RU2408627C2 - Antimony-free photocurable polymeric composition and three-dimensional article - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: invention relates to a photocurable composition for a three-dimensional article containing the following in wt %: (a) a cation-curable component containing an oxetane compound 35-80; (b) a free-radical active component containing poly(meth)acrylate, which is not dipentaerythritol hexaacrylate 15-60; (c) an antimony-free cationic photoinitiator 0.1-10; (d) a free-radical photoinitiator 0.01-10; (e) one or more additives which increase impact resistance 0.01-40. The photocurable composition can be cured under the effect of actinic radiation and optionally heating, which enables to obtain three-dimensional articles which can be used in various aerospace fields and in methods of casting with consumable patterns. Described also is a method of producing a non-toxic photocurable composition by mixing all components and a method of making a three-dimensional article which is free from antimony.

EFFECT: obtaining solid components having sufficient strength, stable resin viscosity, improved impact resistance and elasticity of components.

25 cl, 45 tbl, 85 ex

Description

FIELD OF THE INVENTION

The present invention relates to a low viscosity photo-curable composition comprising (i) a cationically curable component, (ii) a free radical active component, (iii) an antimony-free cationic photoinitiator and optionally (iv) a free radical photoinitiator, and (v) optionally a shockproofing additive , also to the use of the specified composition to obtain three-dimensional products using methods for the rapid manufacture of prototypes.

BACKGROUND

Imaging solid objects using a liquid, such as stereolithography, is a process in which a photoformable liquid is applied in a thin layer to a surface and exposed to actinic radiation, causing the liquid to solidify. Next, new thin layers of photoformable liquids are applied to previous layers of liquid or to previously cured areas. The new layers are then exposed to the image in order to cure the parts in the image and to cause adhesion between parts of the freshly cured area and parts of the previously cured area. Each exposure in images gives a shape that corresponds to a specific cross section of the photocurable object, such that when all layers have been applied and all exhibits have been carried out, the combined photocurable object can be removed from the surrounding liquid composition.

Photoformable resins currently used in the manufacture of a photocurable object typically contain a cationically polymerizable compound, such as an epoxy compound, and / or a radical polymerizable compound, such as acrylate, together with cationic and / or radical photoinitiators. For example, JP 02075618A describes a photocurable resin containing an epoxy resin, acrylate, as well as a cationic photoinitiator containing antimony, and a free radical photoinitiator.

Antimony is a toxic heavy metal, and its presence in photocurable parts makes antimony resins less suitable in many applications. In addition, due to its high activity, antimony hexafluorides are prone to instability and cause an increase in the viscosity of the resin over time. Removing the cationically polymerizable compound, as a result of which the composition would contain only the radical polymerizable compound, does not provide an adequate solution, since these resins give objects with much greater distortion as a result of acrylate shrinkage, which also have insufficient cohesive strength and increased fragility. Adding stabilizers to the polymer composition also does not provide an adequate solution, since stabilizers are consumed over time and must be continuously added to the resin to maintain a low viscosity.

Thus, it would be preferable to produce an antimony-free, stable photocurable composition of low viscosity, which can be quickly cured in the process of displaying a solid object using liquid, which makes it possible to produce a product having high cohesive strength, impact resistance and dimensional accuracy with minimal distortion.

Asahi Denka described the composition of hybrid epoxy acrylate compositions for laser imaging (JP 02075618A). Said document states that cycloaliphatic epoxy resins combined with triarylsulfonium hexafluorostibate are preferred epoxycation initiating systems in optical forming systems. In commercial resins, starting with this patent, the same cationic initiator was used, as well as one or more other features of this patent. Descriptions of subsequent patents have also focused on compositions containing antimony salt. The present description unexpectedly shows that at the moment some compositions may be developed that do not use hexafluoroostate.

Huntsman in WO 03/089991 A2 describes SL resins containing coated core particles with an active core, allowing parts to be obtained with smooth surfaces and good mechanical properties. In this patent, Huntsman uses triarylsulfonium hexafluorostate as a cationic initiator. Active particles are stable and do not separate into phases. In the present description, compositions comprising the active particles described above together with a cationic photoinitiator that does not contain hexafluorostatite provide parts with improved and more balanced mechanical properties.

WO 03/093901 A1 describes the use of hydrogenated epoxy components in combination with oxytane components, which gives the resins "good water resistance".

The present invention uses an antimony salt-free initiator, and also discloses new compositions with a wide range of acrylic compounds. Preferably, it has been found that compositions with more than 25% acrylate content using a cationic initiator that does not contain hexafluoroostate have unexpectedly good general properties.

US 2005/0228064 A1 describes the use of additives to increase impact resistance.

US 6811937 describe the use of low molecular weight polyTHF with certain acrylates, which provides high transparency. Hexaacrylated dipentaerythritol is used in this patent, while the inventors of the present invention showed similar improvement using pentaacrylated dipentaerythritol in PF ₆ compositions of the present invention. Preferably, in the compositions of the present invention, the free radical active component does not include hexaacrylate dipentaerythritol.

US 6379866 describes the use of an active additive to increase impact resistance, consisting of a single active compound that increases impact resistance.

WO 2005/045525 describes the use of nanoparticles.

SUMMARY OF THE INVENTION

The present invention provides a photocurable composition of low viscosity, comprising approximately 35-80% wt. cationically curable component, approximately 5-60% wt. free radical active component, approximately 0.1-10% wt. cationic photoinitiator free of antimony, 0-10% wt. free radical photoinitiator, 0-40% wt. impact resistance additives, and one or more additional components, where% wt. taken from the total mass of the photocurable composition. The photocurable composition can be quickly cured by applying a layer of the composition to the base or surface and exposing the layer from the images under the action of actinic radiation with an intensity sufficient to cause substantial curing of the layer in the exposed areas so that a displayed cross section is formed. Then, a second layer of the photocurable composition can be formed on the previous displayed cross section and, in turn, exposed to actinic radiation with an intensity sufficient to cause substantial curing of the second layer and to cause adhesion to the previous displayed cross section. The cycle can be repeated a sufficient number of times to create a three-dimensional product with exact dimensions, which can be used in various fields.

