
It was added at a rate not exceeding ~ 90 ° C. The reaction was stirred for an additional 3 hours when the addition was complete. Residual starting material was removed using a water aspirator, after which the crude reaction mixture was distilled in vacuo to a purified product (bp 74-76 ° C at 4-7 mmHg). Example 3 Endo, exo-norborn-5-en-5-methyl,
Endo, synthesis of exo-norborn-2-ene-5-carboxylate, III Nonbornene carboxaldehyde (100 g, 8.18)
Mole, Altrich. Chemical company) funnel with constant pressure,
2000 ml, 3-neck, round-bottomed flask equipped with thermometer and effective condenser for isopropoxide aluminum (2
0.0 g) in a nitrogen atmosphere. An external cooling facility was installed to maintain the reaction temperature at 50 ° C. by external cooling, and the addition rate of the aldehyde was slowed down. The reaction mixture was aged at a temperature of 60 ° C. for 2 hours and then cooled. The reaction mixture was then distilled with 100 ml of hexane, water (3 x 400 ml).
(Twice) washing, filtration to remove solid fine particles, and condensation with a rotary evaporator. The crude reaction mixture was then distilled in vacuum to give a purified product (boiling point 1 at 2.5-4 mmHg).
25 to 130 ° C). Example 4 Synthesis of endo, exo-norborn-2-ene-5-isocyanate, IV Sodium azide (22 ml in 250 ml deionized water,
8.47 g, 3.51 mol) was placed in a 4 L beaker, and norborn-2-ene-5-chloride was added to dichloromethane (1000 ml) cooled to a temperature of 5-10 ° C.
Carbonyl (500 g, 3.19 mol) and tetra- (n-butyl) ammonium bromide (2.5 g, 0.007).
(7 mol) was added dropwise to the stirred solution while maintaining the temperature throughout the reaction. After the addition was complete, the organic layer was separated, dried over anhydrous sodium sulfite and filtered. After that, the filtered solution was distilled (500 m) for distillation.
1) was added, and the solution was added dropwise to a 2 L round bottom flask maintained at a temperature of 70 ° C. Dichloromethane was removed by distillation (overhead temperature 50-55 ° C) and collected.
After the addition was complete, the temperature of the reaction temperature was maintained at 70 ° C for 2 hours. The reaction mixture was then condensed on a rotary evaporator and distilled in vacuo. The purified product has a boiling point of 6 at 115 mmHg.
Collected as a 0-65 ° C. cut. Example 5 Endo, exo-2- (norborn-5-ene-5)-
Synthesis of 4,4-dimethyloxazoline-5-one-norbornene azlactone (NAz), V 1000 ml equipped with a magnetic stirrer, effective condenser, constant pressure addition funnel and thermometer, 4-neck, round bottom flask, 2-vinyl- 4,4-Dimethyloxazolin-5-one (50
1.66 g, 3.61 mol, SNPE, Princeton, NJ) was stirred under a nitrogen atmosphere. The solution was kept at a constant temperature of 40 ° C. by a “Thermowatch ^(TM) ” controller, and the reaction temperature was 90 to 90 during the process of adding freshly decomposed and distilled cyclopentadiene monomer (262.3 g, 3.97 mol). It was added at a rate not exceeding 100 ° C. When the addition was complete, the reaction was aged at a temperature of 95 ° C. for 2 hours,
Then, it condensed with the rotary vaporizer and removed the excess cyclopentadiene monomer. Distill the crude mixture in vacuum (0.2 m
The boiling point was 70 to 73 ° C. at mHg, and the purified product was produced as a colorless liquid which rapidly solidified at room temperature (yield 689.
7 g, 93% Th. ). High field
field) Nuclear magnetic resonance analysis (300 MHz) showed that the distillate was essentially pure with the mixture of endo and exo isomers of the desired product. Example 6 Synthesis of methyl norborn-5-ene-2-chloroformate,
VI Norborn-5-ene-2-methanol (196.20
g, 1.58 mol, Aldrich Chemical Co.) was stirred with 1000 ml of a magnetic stirrer, dry ice condenser, constant pressure addition funnel and thermometer, 3 neck, toluene (250 ml) in a round bottom flask. The reaction was carried out in a nitrogen atmosphere and the outlet of the bubble tube was vented to a dilute solution of sodium hydroxide. The solution is cooled to a temperature of about 10 ° C. and a solution of phosgene (171.9 g, 1.738 mol) in toluene (250 ml) is added at a reaction temperature of 25
It was added by instillation at a rate not exceeding ° C. Upon completion of addition, the reaction was warmed to room temperature and stirred for 6 hours. Excess phosgene was removed by internal nitrogen sparge at a temperature of 30 ° C. for 3 hours. Excess phosgene was removed on a rotary evaporator and the purified product was flash vacuum distilled (oil temperature 150 ° C, 1.5 mmH
boiling point 75 g to 80 ° C.). Example 7 1,6-hexamethylenedi (norborn-2-ene-5)