DETAILED DESCRIPTION OF THE INVENTION

The present invention relates to photo-curable compositions comprising a cation-curable component, a free radical active component, an antimony-free cationic photoinitiator, and optionally a free radical photoinitiator, an impact resistance improver, and one or more other additional components. It was unexpectedly found that by combining these components, it is possible to obtain a non-toxic photo-curable composition of low viscosity, which, when quickly cured by a laser, can produce a three-dimensional product that has an excellent balance of cohesive strength, impact resistance, elasticity, dimensional accuracy, wear resistance, increased water resistance, high color fastness , increased transparency, increased stability in the cured and uncured form, moisture resistance in room conditions and durability ty, while the concept of "three-dimensional product" refers to the product obtained from at least two layers of the cured polymer composition. At the same time, without being bound by any particular theory, it is assumed that the antimony-free cationic photoinitiator forms active cationically curable components with different kinetics compared to antimony-based photoinitiators. During curing, the active cation-curable components formed by the antimony-free photoinitiator also act by a different curing method, which leads to less residual stress in the cured product and, thus, allows the production of a product having lower brittleness and greater impact resistance.

The present invention allows to solve several technical problems:

1. The presence of heavy metals

The commercially available SL resins based on hybrid acrylate / epoxy chemistry use a cationic photoinitiator containing antimony salts. Cationic photoinitiators containing antimony salts are the most active and have been used in SL compositions for many years. The presence of toxic heavy metal makes them less suitable in many areas. Salts of phosphorus are less active and their use in the present compositions instead of antimony salts does not allow to obtain solid parts of sufficient strength by the method of stereolithography.

The solution is to use the PF ₆ sulfonium salt instead of the SbF ₆ salt. However, simply the transition from the SbF ₆ salt to the salt in the present compositions is not sufficient: the cohesive strength is extremely low, and the details cannot be obtained using the stereolithography method. To compensate for the lower rate of action of the salt of PF ₆ , the composition must be modified. The present disclosure discloses unexpected compositions that can provide high cohesive strength using a cationic photoinitiator free of any antimony salt. In addition, it was found that parts may have improved mechanical properties compared to currently available SL resins that use antimony salt.

2. The instability of viscosity

Highly active hexafluorostates are also responsible for the instability of the viscosity of the resin. From the very beginning of the stereolithography method, the resin is regularly subjected to low doses of UV radiation that cause photodegradation of the photoinitiator, resulting in the formation of small amounts of active molecules. The cationic photoinitiator containing the antimony salt is known to be particularly unstable due to the high activity of the antimony salt. Several attempts have been made to stabilize the composition by adding slightly alkaline compounds of various types. In its literature, Dow Chemicals, a supplier of both salts, indicates that compositions containing PF ₆ salts are more stable over time than compositions containing SbF ₆ salts.

Several attempts have been made to solve the problems of viscosity stability:

US 5,665,792 (Du Pont de Nemours) describes the use of stabilizers that are sparingly soluble in the composition. They are present as a solid phase in the composition in an amount in excess of their ultimate solubility. The stabilizer concentration is continuously restored as the stabilizer reacts with undesired free acid.

US 6099787 (Ciba Specialty chemicals) describes the use of an organic viscosity stabilizer for SL-filled resins.

US 5,783,358 (Ciba Specialty chemicals) describes the use of a basic ion exchanger in contact with a radiation curable liquid composition for at least some time. Ionite is preferably removed prior to radiation curing.

WO 03/104296 (Vantico AG) describes the use of a boro-aminotrichloride complex as a stabilizer for actinic radiation curable compositions.

However, in the prior art, when using the initial amount of stabilizer, the viscosity began to increase.

3. Improved impact resistance and elasticity

Salts SbF ₆ and salts PF ₆ form active molecules with different kinetics. Subsequent polymerization of epoxy compounds also proceeds through various curing mechanisms. The authors of the present invention also believe that a different curing method induced by the PF ₆ salt leads to lower residual stress in the cured parts, which thus allows parts with reduced brittleness and improved impact resistance.

US 5476748 (Ciba-Geigy Corporation) describes the use of OH-terminated polyester, polyester, polyurethane to improve mechanical properties, especially elongation at break. That is, the addition of these polyols reduces brittleness.

US 6413697 (Vantico AT&T US) describes the use of cationically active modifiers and polyols to increase the elasticity and impact resistance of cured products.

US 6379866 (DSM) describes the use of polyols and active additives that increase impact resistance, in order to obtain elastic parts having the appearance and tactile properties of polypropylene products.

All 3 aspects (the presence of heavy metals, viscosity instability, and the desired improvement in mechanical properties) can be improved in the compositions disclosed herein. The compositions described herein include:

A) 40-80% of the resin as a cationically curable component;

B) 5-60% of one or more acrylate components with a functionality of 2 or higher;

C) 0-15% of one or more acrylate components with functionality> 2. A preferred multifunctional acrylate will be a hyperbranched (dendritic) polyester acrylate (such as CN2301 from Sartomer);

D) 0-30% oxytane as a cationic component;

E) optionally, from 0 to 40% of one or more impact enhancing additives. Said impact resistance enhancing additive may be a component containing one or more hydroxyl groups, or may be an active particle comprising a core of cross-linked polysiloxane and a shell of active groups on the outer surface of the core, where the active group includes epoxy groups, ethylene unsaturated groups, or hydroxyl groups;

F) 0.1-10% of a free radical photoinitiator;

G) 0.1-10% of a cationic photoinitiator that does not contain any antimony salts.

Cationically Curable Component

As a first essential component, the photocurable composition of the present invention comprises about 35-80% of the total weight of the photocurable composition of the cationic solidification component. The cationically curable component includes at least one cationically curable compound characterized by the presence of functional groups capable of reaction by or as a result of the ring opening mechanism initiated by cations, resulting in the formation of a crosslinked polymer structure. Examples of these functional groups in the compound include oxirane (epoxy), oxitan, tetrahydrofuran and lactone rings. These compounds may have an aliphatic, aromatic, cycloaliphatic, araliphatic or heterocyclic structure, and they may contain ring groups as side groups, or the functional group may be part of an alicyclic or heterocyclic ring system. The cationically curable compound may be bifunctional or trifunctional, or may include more than three cationically curable groups.

The cationically curable component may include a single liquid cationically curable compound, a combination of liquid cationically curable compounds, or a combination of one or more liquid cationically curable compounds, as well as one or more solid cationically curable compounds that are soluble in the liquid.

In one embodiment of the present invention, the cationically curable compound is an epoxy-containing compound. In general, any epoxy-containing compound is suitable for use in the present invention, such as, for example, the epoxy-containing compounds disclosed in US Pat. No. 5,476,748, which is incorporated herein by reference. Examples of epoxy-containing compounds include polyglycidyl epoxy compounds, non-glycidyl epoxy compounds, epoxycresol-novolac compounds and epoxyphenol-novolac compounds.

The polyglycidyl epoxy compound can be a polyglycidyl ether, a poly (β-methylglycidyl) ether, a polyglycidyl ester or a poly (β-methylglycidyl) ester. The synthesis and examples of polyglycidyl ethers, poly (β-methylglycidyl) ethers, polyglycidyl ethers and poly (β-methylglycidyl) esters are disclosed in US Patent No. 5,972,563, which is incorporated herein by reference. For example, esters can be prepared by reacting a compound having at least one free alcoholic hydroxyl group and / or phenolic hydroxyl group with substituted epichlorohydrin under alkaline conditions or in the presence of an acidic catalyst followed by treatment with alkali. Alcohols can be, for example, acyclic alcohols, such as ethylene glycol, diethylene glycol and higher poly (hydroxyethylene) glycols, propane-1,2-diol, or poly (hydroxypropylene) glycols, propane-1,3-diol, butane-1, 4-diol, poly (oxytetramethylene) glycols, pentane-l, 5-diol, hexane-l, 6-diol, hexane-2,4,6-triol, glycerol, 1,1,1-trimethylolpropane, bis (trimethylolpropane) pentaerythritol and sorbitol. Suitable glycidyl ethers can also be prepared with cycloaliphatic alcohols such as 1,3- or 1,4-dihydroxycyclohexane, bis (4-hydroxycyclohexyl) methane, 2,2-bis (4-hydroxycyclohexyl) propane or 1, 1-bis (hydroxymethyl) cyclohex-3-ene, or they may have aromatic rings such as N, N-bis (2-hydroxyethyl) aniline or p, p'-bis (2-hydroxyethylamino) diphenylmethane.

The most important representatives of polyglycidyl ethers or poly (β-methylglycidyl) ethers as the main part include monocyclic phenols, for example resorcinol or hydroquinone, polycyclic phenols, for example bis (4-hydroxyphenyl) methane (Bisphenol F), 2,2-bis (4- hydroxyphenyl) propane (Bisphenol A), bis (4-hydroxyphenyl) S (Bisphenol S), alkoxylated Bisphenol A, F or S, triol-substituted Bisphenol A, F, or S, brominated Bisphenol A, F or S, hydrogenated Bisphenol A , F or S, glycidyl ethers of phenols and phenols with side groups or chains, Recreatives Products condensation under acidic conditions, of phenols or cresols with formaldehyde, such as phenol novolaks and cresol novolaks or siloksandiglitsidily.

Polyglycidyl esters and poly (β-methylglycidyl) esters can be prepared by reacting epichlorohydrin or glycerol dichlorohydrin, or β-methylepichlorohydrin with polycarboxylic acid. The reaction is expediently carried out in the presence of bases. The polycarboxylic acids can be, for example, glutaric acid, adipic acid, pimelic acid, slug acid, azelaic acid, sebacic acid, or dimerized or trimerized linoleic acid. However, in a similar manner, it is also possible to use cycloaliphatic polycarboxylic acids, for example tetrahydrophthalic acid, 4-methyltetrahydrophthalic acid, hexahydrophthalic acid or 4-methylhexahydrophthalic acid. Aromatic polycarboxylic acids can also be used, such as, for example, phthalic acid, isophthalic acid, trimellitic acid or pyromellitic acid, or other carboxylic acid terminal adducts, e.g. trimellitic acid and polyols, e.g. glycerol or 2,2-bis (4 -hydroxycyclohexyl) propane.

In another embodiment of the present invention, the epoxy compound is a non-glycidyl epoxy compound. Non-glycidyl epoxy compounds may be linear, branched or cyclic in structure. For example, one or more epoxy compounds in which the epoxy groups are part of an alicyclic or heterocyclic ring system may be included in said embodiment. Other options include epoxy compounds with at least one epoxycyclohexyl group, which is bonded directly or indirectly to a group containing at least one silicon atom. Examples are disclosed in US Patent No. 5639413, which is incorporated herein by reference. Other options include epoxides that contain one or more cyclohexene oxide groups and epoxides that contain one or more cyclopentene oxide groups.

A particularly suitable non-glycidyl epoxy compound includes the following bifunctional non-glycidyl epoxy compounds, the epoxy groups of which are part of an alicyclic or heterocyclic ring system: bis (2,3-epoxycyclopentyl) ether, l, 2-bis (2,3-epoxycyclopentyloxy) ethane, 3,4-epoxycyclohex -3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-6-methyl-cyclohexylmethyl-3,4-epoxy-6-methylcyclohexanecarboxylate, di (3,4-epoxycyclohexylmethyl) hexanedioate, di- (3,4-epoxy-6- methylcyclohexylmethyl) hexanedioate, ethylene bis (3,4-epo xicyclohexanecarboxylate), di (3,4-epoxycyclohexylmethyl) ethanediol ether, vinylcyclohexene dioxide, dicyclopentadiene dietepoxide or 2- (3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane-1,3-dioxane, and 2,2'-bis- (3,4-epoxycyclohexyl) propane.

Particularly preferred bifunctional non-glycidyl epoxy compounds include cycloaliphatic bifunctional non-glycidyl epoxy compounds such as 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexanecarboxylate and the 2,2'-bis (3,4-epoxycyclohexyl) propane compound, the first being preferred.

In another embodiment, the cationically curable compound is a poly (N-glycidyl) compound or a poly (S-glycidyl) compound. Poly (N-glycidyl) compounds can be obtained, for example, by dehydrochlorinating the reaction products of epichlorohydrin with amines containing an amine with at least two hydrogen atoms. These amines can be, for example, n- butylamine, aniline, toluidine, m- xylylenediamine, bis (4-aminophenyl) methane or bis (4-methylaminophenyl) methane. Other examples of poly (N-glycidyl) compounds include N, N'-diglycidyl derivatives of cycloalkylene ureas, such as ethylene urea or 1,3-propylene urea, and N, N'-diglycidyl derivatives of hydantoins, such as 5,5-dimethyl hydantoin. Examples of poly (S-glycidyl) compounds are di-S-glycidyl derivatives derived from dithiols, for example ethane-1,2-dithiol or bis (4-mercaptomethylphenyl) ether.

Epoxy compounds in which 1,2-epoxy groups are bonded to various heteroatoms or functional groups can also be used. Examples of these compounds include N, N, O-triglycidyl derivative of 4-aminophenol, glycidyl ether / glycidyl ester of salicylic acid, N-glycidyl-N '- (2-glycidyloxypropyl) -5,5-dimethylhydantoin or 2-glycidyloxy-l, 3-bis (5,5-dimethyl-l-glycidylhydantoin-3-yl) propane.