-Methyl) carbonate synthesis, VII Norborn-2-ene-methanol (314 g, 2.5
32 mol) and pyridine (217 g, 2.75 mol) under nitrogen atmosphere, effective condenser, thermometer and 1,6-hexemethylene bis-chloroformate (300 g, 1.235).
Mol) and placed in a 2000 ml, 4-neck, round bottom flask equipped with a normal pressure addition funnel and stirred. The chloroformate was added at such a rate that the reaction temperature did not exceed 80 ° C during the addition. Upon complete addition, the reaction mixture was aged for 3 hours and then cooled to ambient temperature. Celite the reaction mixture.
Filtered through ^(TM) diatomaceous earth and the filtrate condensed on a rotary evaporator. The crude liquid was then placed in a 2 inch wipe film vaporizer (Pop Scientific, Menomonie, Wis.) At a temperature of 125 ° C. and 0.5 mm.
Permeation was carried out at a pressure of Hg. The yield of viscous oil is 473.1 g.
Met. Example 8 1,6-hexamethylenedi- (norborn-2-ene-
5-Carbamate), VIII Norborn-5-ene-methanol (145.04 g,
1.168 mol, manufactured by Aldrich Chemical Co., in a nitrogen atmosphere, together with toluene (200 ml) and diazabicycloundecane (DBU, 2.0 g), mechanical stirrer, thermometer and hexamethylene diisocyanate (95.34).
(g, 0.567 mol) with a normal pressure addition funnel 1
The mixture was placed in a 000 ml 4-neck, round bottom flask and stirred. Diisocyanate was added dropwise to bring the reaction temperature to 70
Raised to 0 ° C. Once the addition was complete, the reaction mixture was held at this temperature for 3 hours and the progress of the reaction was monitored by infrared spectroscopy (ca, 2271 cm ⁻¹ -NCO zone). Upon completion, the reaction mixture was cooled and toluene was removed on a rotary evaporator. The product was collected as a pale yellow syrup, which gradually crystallized on standing at room temperature. The yield of crude product was 238.5 g. Example 9 1,6-hexamethylenedi- (norborn-2-ene-5
-Carboxamide), IX Hexamethylenediamine (100 g, 0.861 mol)
And pyridine (153.3g, 1.94mol) are equipped with a mechanical stirrer, a thermometer attached to a "Thermowatch ^(TM) " thermostatic controller, and a constant pressure addition funnel equipped with 2000ml, 4-neck, round bottom flask with toluene (750ml). ) Was added and the mixture was stirred in a nitrogen atmosphere. Norborn-2-ene-5 carbonyl chloride (1,276.09 g, 1.76 mol) was added dropwise at a rate such that the temperature gradually increased to 75 ° C during the addition process. After the addition was complete, the reaction mixture was stirred for 2 hours and then methanol (5 g, 0.156 mol).
Was also added to react with a slight excess of acid chloride. Filtration of pyridine hydrochloride followed by condensation of the filtrate on a rotary evaporator gave a crude product as a viscous oil which solidified on standing. The yield of crude product was 159.4 g. Example 10 Synthesis of 1,6-hexanediol di- (endo, exo-norborn-2-ene-5-carboxylic acid salt (HDDN), X hexanediol diacrylate (6054.5 g, 2
(6.79 mol) was placed in a 12 l, 4-neck, round bottom flask equipped with a mechanical stirrer constant pressure addition funnel, an effective condenser and a thermometer connected to a "Thermowatch ^(TM) " temperature controller and stirred under a nitrogen atmosphere. Freshly decomposed, distilled cyclopentadiene monomer (3541.6 g, 53.58 mol) was added at a rate such that the reaction temperature did not always exceed 65 ° C during the addition. When the addition was complete, the reaction mixture was heated to a temperature of 90 ° C. and aged at this temperature for 2 hours. Excess cyclopentadiene was removed by vacuum distillation and the crude product was stripped there in a 2 inch wiped film vaporizer at a temperature of 50-60 ° C. and a pressure of 0.2 mm Hg. The resin yield was 9331.9 g. Example 11 Bis-2,2- [4- (2- [norborn-2-ene-
5-carboxy] ethoxy) phenyl] propane,
(Ethoxylated bisphenol A di- (norborn-2-
Ene-5-carboxylate), synthesis of (EBPA DN), XI ethoxylated bisphenol A diacrylate (700
g, 144 moles, 2.88 equivalents “Saltomer (Sar
Tomer) a ^(TM) 349) equipped those above 20
00 ml, 4 neck, round bottom flask was placed and stirred.
Cyclopentadiene monomer (198g, 3.0mol)
Was added at such a rate that the reaction temperature remained at about 90 ° C. at the end of the addition. The extent of reaction was monitored by HPLC (acetonitrile water, UV detector 254 nm). When the reaction was complete, the reaction mixture was heated to a temperature of 120 ° C. to remove excess cyclopentadiene monomer and dimer in a vacuum condenser. The norbornene functionalized resin was recovered in quantitative yield and the absence of acrylic unsaturation was measured using NMR spectroscopy to equalize the resin (bicyclic unsaturation vs. ether methylene group integration). Example 12 Synthesis of trimethylolpropane tri- (norborn-2-ene-5-carboxylate) (TMPTN), XII Trimethylolpropane triacrylate (338 g,
1.0 mol) to Friedrich
1000 ml equipped with a condenser, a thermometer, a constant pressure addition funnel and a mechanical stirrer, was placed in a 4-neck, round bottom flask and stirred at a temperature of 40 ° C. in a nitrogen atmosphere. The reaction temperature of freshly decomposed cyclopentadiene monomer (217 g, 3.3 mol)
It was added at such a rate that it gradually rose to about 90 ° C. by the end of the addition. The extent of reaction was monitored by the decrease in the infrared absorption band at 1636 cm ^-1 . When the reaction was judged to be complete (no change in infrared absorption was observed), excess cyclopentadiene was removed by vacuum condensation of the resin. The resin yield was 534 g. Example 13 Synthesis of pentaerythritol tetra- (norborn-2-ene-5-carboxylate) (PETN), XIII pentaerythritol tetraacrylate (2500
g, 7.89 mol, acrylate equivalent of 16.59)
Was placed in a 5 l, 4-neck, round bottom flask equipped with mechanical agitation, a Friedrich condenser, a constant pressure addition funnel and a thermometer connected to a "Thermowatch ^(R) temperature controller" and stirred under a nitrogen atmosphere. Pentazine monomer (1151.38 g, 17.48 mol) was added to the stirred reaction mixture at a rate such that the reaction temperature gradually increased to 50 ° C. during the addition process, sometimes requiring external cooling.
When the addition was complete, the reaction mixture was stirred at a temperature of 50 ° C. for 2 hours, after which excess cyclopentadiene was removed by vacuum distillation. The crude product is then added to 2 inches (about 5.1
cm) with a wipe film vaporizer at a temperature of 50 ° C. and a pressure of 0.
Stripped at 2 mmHg. Product recovery was quantitative. Example 14 2,2-Bis- [4- (norborn-2-ene-5-carboxy) cyclohexyl] propane, hydrogenated bisphenol A di- (norborn-2-ene-5-carboxylate) (HBPADN) Synthesis, XIV Hydrogenated Bisphenol A (441g, 1.84mol)
Mechanical stirring, constant pressure addition funnel, and "Thermo Watch
^(TM) ”in a 3L, 4 neck, round bottom flask equipped with a thermometer connected to a temperature controller, add triethylamine (39
4.64 g, 3.90 mol) and 4-dimethylaminopyridine (0.10 g) with dioxane (1750 ml)
And stirred in a nitrogen atmosphere at a temperature of 70 ° C. Norborn-2-ene-5-carbonyl chloride (1,581.40
g, 3.71 mol) was added dropwise so that the reaction temperature never exceeded 90 ° C. Once the addition was complete, the reaction mixture was stirred at a temperature of 90 ° C. for a further 4 hours and then cooled to room temperature. Triethylamine hydrochloride was removed by filtration. After that, the filtrate was diluted with 2000 ml of dichloromethane and diluted with 5% aqueous sodium hydroxide solution (300 ml, 2 ml).
Washed 2 times), 2MHcl (300 ml, 2 times), and finally with deionized water (300 ml, 3 times). The solution was dried over anhydrous sodium sulfite, filtered and condensed on a rotary evaporator. The crude product, which was recrystallized from heptane and dried overnight in a vacuum oven, had a melting point of 166-176 ° C. The yield of purified product was 334 g. Example 15 Bis-2,2- [4- (2-norborn-2-ene-6
Synthesis of -carboxy-5-carboxy] ethoxy) phenyl] propane, XV ethoxylated bisphenol A (dianol 22, 158)
g, 0.50 mol), nadic anhydride (168.9 g,
1.03 mol), pyridine (81.37 g, 1.03 mol) and 4-dimethylaminopyridine (12.2 g,
0.1 mol) was placed in a 2000 ml, 4-neck, round bottom flask equipped with mechanical stirring, effective condenser and thermometer and stirred in toluene (600 ml) under nitrogen atmosphere. The reaction mixture was heated at a temperature of 70 ° C. for 3 hours and then at a temperature of 100 ° C. for 6 hours. Infrared spectroscopy of the reaction (1740c
m ⁻¹ band). When the reaction was judged to be complete, the solution was cooled to room temperature, 3 MHcl (600 m
1, once) and the organic phase was separated. The solvent was removed on a rotary evaporator and replaced with dichloromethane (600 ml). Then, the solution is deionized water (200 ml, twice).
After washing with water, drying over sodium sulfite, filtering and condensing in a rotary evaporator, the crude composition was obtained as a glassy solid. The product yield was 320 g. Example 16 Poly (tetramethylene oxide 650) di- (norborn-