Other epoxy derivatives such as vinylcyclohexene dioxide, limonene dioxide, limonene monoxide, vinyl cyclohexene monoxide, 3,4-epoxycyclohexylmethyl acrylate, 3,4-epoxy-6-methylcyclohexylmethyl-9,10-epoxy-stearate and l, 2-bis (2,3-epoxy) can also be used. 2-methylpropoxy) ethane.

It is also possible to use liquid pre-reacted adducts of epoxy compounds, such as those mentioned above, with hardeners for epoxy resins. Of course, you can also use liquid mixtures of liquid or solid epoxy resins in new compositions.

The following compounds are examples of commercial epoxy compounds suitable for use in the present invention: Uvacure® 1500 (3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexanecarboxylate, available from UCB Chemicals Corp.); Epalloy® 5000 (epoxidized hydrogenated Bisphenol A, available from CVC Specialties Chemicals, Inc), Heloxy ^TM 48 (trimethylolpropane-triglycidyl ether, available from Resolution Performance Products LLC); Heloxy ^TM 107 (cyclohexanedimethanol diglycidyl ether, available from Resolution Performance Products LLC); Uvacure® 1501 and 1502, which are proprietary cycloaliphatic epoxides, Uvacure® 1530-1534, which are cycloaliphatic epoxides mixed with a patented polyol, Uvacure® 1561 and Uvacure® 1562, which are patented cycloaliphatic epoxides (containing) all available from UCB Chemicals Corp.); Cyracure® UVR-6100, -6105, -6107 and -6110, all of which are 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexanecarboxylate, Cyracure® UVR-6128, bis (3,4-epoxycyclohexyl) adipate (all available from Dow Chemical Co.); Araldite® CY 179, 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexanecarboxylate and Araldite® PY 284, diglycidyl hexahydrophthalate polymer (available from Huntsman Advanced Materials Americas Inc); Celoxide ^TM 2021, 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexylcarboxylate, Celoxide ™ 2021 P, 3', 4'-epoxycyclohexanomethyl-3 ', 4'-epoxycyclohexylcarboxylate, Celoxide ^TM 2081, 3', 4'-epoxycyclohexylcarboxylate -3, '4'-epoxycyclohexylcarboxylate modified with caprolactone, Celoxide ^TM 2083, Celoxide ^TM 2085, Celoxide ^TM 2000, Celoxide ^TM 3000, Epolead GT-300, Epolead GT-302, Epolead GT-400, Epolead 401, Epolead 403 (all available from Daicel Chemical Industries Co., Ltd.), DCA, alicyclic epoxide (available from Asahi Denka Co. Ltd); and E1, an epoxy hyperbranched polymer obtained by polycondensation of 2,2-dimethylolpropionic acid functionalized with glycidyl groups (available from Perstorp AB).

In another embodiment, the cationically curable compound is an oxitane compound. The following compounds are given as examples of oxytane compounds having one oxytane ring in the compound and which can be used in the present invention: 3-ethyl-3-hydroxymethyloxytane, 3- (meth) allyloxymethyl-3-ethyloxytane, (3-ethyl-3- hydroxytanylmethoxy) methylbenzene, 4-fluoro- [1- (3-ethyl-3-hydroxytanylmethoxy) methyl] benzene, 4-methoxy- [1- (3-ethyl-3-hydroxytanylmethoxy) methyl] benzene, [1- (3- ethyl 3-hydroxytanylmethoxy) ethyl] phenyl ether, isobutoxymethyl- (3-ethyl-3-hydroxytanylmethyl) ether, isobomyloxyethyl- (3-ethyl-3-hydroxytanylmethyl) ether, isobomyl- (3-et l-3-hydroxytanylmethyl) ether, 2-ethylhexyl- (3-ethyl-3-hydroxytanylmethyl) ether, (3-ethyl-3-hydroxytanylmethyl) -ethylethylethylene glycol ether, dicyclopentadiene- (3-ethyl-3-hydroxytanylmethyl) ether, dicyclopentenyl - (3-ethyl-3-hydroxytanylmethyl) ether, dicyclopentenyl- (3-ethyl-3-hydroxytanylmethyl) ether, tetrahydrofurfuryl- (3-ethyl-3-hydroxytanylmethyl) ether, tetrabromophenyl- (3-ethyl-3-hydroxytanylmethyl) ether , 2-tetrabromophenoxyethyl- (3-ethyl-3-hydroxytanylmethyl) ether, tribromophenyl- (3-ethyl-3-hydroxytanylmethyl) ether, 2-tribromophenoxyethyl- (3-ethyl-3-hydroxytanylmethyl high) ether, 2-hydroxyethyl- (3-ethyl-3-hydroxytanylmethyl) ether, 2-hydroxypropyl (3-ethyl-3-hydroxytanylmethyl) ether, butoxyethyl- (3-ethyl-3-hydroxytanylmethyl) ether, pentachlorophenyl- (3 ethyl-3-hydroxytanylmethyl) ether, pentabromophenyl- (3-ethyl-3-hydroxytanylmethyl) ether, bornyl- (3-ethyl-3-hydroxytanylmethyl) ether and the like. Other examples of oxytane compounds suitable for use in the present invention include trimethylene oxide, 3,3-dimethyloxytane, 3,3-dichloromethyloxytane, 3,3- [1,4-phenylene bis (methyleneoxymethylene)] - bis (3-ethyloxytane) , 3-ethyl-3-hydroxymethyl-oxitane, and bis [(l-ethyl- (3-hydroxytanyl) methyl)] ether.