Synthesis of 5-ene-2-) methyl carbonate, XVI hydroxy-terminated poly (tetramethylene ether 650) (232.91 g, 0.719 equivalent OH)
1000 ml, 4-neck equipped with a mechanical stirring, pyridine (64.3 g, 0.814 mol), a thermometer, and a constant pressure addition funnel containing methyl norborn-5-ene-2-chloroformate (150 g, 0.74 mol). , Placed in a round bottom flask and stirred in toluene (300 ml) under nitrogen atmosphere. Chloroformic acid was added at such a rate that the reaction temperature gradually increased to 60 ° C during the addition. When the addition was complete, the reaction mixture was aged at a temperature of 70 ° C. for 3 hours, at which time methanol (5.0 g, 0.16 mol) was added to the reaction mixture. The reaction mixture was designated as “Celite”.
e ^(TM) ) diatomaceous earth and the filtrate was condensed in a rotary evaporator to remove the solvent. The crude yellow oil was then passed through a 2 inch wipe film vaporizer at a temperature of 125 ° C. and a pressure of 0.3 mm Hg. The product yield was 328 g. Example 17 Synthesis of poly (tetramethylene oxide 650) -di- (norborn-2-ene-5-carboxylic acid salt) XVII Hydroxy terminated poly (tetramethylene oxide 6)
50, poly TMO) (401.94 g, 1.241 eq OH, BASF Corp. of Parsippany, NJ) and pyridine (111.06 g, 1.41 mol) mechanically stirred, thermometer and norborn-2- It was placed in a 2000 ml, 4-neck, round bottom flask equipped with a constant pressure addition funnel containing ene-5-carbonyl chloride (200 g, 1.278 mol) and stirred in toluene (400 ml) under nitrogen atmosphere. The acid chloride was added at such a rate that the reaction temperature gradually increased to 70 ° C during the addition. When the addition was complete, the reaction mixture was aged at a temperature of 70 ° C. for 3 hours, at which time methanol (5.0 g, 0.16 mol) was added to the reaction mixture. The reaction additive was filtered through "Celite ^(TM) " diatomaceous earth and the filtrate was condensed on a rotary evaporator to remove the solvent. After that, add 2 inches of crude oil (about 5.1c
m) The temperature of 125 ° C, 0.4m in the wipe film vaporizer
Permeation was carried out at a pressure of mHg. Product yield 535 g
(96.5% Th.). Example 18 Poly (tetramethylene oxide 650) di- (norborn-
Synthesis of 2-ene-5-carbamate, XVIII Hydroxy-terminated poly (tetramethylene oxide 6)
50) (174.74 g) with mechanical stirring, thermometer, and norborn-2-ene-5-isocyanate (75 g,
0.556 mol) 500 with a constant pressure addition funnel
ml, 4-necked, placed in a round bottom flask and stirred with diazabicycloundecane (0.5 g) in a nitrogen atmosphere. Isocyanate was added at a rate such that the reaction temperature did not exceed 35 ° C during the addition. Then the reaction mixture is heated to 70 ° C.
It was heated to and maintained at that temperature for 6 hours. If there is no further change in the NCO band by infrared spectroscopy analysis, the reaction mixture is cooled and the crude oil is then removed by 2 inches (about 5.1 cm).
Use a wipe film vaporizer at a temperature of 125 ° C and 0.4 mmH.
It was permeated at a pressure of g. The crude oil yield was 243.3 g. Example 19 Synthesis of poly (tetramethylene oxide 650) di- [2- (norborn-2-ene-5-carboxamide) -2,2-dimethylacetate], XIX 2- (nonborn-2-ene-5)- 4,4-Dimethyloxazolin-5-one (130.36 g, 0.636
Mol), poly (tetramethylene oxide 650) with hydroxy end groups (200 g) and diazabicycloundecane (3.31 g) in a 1000 ml, 4-neck, round bottom flask equipped with mechanical agitation and an effective condenser and thermometer. And stirred in a nitrogen atmosphere. The reaction mixture was heated to a temperature of 100 ° C. 8 hours later, 1817 cm by infrared spectroscopy
It was found that the unique azlactone carbonyl band at ^-1 had completely disappeared. The crude product was then placed in a 2 inch wipe film vaporizer at 125
It permeated at a temperature of ° C and a pressure of 0.4 mmHg. The yield of viscous oil was 314.8 g. Example 20 Mechanical Properties of Norbornene-Thiol Copolymer A curable composition was prepared by mixing equal amounts of norbornene functional resin with a crosslinked thiol and a photoinitiator. The specimen mechanical testing were cured in "Fusion ^(TM) (Fusion)" conveyor of dual lamp devices of the system (2H sphere). Direction perpendicular torsion in tensile properties "Instron ^{(TM) (Instron)} modified using the 20 mil film at universal testing machine model 4505 ASTM, D-883 rheometric dynamic analyzer RDAII Dynamic mechanical test was measured according to the test The strain and repetitive sweeps were performed on duplicate samples to ensure that they were done in the linear response region of the temperature sweep.

The mechanical and dynamic mechanical properties of these resins were first focused on the study of the properties of thin films produced from the copolymerization of PETMP with norbornene functional monomers.
Thin film and norbornene resin and cross-linked thiol (PE
Not only the behavior of the different functional groups (such as ester vs. amidourethane) studied as a single component mixture (constant throughout the TMP study), but also the effect of the level of functionality (f) in the norbornene resin is featured (f = 2). Vs. 3, 4, etc.). The properties of cured films of these materials are shown in Table 1.

While Tg correlates well with functionality, the tensile modulus correlation appears to be somewhat sporadic. Best Tg
Was achieved with a film of resin XIII (tetrafunctional pentaerythritol norbornene ester). However, this material was not as rigid as films prepared with some di- and tri-functional resins. For example, PET
PET and resin XII which are trifunctional of MP and resin XII
Has the highest tensile modulus and second highest T
It was equipped with g.

The relationship between the functional group structure and properties is shown in Resin IX.
Shown are the results for films containing (difunctional norbornene amide). Here, it is conceivable that the restricted rotation around the amide bond and the hydrogen bond between the amides contributes not only to the high tensile modulus and tensile strength but also to the Tg.

This point is further compared with a hard hydrogen-bonded C ₆ amide resin by comparing all bonds considered to be covalent bonds with a system having a similar crosslink density in which the contribution by the hard resonance structure can be neglected. Shown (C ₆ ester or C ₆ carbonate). Esters and carbonates are relatively soft materials because their molecular structure does not incorporate stiffening building blocks into the backbone. The resulting cured film exhibits a much lower modulus and has a higher elongation at break.

[0025]

[Table 1] Tensile properties and glass transition temperature of a film containing a single norbornene resin ―――――――――――――――――――――――――――――――― ―――― N-resin Tensile modulus Tensile strength Elongation at break Tg (PETMP blended) MPa MPa% ℃ ――――――――――――――――――――――――― ――――――――――― XI 1900 ± 300 40.0 ± 5.1 2.9 ± 0.5 36.4 (Aromatic ester f = 2) XII 2300 ± 50 61.0 ± 3.3 4.1 ± 0.6 67.5 (Alkyl ester f = 3) XIII 1550 ± 180 47.2 ± 6.0 4.9 ± 0.5 71.5 (Alkyl ester f = 4) X 810 ± 200 17.0 ± 1.5 105 ± 12 30.1 (C ₆ ester f = 2) IX 1720 ± 144 52.7 ± 1.9 4.15 ± 0.45 62.1 (C ₆ amide f = 2) VIII 504 ± 72 15.3 ± 3.9 212 ± 16 36 (C ₆ urethane f = 2) VII 127.8 ± 3.2 8.1 ± 1.3 106.0 ± 8.8 NA (C ₆ carbonate f = 2) III 2115 ± 53 36.0 ± 7.64 6.18 ± 2.08 45 (Alkyl ester f = 2) ―――― ―――――――――――――――――――――――――――――――― Example 21 Characteristics of Mixed Nene Resin This example shows the effect of mixing norbornene resin. Show. The behavior of multi-component mixtures is of interest as some of the norbornene monomers are attractive as reactive diluents for high molecular weight low polymer species. Binary mixtures with increasing functionality were also investigated.

The four binary formulations were made up of 1: 1 resin (W:
W) The mixture was investigated. The three mixtures contained a combination of the X, XI and XIII resins described above. III
Blends of XIV and XIV were also investigated to evaluate the usefulness of III as a highly crystalline XIV diluent solvent. Cured films were prepared with these formulations and calculated equivalents of PETMP. Table 2 shows the properties of these cured materials.