Examples of compounds having two or more oxitane rings in a molecule that can be used in the present invention include 3,7-bis (3-hydroxytanyl) 5-oxononan, 3,3 '- (l, 3- (2-methylenyl) propanediyl bis (oxymethylene)) bis (3-ethyloxytane), l, 4-bis [(3-ethyl-3-hydroxytanylmethoxy) methyl] benzene, 1,2-bis [(3-ethyl-3-hydroxytanylmethoxy) methyl] ethane 1,3-bis [(3-ethyl-3-hydroxytanylmethoxy) methyl] propane, ethylene glycol bis (3-ethyl-3-hydroxytanylmethyl) ether, dicyclopentenyl bis (3-ethyl-3-hydroxytanylmethyl) ether, triethylene glycol- bis (3-ethyl-3-hydroxytanylmethyl) ether, tetraethylene glycol ol-bis (3-ethyl-3-hydroxytanylmethyl) ether, tricyclodecanediyl dimethylene- (3-ethyl-3-hydroxytanylmethyl) ether, trimethylolpropane-tris (3-ethyl-3-hydroxytanylmethyl) ether, 1,4-bis (3-ethyl -3-hydroxytanylmethoxy) butane, 1,6-bis (3-ethyl-3-hydroxytanylmethoxy) hexane, pentaerythritol-tris- (3-ethyl-3-hydroxytanylmethyl) ether, pentaerythritol-tetrakis (3-ethyl-3-hydroxytanylmethyl) ether, polyethylene glycol bis (3-ethyl-3-hydroxytanylmethyl) ether, dipentaerythritol-hexakis (3-ethyl-3-hydroxytanylmethyl) ether, dipentaerythritol-pentakis (3-ethyl-3-hydroxytanylmethyl) ether, dipentaerythritol tetrakis (3 tyl-3-hydroxytanylmethyl) ether, caprolactone-modified dipentaerythritol-hexakis (3-ethyl-3-hydroxytanylmethyl) ether, caprolactone-modified dipentaerythritol-pentakis (3-ethyl-3-hydroxytanylmethyl) ether, ditrimethylolpropane-3-tetra-tetra oxytanylmethyl) ether, EO-modified bisphenol A bis (3-ethyl-3-oxytanylmethyl) ether, BO-modified bis (3-ethyl-3-hydroxytanylmethyl) bisphenol A ether, EO-modified hydrogenated bis (3-ethyl-3- oxytanylmethyl) Bisphenol A ether, PO-modified hydrogenated Bisphenol A ester bis (3-ethyl-3-hydroxytanylmethyl) ester, Bisphenol F EO-modified (3-ethyl-3-hydroxytanylmethyl) ester, etc.

Preferably, the aforementioned oxitane compounds have 1-10, preferably 1-4, and most preferably 1 oxitane ring. In particular, 3-ethyl-3-hydroxymethyloxytane, (3-ethyl-3-hydroxymethylmethoxy) methylbenzene, 1,4-bis [(3-ethyl-3-hydroxymethylmethoxy) methyl] benzene, 1,2-bis (3 ethyl 3-hydroxytanylmethoxy) ethane and trimethylolpropane-tris (3-ethyl-3-hydroxytanylmethyl) ether. Commercially available oxytane compounds include Cyracure® UVR 6000 (available from Dow Chemical Co.) and Aron Oxetane OXT-101, OXT-121, OXT-211, OXT-212, OXT-221, OXT-610 and OX-SQ (available from Toagosei Co. Ltd.).

The cationically curable compound may also be a cyclic ether, a cyclic lactone, a cyclic acetal, a cyclic thioester, a spiro orthoester or a vinyl ester.

In addition, as noted above, it is possible that the cationically curable component of the present invention includes a mixture of cationically curable compounds described above. In one embodiment, the cationically curable component comprises at least one hydrogenated bisphenol epoxy compound having an average epoxy functionality of at least 2 and an epoxy equivalent weight (EEW) of 100-500. The hydrogenated bisphenol epoxy compound may be present in the photocurable composition in a proportion of at least about 35 wt.%, More preferably at least about 40 wt.%, And most preferably at least about 45 wt.%, total weight of the photocurable composition. In yet another embodiment, the hydrogenated bisphenol epoxy compound may be present in an amount of at most about 80% by weight, preferably in an amount of at most about 70% by weight. and most preferably in an amount of at most about 55% by weight, based on the total weight of the photocurable composition. In yet another embodiment, the hydrogenated bisphenol epoxy compound may be present in the range of from about 35-80% by weight, preferably from about 40-60% by weight. and most preferably from about 45-55% wt. the total weight of the photocurable composition.

In another embodiment, the cationically curable component may further include one or more oxytane compounds in such an amount that the oxytane is present in the photocurable composition in an amount of at least about 5% by weight, more preferably at least about 15% by weight . and most preferably at least about 19% wt. the total weight of the photocurable composition. In a further embodiment, the oxytane compound may be present in an amount of at most about 40% by weight, more preferably at most about 30% by weight. and most preferably at most about 25% wt. the total weight of the photocurable composition. In another additional embodiment, the oxytane compound may be present in the range of about 0.01-40% wt., More preferably 0.1-25% wt. and most preferably about 0.5-15% wt. the total weight of the photocurable composition.

In yet another embodiment, the cationically curable component may further include one or more bifunctional non-glycidyl epoxy compounds. The bifunctional non-glycidyl epoxy compound may be present in the photocurable composition in an amount of about 0.01-20% by weight, more preferably about 0.5-15% by weight. and most preferably about 1-10% wt. the total weight of the photocurable composition.

The total amount of cationically curable compound present in the photocurable composition may typically be at least about 35% by weight, more preferably at least about 45% by weight. and most preferably at least about 55% wt. the total weight of the photocurable composition. In another embodiment, the total amount of cationically curable compound present is at most about 80% by weight, more preferably at most about 70% by weight. and most preferably, at most, about 65% wt. the total weight of the photocurable composition. In yet another embodiment, the total amount of cationically curable compound present is in the range of about 35-80% by weight, preferably about 40-70% by weight. and most preferably about 45-65% wt. the total weight of the photocurable composition.

Free radical active ingredient

As a second essential component, the photocurable composition of the present invention includes a free radical active ingredient in an amount of at least about 5% to about 60% of the total mass of the photocurable composition. The free radical active component includes at least one free radical active compound that is activated in the presence of an initiator capable of causing free radical polymerization in such a way that a reaction with other compounds carrying free radical functional groups becomes possible. Examples of free radical active compounds include compounds bearing one or more ethylene unsaturated groups, such as compounds having (meth) acrylate groups. The term “(meth) acrylate” refers to acrylate, methacrylate or mixtures thereof and includes monofunctional monomers containing one ethylenically unsaturated bond and multifunctional monomers containing two or more unsaturated bonds in a single molecule. In one embodiment, the implementation of (meth) acrylate is a monofunctional monomer. Examples of monofunctional monomers that can be used include (meth) acrylamide, (meth) acryloylmorpholine, 7-amino-3,7-dimethyloctyl- (meth) acrylate, isobutoxymethyl- (meth) acrylamide, isobornyloxyethyl- (meth) acrylate, isobornyl- (meth) acrylate, 2-ethylhexyl- (meth) acrylate, ethyl diethylene glycol- (meth) acrylate, t- octyl- (meth) acrylamide, diacetone- (meth) acrylamide, dimethylaminoethyl- (meth) acrylate, diethylaminoethyl- (meth) acrylate , lauryl- (meth) acrylate, dicyclopentadiene- (meth) acrylate, dicyclopentenyloxyethyl- (meth) acrylate, dicyclopentenyl- (meth) acrylate, N, N-dimethyl- (meth) a rilamide, tetrachlorophenyl- (meth) acrylate, 2-tetrachlorophenoxyethyl- (meth) acrylate, tetrahydrofurfuryl- (meth) acrylate, tetrabromophenyl- (meth) acrylate, 2-tetrabromophenoxyethyl (meth) acrylate, 2-trichlorophenoxyethyl, tribromophenyl (meth) acrylate, 2-tribromophenoxyethyl- (meth) acrylate, 2-hydroxyethyl- (meth) acrylate, 2-hydroxypropyl- (meth) acrylate, vinylcaprolactam, N-vinylpyrrolidone, phenoxyethyl- (meth) acrylate, butoxyethyl- (meth) acrylate, pentachlorophenyl- (meth) acrylate, pentabromophenyl- (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acryl t, bornil- (meth) acrylate and metiltrietilendiglikol- (meth) acrylate, and mixtures thereof.