[0027]

[Table 2] Tensile properties and glass transition temperature of compounded norbornene resin / PETMP cured film ―――――――――――――――――――――――――――――――― ―――― N-resin Tensile modulus Tensile strength Elongation at break Tg (PETMP blended) MPa MPa% ℃ ――――――――――――――――――――――――― ――――――――――― X: XII 1700 ± 40 44 ± 2.3 3.4 ± 0.4 46.9 (1: 1) X: XI 2000 ± 50 39 ± 4.1 2.8 ± 0.4 35.9 (1: 1) XI: XII 2600 ± 300 44 ± 16 2.2 ± 0.9 52.7 (1: 1) III: XIV 2030 ± 74 55 ± 2 4.5 ± 0.3 64.3 (1: 1) ――――――――――――――――― ――――――――――――――――――― These results show that the combination of X and XII produces materials with tensile properties close to the arithmetic mean of the individual homopolymers. . However, the elongation at break is essentially that of a single XII resin film (4.1% vs.> 100%). This is observed in both mixtures containing X.

The property modification is also notable for mixtures containing III and XIV. Films made of pure XIV resin are so brittle that extensive disintegration and crushing made obtaining test samples difficult. Formulation with III does not produce materials with tensile properties that differ significantly from the other formulations tested. But,
An increase in elongation at break was noted for the blend over the XIV single component film. The results show that formulations incorporating III are useful for elongation modification of brittle systems. As another example, the tensile results can be used to increase the stiffness of small amounts of XIV and to reduce the elongation of relatively soft and rubber-elastic materials.

All norbornene formulations investigated were mixed at room temperature in the proportions studied. The low polymer was miscible, as the temperature sweep of the cured film obtained by dynamic mechanical analysis showed a single Tg for each formulation.
It was thought to form a random polymer. Moreover, all films are optically clear, another indication of miscibility.

The effect of increasing the level of energy functionality on the glass transition and the mechanical properties of further mixtures have been focused on. A single mixture of the difunctional ene, XI (EBPADN) and the trifunctional ene, XII (TMPTN) was investigated. It is believed that these two ene components and the crosslinker form a random copolymer mixture. The results are listed in Table 3 below.

[0031]

Table 3 Effect of mixture composition on mechanical properties of blends of non-bornene resins XI and XII cross-linked with PETMP ――――――――――――――――――――――― ――――――――――――― Resin * Modulus of elasticity Tensile strength Elongation Tg (W / W) (MPa) (MPa) (%) (℃) ――――――――― ――――――――――――――――――――――――――― XI 1434 30.35 3.83 38 (EBPA DN) XI: XII 1500 33.10 4.04 39 (39: 1) XI: XII 1603 33.58 3.85 41 (19: 1) Xi: XII 1603 42.60 3.88 42 (9: 1) XI: XII 2600 44 2.20 52 (1: 1) XII 2300 61 4.10 67 (TMPTN) ―――――――― ―――――――――――――――――――――――――――― These results predict that this mixture of ene components will cause the glass transition of random copolymers. Those showing sufficient agreement with the relationships predicted in the so-called "law of mixtures" It pointed out to that. Therefore, complete mixing can be guaranteed. Example 22 Effect of Main Chain A single low polymer main chain (poly [TMO65
0]) was also investigated. Table 4 outlines the mechanical properties and glass transition temperatures of these materials. Poly (TMO
It can be seen that in the 650) based system the end group personality does not significantly affect the final mechanical as well as thermal properties. On the contrary, the flexibility of the poly (TMO) 650 backbone has a lasting effect on the properties of the cured film, regardless of the end groups, creating a material that is rubbery at room temperature.
If the long backbone is not incorporated into the starting material, it will have a greater impact on the end group functionality Tg and tensile properties.
This is shown by comparing the properties of IX (the C ₆ amide) with those of XIX (the poly (TMO650] amide) .Hydrogen bonds between amide groups are possible in both systems, with a Tg of almost 100. It changes with the temperature of ° C. Tensile modulus is 1000
It depends on the multiple of. The tensile strengths of these two films differ by a factor of 100.

[0032]

[Table 4] Tensile properties and glass transition temperatures of various non-bornene-functionalized poly (TMO650) resins ―――――――――――――――――――――――――――― ―――――――― N-functionality Tensile elastic modulus Tensile strength Elongation at break Tg (PETMP blended) MPa MPa% ℃ ―――――――――――――――――――― ―――――――――――――――― XVI 4.70 ± 0.23 0.69 ± 0.05 17.3 ± 2.0 -39.0 Nonbornene methyl carbonate ester XVII 5.62 ± 1.03 0.81 ± 0.11 16.7 -39.0 Nonbornene ester XVIII 5.86 ± 0.28 1.17 ± 0.25 25.0 ± 6.6 -16.0 Non-bornene urethane XIX 1.38 ± 0.28 0.53 ± 0.06 51.5 ± 7.7 -20.0 Non-bornene amide dimethyl acetate ―――――――――――――――― -------------------- structure VII (wherein _{C 6} carbonate esters) may, XVI
(Structure similar to that of the above-mentioned poly (TMO650) carbonate). VII is soft and somewhat difficult to handle at room temperature, but its tensile properties, by grade, are low polymer
It is more than a cured film containing XVI.

Finally, T of a low polymer system having the same polar functional group is used.
The effect on g becomes stronger. XIX (amide function) and XVII
Numerical value of Tg of I (urethane functionality) and T of XVI (carbonate ester) and XVII (carboxylate ester)
Comparison with the numerical value of g shows limited rotation of the amide and urethane groups and stiffening due to hydrogen bond formation. The Tg value of the former material exceeds that of the latter by approximately 20 to 25 ° C. Obviously, the end group functionality of this kind affects the physical as well as the mechanical properties of the films of the homologous series. This effect can be large or small depending on the main chain. Example 23 Photopolymerization Studies UV curing studies were incorporated into studies on the photoresponse of norbornene resins. The method used was to analyze the samples at various UV irradiation doses to determine the effect of functionality on conversion. A sample study was conducted using an equal amount of norbornene resin as pentaerythritol tetramercaptopropionate (P
ETMP). A standard acrylate monomer, ethoxylated diphenol A diacrylate, was also studied (without polythiol compounding), but at a higher irradiation dose (13.3 vs. 2.13 mJ-cm ⁻² ).
At lower doses, acrylate was non-reactive due to oxygen interference. Even this high dose rate is probably not sufficient to completely overcome the effects of oxygen interference, which is also evident at the high UV dose required to reach 65% cathodic conversion. When non-bornene systems were subjected to high dose rates, it was too rapid to measure the polymerization in the intermediate stage. The results are shown in Table 5 below.

[0034]

[Table 5] Conversion rate and UV dose parameters ―――――――――――――――――――――――――――――――――――― N-resin part Total dose 50% Conversion dose UV intensity (PETMP blend) Conversion (mJ-cm ² ) (mJ-cm ² ) (mW-cm ² ) ― ―――――――――――――――――― ――――――――――――――――――― Ethoxylated 0.65 600 65 2.13 Bisphenol A Di- (N-carboxylate) (EBPA DN) 1,6-hexanedioldi-0.76 380 30 2.13 (N-carboxylate) (HDDN) Trimethylolpropane 0.60 300 85 2.13 Tri- (N-carboxylate) (TMP TN) Pentaerythritol 0.49 520 390 2.13 Tetra- (N-carboxylate) (PETN) Comparative resin ethoxylation 0.65 8000 2800 13.3 Bisphenol A diacrylate ―――――――――――――― --------------------- were prepared Example 24 stereolithography test two resins formulated as follows supra. That is: Combination A Combination B TMP-TN ¹ 60 --- HDDN ² 60 200 PETMP ³ 85.3 135.7 Photoinitiator ⁴ 4.19 6.85 Stabilizer ⁵ 1000ppm 1000ppm 1. Trimethylolpropane trinorbornenecarboxylate 2. Hexanediol dinorbornene carboxylate 3. Pentaerythritol tetramercaptopropionate 4. Darocure ^{(TM) (Darocur (TM)} ) 1173 5. Wako, Federal Republic of Germany. Chemical Company (Wako
Chemical GmbH) SLA250 from 3D Systems Inc. using a He-Cd laser at about 8 mW ammonium salt of N-nitrosophenylhydroxylamine.
Using the testing machine, four sets of five railroad ties were made according to standard 3D Systems quality control procedures. The exposure was varied for each sleeper, and the resulting tie thickness was measured to create a dose-response curve. Four
At a depth of 0 mm or more, the curing spreads beyond the edge of the laser beam on the surface of the resin, so the shape of the sleeper became unclear. This problem was not observed below about 40 mm.

FIGS. 1 and 2 are UV response curves obtained from railroad tie measurements for Resins A and B, respectively. As can be seen from these figures, the UV response is extremely fast.
For example, at a cure depth of 20 mils, exposure of Formulation A (mJ /
cm ² ) was about 50 and Formulation B was about 23. This is Murphy et al., “Reduced. Distortion in Optical Free Form.
Fabrication. With. UV laser (Redu
ced Distribution in Optica
l Free Form Fabrication w
entitled "Its UV Lasers", "Radiation Curin"
g) ”can be compared very well with the results reported for the acrylic resin in the paper published in the February to May, 1989 issue, pages 3 to 7. There, about 1 mil for a 20 mil deep cure.
A similar procedure is described requiring 5-5 Joules / cm ² .