Examples of commercially available monofunctional monomers include SR 313A, 313B and 313D (C ₁₂ -C ₁₄ -alkyl- (meth) acrylates, available from Sartomer Co. Inc.) and Ciba® Agefiex FM6 ( n- hexyl- (meth) acrylate, available from Ciba Specialty Chemicals).

In another embodiment, the (meth) acrylate is a multifunctional or poly (meth) acrylate monomer having a functionality of 2 or higher. Examples of poly (meth) acrylate monomers include ethylene glycol di (meth) acrylate, dicyclopentenyl di (meth) acrylate, triethylene glycol diacrylate, tetraethylene glycol di (meth) acrylate, tricyclodecanediyl dimethylene di (meth) acrylate, tris (2-hydroxyethyl) di (meth) acrylate, tris (2-hydroxyethyl) isocyanurate-tri (meth) acrylate modified with caprolactone tris (2-hydroxyethyl) isocyanurate-tri (meth) acrylate, trimethylolpropane-tri (meth) acrylate, EO-modified trimethylolpropane-three (meth) acrylate, PO-modified trimethylolpropane-tri (meth) acrylate, tri opylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, pentaerythritol-tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, polyester-di (meth) acrylate, polyethylene glycol-di (meth) acrylate, dipentaerythritol-penta (meth) acrylate, dipentaerythritol-tetra (meth) acrylate, modified caprolactone dipentaerythritol-hexa (meth) acrylate, modified caprolactone dipentaerythritol-penta (meth) acrylate, ditrimethylolpropane-tetra (meth) acrylate, EO-modified bisphenol A di- (meth) acrylate, PO-modifications bisphenol A di- (meth) acrylate, EO-modified hydrogenated bisphenol A di- (meth) acrylate, PO-modified hydrogenated bisphenol A di- (meth) acrylate, EO-modified bisphenol F di- (meth) acrylate and mixtures thereof . The multifunctional monomer is not dipentaerythritol hexaacrylate.

The following are examples of commercially available poly (meth) acrylates: SR 295 (pentaerythritol tetraacrylate); SR 350 (trimethylol propane trimethacrylate); SR 351 (trimethylolpropane triacrylate); SR 367 (tetramethylol methane tetramethacrylate); SR 368 (Tris (2-acryloxyethyl) isocyanurate triacrylate); SR 399 (dipentaerythritol pentaacrylate); SR 444 (pentaerythritol triacrylate); SR 454 (ethoxylated (3) -trimethylolpropane triacrylate); SR 833S (tricyclodecane dimethanol diacrylate) and SR 9041 (dipentaerythritol pentaacrylate ester), available from Sartomer Co. Inc. In one embodiment, the implementation of the poly (meth) acrylate includes a bifunctional acrylate compound, for example SR 833S.

Additional examples of commercially available acrylates that can be used in the present invention include Kayarad® R-526 (bis [2,2-dimethyl-3 - [(1-oxo-2-propenyl) oxy] propyl] hexanedioic acid ester), SR 238 (hexamethylenediol diacrylate), SR 247 (neopentyl glycol diacrylate), SR 06 (tripropylene glycol diacrylate), Kayarad® R-551 (bisphenol A and polyethylene glycol diacrylate diacrylate), Kayarad® R-712 (2,2'- p -methylene-bis-phenylene) poly (oxyethylene) oxy] diethyl diacrylate), Kayarad® R-604 ([2- [1,1-dimethyl-2 - [(1-oxo-2-propenyl) oxy] ethyl] -5-ethyl-1, 2-propeno 3-dioxan-5-yl] methyl ester acid), Kayarad® R-684 (dimethyltricyclodecanediacrylate), Kayarad® PET-30 (pentaerythritol triacrylate), GPO-303 (polyethylene glycol dimethacrylate), Kayarad® THE-330 (ethoxylated trimethylolpropanetriacryl-2-D, DP), 310 (DPHA), Kayarad® D-330 (DPHA), DPCA-20, DPCA-30, DPCA-60, DPCA-120, DN-0075, DN-2475, Kayarad® T-1420 (dithrimethylol propane tetraacrylate), Kayarad® T -2020 (ditrimethylol propane tetraacrylate), TPA-2040, TPA-320, TPA-330, Kayarad® RP-1040 (pentaerythritol tetraacrylate) (available from Sartomer Co. Inc.); R-011, R-300, R-205 (methacrylic acid as zinc salt, same as SR 634) (available from Nippon Kayaku Co., Ltd.); Aronix M-210, M-220, M-233, M-240, M-215, M-305, M-309, M-310, M-315, M-325, M-400, M-6200, M -6400 (available from Toagosei Chemical Industry Co, Ltd.); Light acrylate BP-4EA, BP-4PA, BP-2EA, BP-2PA, DCP-A (available from Kyoeisha Chemical Industry Co., Ltd.); New Frontier BPE-4, TEICA, BR-42M, GX-8345 (available from Daichi Kogyo Seiyaku Co., Ltd.); ASF-400 (available from Nippon Steel Chemical Co.); Ripoxy SP-1506, SP-1507, SP-1509, VR-77, SP-4010, SP-4060 (available from Showa Highpolymer Co., Ltd.); NK Ester A-BPE-4 (available from Shin-Nakamura Chemical Industry Co., Ltd.); SA-1002 (available from Mitsubishi Chemical Co., Ltd.); Viscoat-195, Viscoat-230, Viscoat-260, Viscoat-310, Viscoat-214HP, Viscoat-295, Viscoat-300, Viscoat-360, Viscoat-GPT, Viscoat-400, Viscoat-700, Viscoat-540, Viscoat- 3000, Viscoat-3700 (available from Osaka Organic Chemical Industry Co., Ltd.)