"Green" 20 mm single layer pull bar (p
ulbar) was formed by laser curing on a 3D Systems 3D lithographic printing machine. Tensile strength, modulus and elongation at break were measured on the "green" sample. The pull bar prepared in the same manner was post-cured by using a UV floodlight in a post-curing device of 3D Systems. Table 6 shows the same values as the average values obtained for Nene-Thiol formulations A and B. Geigy's "Cibatool"
We will report together with the reported numerical values of the prior art acrylic derivative-based three-dimensional lithographic printing resin of XLSB5081.

[0037]

[Table 6] ―――――――――――――――――――――――――――――――――――― Elasticity Tensile strength Stretching (N / Mm ² ) (N / mm ² ) (%) ―――――――――――――――――――――――――――――――――――― Resin A Green 65 4 to 100 Post-curing 423 23 13 Resin B Green 106 4.4 91 Post-curing 523 50 12 Cibatour 5081 Green 80-100 5-10 5-10 Post-curing 2500-3500 50-70 2-3 ――――― ―――――――――――――――――――――――――――――――

[0038]

As can be seen from the data, both thiol-nene formulations according to the present invention produce much more brittle products than prior art acrylic formulations while retaining conditioned tensile strength properties. To do.

[Brief description of drawings]

1 is a UV response curve showing the relationship between dose and cure depth measured on railroad ties data obtained from Example A. FIG.

FIG. 2 is a view similar to FIG. 1 measured with railroad sleeper data obtained from Example B.

Continuation of the front page (51) Int.Cl. ⁵ Identification number Office reference number FI Technical indication location G03F 7/00 501 7124-2H 7/028 9019-2H (72) Inventor Margaret. Ann. Lacas United States. 01106. Massachusetts State. Long meadow. Long meadow. Street. 1203 (72) Inventor Dave Tutt. M. Glacer USA. 06051. Connecticut. New Britain. Benson. Street. 52

Claims (12)

[Claims] 1. A three-dimensional lithographic printing method for depositing a three-dimensional article, which comprises successively curing successive layers of a curable resin blending bath in a pattern until the three-dimensional article is completely deposited.
In a three-dimensional lithographic printing method comprising a step of removing the three-dimensional product from the liquid resin bath, and a step of post-curing the liquid resin, the liquid resin is (a) a first compound having a plurality of norbornene groups. , (B) a second compound having a plurality of thiol groups therein, and (c) a free radical photoinitiator, wherein the total functional group of the compound is thiol-ene having a total of 4 or more. 3D lithographic printing method. 2. The three-dimensional lithographic printing method according to claim 1, wherein the first compound is a non-bornene carboxylic acid polyrole ester. 3. The first compound is trimethylolpropane, hexanediol, ethoxylated bisphenol A or a mixture thereof.
Three-dimensional lithographic printing method. 4. The three-dimensional lithographic printing method according to claim 2, wherein the second compound is an α- or β-mercaptocarboxylic acid salt polyrole ester. 5. The three-dimensional lithographic printing method according to claim 4, wherein the second compound is an α or β-mercaptopropionate ester of a tri- or higher-functional alcohol. 6. The three-dimensional lithographic printing method according to claim 5, wherein the second compound is pentaerythritol tetrakis β-mercaptopropionate. 7. The three-dimensional lithographic printing method according to claim 1, wherein the thickness of each layer is 40 mils or less. 8. The three-dimensional lithographic printing method according to claim 7, wherein the layer thickness is about 20 mils or less. 9. In the pattern-based curing, a cross-sectional image of the three-dimensional product is continuously traced on the surface of a liquid resin with a UV laser bath to provide a cured cross-sectional layer of the three-dimensional product on the bath surface, and each layer The method of claim 7, wherein the method is accomplished by curing the product until all the products have been deposited, and then incrementally reducing the product below the surface of the bath by a depth of one layer. 10. The three-dimensional lithographic printing method of claim 1, wherein the thiol-nene blend further comprises a shelf-life stable and effective amount of polyiodide. 11. The polyiodide stabilizer has a weight ratio of about 1: 2 kl / l ₂ and a weight ratio of about 10 to 2,000 p.
11. The three-dimensional lithographic printing method according to claim 10, characterized in that it is present in an amount of pml ₂ . 12. A curable composition comprising: (a) a first compound having a plurality of norbornene groups thereon, (b) a second compound having a plurality of thiol groups therein, and (c) a free radical. A curable composition comprising a photoinitiator and (d) a storage-life stable and effective amount of polyiodide, and having a total functionality of 4 or more.