The free radical active component may be or may include a copolymer obtained by (co) polymerizing a monomer comprising at least 1 (meth) acrylate group, preferably at least 2 (meth) acrylate functional groups. Commercial examples: a fluorinated polyoxytane oligomer with the same acrylate functionality as Polyfox PF 3320, PF3305, from Omnova and polybutadiene (meth) acrylate (CN307, CN303 from Sartomer).

The Polyfox fluorine-containing surfactant family includes polymers with a molecular weight greater than 1000. Polyfox polymers are based on ether bonds, both on the backbone of the polymer and on the bond between the backbone and the perfluoroalkyl side chains. Polyfox fluorine-containing surfactants are synthesized from perfluoroalkyl starting materials with a fully fluorinated carbon chain of C ₄ or less in length. These products are obtained with perfluoroalkyl side chains of C ₂ F ₅ or CF ₃ . The fluorinated polyester carries an acrylate group as a terminal group. Occitan rings are open.

The basic structure of the Polyfox 3320 connection is as follows (x + y equals approximately 20):

Structure 1

The free radical active compound may also be a (hyperbranched) dendritic acrylate polymer compound. Dendritic acrylate polymer compounds are compounds consisting essentially of ether or polyester units, optionally in combination with ether or polyester units, resulting in a tree-like amorphous structure. These compounds, characterized by the presence of a tightly branched backbone and a large number of active terminal groups, are usually prepared from hyperbranched polymer polyols with hydroxyl functional groups by any means suitable for the preparation of acrylate esters, including transesterification, direct esterification or reaction with (meth) acryloyl halides.

An example of a dendritic acrylate polymer suitable for use in the present invention includes a dendritic polyester acrylate compound. Said dendritic polyester acrylate compound preferably has an acrylate functionality of at least 12, and more preferably at least 14. Examples of commercially available dendritic polyester acrylates include CN 2301 and CN 2302 (available from Sartomer Co. Inc.). Siloxane acrylates (Wacker Chemie AG) are also available.

The free radical active compound may also be an epoxy functionalized compound. The specified epoxyfunctionalized compound can be obtained by known methods, for example, from the reaction of a di- or polyepoxide with one or more equivalents of ethylenically unsaturated carboxylic acid. An example of this compound is the reaction product of UVR-6105 with one equivalent of methacrylic acid. Commercially available compounds bearing epoxy and free radical active functional groups included in the Cyclomer group, such as Cyclomer M-100, M-101, A-200 and A-400, are available from Daice1 Chemical Industries Ltd., Japan, and also Ebecryl-3605 and -3700, available from UCB Chemical Corp.

It is possible that the free radical active component of the present invention includes a mixture of free radical active compounds described above. The free radical active component is not dipentaerythritol hexaacrylate.

In one embodiment of the present invention, the free radical active component comprises at least one poly (meth) acrylate having a functionality of 2 and a molecular weight within the range of about 200-500. The photocurable composition may contain more than 5% wt., Preferably more than 15% wt. and most preferably more than 25% wt. based on the total weight of the photocurable composition, a poly (meth) acrylate having functionality 2. In another embodiment, the free radical active component comprises at most about 60 wt.%, more preferably at most about 45% wt. and most preferably at most about 40% wt. based on the total weight of the photocurable composition, a poly (meth) acrylate having a functionality of 2. In yet another embodiment, the poly (meth) acrylate having a functionality of 2 is present in the photocurable composition in the range of about 5-60 wt.%, more preferably about 10 -40% wt. and most preferably about 15-25% wt. of the total mass of the photocurable composition.

In another embodiment of the present invention, the free radical active component may further include at least one hyperbranched (dendritic) polyester acrylate compound in such an amount that the dendritic polyester acrylate is present in the photocurable composition in an amount of at least 1% by weight, preferably at least about 5% wt. and most preferably at least about 10% wt. of the total mass of the photocurable composition. In yet another embodiment, the dendritic polyester acrylate is present in an amount of at most about 40% by weight, preferably at most about 30% by weight. and most preferably at most about 20% wt. of the total mass of the photocurable composition. In yet another embodiment, the dendritic polyester acrylate is present in the range of about 0.01-35% by weight, more preferably about 0.5-25% by weight. and most preferably about 1-15% wt. of the total mass of the photocurable composition.

In yet another embodiment of the present invention, the free radical active component may further include at least one epoxy functionalized compound. In the photocurable composition, the epoxy-functionalizable compound is preferably present in an amount of about 0.01-30% by weight, preferably about 0.5-25%, by weight. and most preferably from about 1-20% wt. of the total mass of the photocurable composition.

The total amount of free radical active compound present in the photocurable composition is usually at least about 5% by weight, more preferably at least about 10% by weight. and most preferably at least about 15% wt. of the total mass of the photocurable composition. In another embodiment of the present invention, the free radical active component may be present in an amount of at most about 60% by weight, more preferably at most about 50% by weight. and most preferably at most about 40% wt. of the total mass of the photocurable composition. In yet another embodiment, the free radical active component may be present in the range of about 5-60 wt.%, Preferably about 15-60 wt.%, More preferably more than 25% wt. and less than about 40% wt. and most preferably about 30-40% wt. of the total mass of the photocurable composition.

Antimony Free Cationic Photoinitiator

As a third essential component, the photocurable composition of the present invention comprises about 0.1-10% by weight. of the total weight of the photocurable composition of at least one antimony-free cationic photoinitiator. It has been unexpectedly found that the use of an antimony-free cationic photoinitiator in a photocurable composition of the present invention allows a non-toxic photocurable composition to be obtained whose cure rate is similar to that of a photocurable composition containing antimony-based cationic initiator, with the product having significantly improved mechanical properties after curing .

The antimony-free cationic photoinitiator can be selected from photoinitiators commonly used to initiate cationic photopolymerization. Examples include onium salts with slightly nucleophilic anions, for example, halon salts, iodosil salts, sulfonium salts, sulfoxonium salts, diazonium salts, pyrilium salts or pyridinium salts. Metallocene salts are also suitable as photoinitiators. Onium and metallocene salt photoinitiators are described in US Pat. No. 3,708,296; in JV Crivello, "Photoinitiated Cationic Polymerization," UV Curing: Science & Technology, (SP Pappas, ed., Technology Marketing Corp. 1978), as well as in JV Crivello and K. Dietliker, "Photoinitiators for Cationic Polymerisation," Chemistry and Technology of UV & EV Formulation for Coatings, Inks & Paints 327-478 (PK Oldring, ed., SITA Technology Ltd 1991), each of which is incorporated herein by reference.

The antimony-free cationic photoinitiator may also be a dialkylphenylacylsulfonium salt, as described in US Pat. No. 6,863,701, which is incorporated herein by reference. Said antimony-free cationic photoinitiators have the general formula A ₁ (CA ₂ A ₃ OH) _n , where A _{1 is} selected from phenyl, polycyclic aryl and polycyclic heteroaryl, each of which is optionally substituted with one or more electron-donating groups, A ₂ and A ₃ independently selected from hydrogen, alkyl, aryl, alkylaryl, substituted alkyl, substituted aryl and substituted alkylaryl, and n is an integer from 1 to 10. Preferably, antimony-free cationic photoinitiators are compounds corresponding to formula (I):

Where

R ₁ , R ₂ and R ₃ are each independently from each other, C _6-18 aryl, which is unsubstituted or substituted by suitable radicals,

Q represents boron or phosphorus,

X are a halogen atom, and

m is an integer corresponding to the valency of Q plus 1.

Examples of C _6-18 aryl include phenyl, naphthyl, antryl and phenanthryl. Suitable radicals include alkyl, preferably C _1-6 alkyl, such as methyl, ethyl, n- propyl, isopropyl, n -butyl, sec -butyl, iso- butyl, tert -butyl or various isomers of pentyl or hexyl, alkoxy, preferably C _1-6 alkoxy, such as methoxy, ethoxy, propoxy, butoxy, pentyloxy, or hexyloxy, alkylthio, preferably C _1-6 alkylthio, such as methylthio, ethylthio, propylthio, butylthio, pentylthio, or hexylthio, halogen, such such as fluoro, chloro, bromo or iodo, amino groups, cyano groups, nitro groups or arylthio groups such as phenylthio group. Preferred QX _m groups include BF ₄ and PF ₆ . A further example of a group QX _m suitable for use in the present invention includes perfluorophenyl borate, for example tetrakis (perfluorophenyl) borate.

Examples of commercially available antimony-free cationic photoinitiators include: (1) hexafluorophosphates (PF ₆ ), including (i) Cyracure® UVI-6992 (Dow Chemical Co.), CPI 6992 (Aceto Corp.), Esacure® 1064 (Lamberti spa) and Omnicat 432 (IGM Resins BV), which are triarylsulfonium hexafluorophosphates (a mixture of thio and bis salts); (ii) SP-55 (Asahi Denka Co. Ltd.), Degacure KI 85 (Degussa Corp.) and SarCat KI-85 (available from Sartomer Co. Inc.), which are triarylsulfonium hexafluorophosphates (bis salts); (iii) SP-150 (Asahi Denka Co. Ltd.) bis-hexafluorophosphate bis [4- (di- (4- (2-hydroxyethyl) phenyl) sulfonio) phenyl] sulfide; (iv) Esacure® 1187 (Lamberti spa) - modified sulfonium hexafluorophosphate; (v) metallocene salts, including cumenylcyclopentadienyl iron hexafluorophosphate (II), Irgacure® 261 (Ciba Specia1ty Chemicals), naphthalenyl cyclopentadienyl iron hexafluorophosphate (II), benzyl cyclopentadienyl iron fluorophosphate (II) hexafluorophosphate (II) g; (vi) iodonium salts, including UV1242 - bis (dodecylphenyl) iodonium hexafluorophosphate (Deuteron), UV2257 - bis (4-methylphenyl) iodonium hexafluorophosphate (Deuteron), and Omnicat 440 (IGM Resins BV), Irgacure® 250 (Ciba Spec) - hexafluorophosphate (4-methylphenyl) - (4- (2-methylpropyl) phenyl) iodonium; (vii) thioxanthene salts, including Omnicat 550 (IGM Resins BV) - 10-biphenyl-4-yl-2-isopropyl-9-oxo-9H-thioxanthen-10-ium hexafluorophosphate, Omnicat 650 (IGM Resins BV) - hexafluorophosphate adduct 10-biphenyl-4-yl-2-isopropyl-9-oxo-9H-thioxanthen-10-yum with a polyol; and (2) pentafluorophenylborates, including Rhodorsil 2074 (Rhodia) tetrakis (pentafluorophenyl) borate (tolylcumyl) iodonium. The antimony-free cationic photoinitiator may include one antimony-free cationic photoinitiator or a mixture of two or more antimony-free cationic photoinitiators.

The proportion of the antimony-free cationic photoinitiator in the photocurable composition may be at least about 0.1% by weight, preferably at least about 1% by weight. and most preferably at least about 4% wt. of the total mass of the photocurable composition. In another embodiment of the present invention, the antimony-free cationic photoinitiator is present in an amount of at most about 10% by weight, more preferably at most about 8% by weight. and most preferably at most about 7% wt. of the total mass of the photocurable composition. In yet another embodiment, the antimony-free cationic photoinitiator is present in the range of about 0.1-10 wt.%, Preferably about 0.5-8 wt.%. and more preferably about 2-7% wt. of the total mass of the photocurable composition.

Free radical photoinitiator

The photocurable composition of the present invention may also include at least one free radical photoinitiator in an amount of 0-10% by weight, preferably about 0.01-10% by weight. the total weight of the photocurable composition. The free radical photoinitiator can be selected from photoinitiators commonly used to initiate radical photopolymerization. Examples of free radical photoinitiators include benzoins, for example benzoin, benzoin esters such as benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin phenyl ether and benzoin acetate; acetophenones, for example acetophenone, 2,2-dimethoxyacetophenone and 1,1-dichloroacetophenone; benzyl ketals, for example benzyl dimethyl ketal and diethyl benzyl ketal; anthraquinones, for example 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-chlorantraquinone and 2-amylanthraquinone; triphenylphosphine; benzoylphosphine oxides, e.g. 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (Luzirin TPO); bisacylphosphine oxides; benzophenones, e.g. benzophenone and 4,4'-bis (N, N'-dimethylamino) benzophenone; thioxanthones and xanthones; acridine derivatives; phenazine derivatives; quinoxaline derivatives; 1-phenyl-1,2-propanedione-2-O-benzoyloxime; 4- (2-hydroxyethoxy) phenyl- (2-propyl) ketone (Irgacure® 2959); 1-aminophenylketones or 1-hydroxyphenylketones, for example 1-hydroxycyclohexylphenylketone, 2-hydroxyisopropylphenylketone, 1-hydroxyisopropylphenylketone and 4-isopropylphenyl-1-hydroxyisopropylketone. Polymer free radical photoinitiators such as Genopol BP-1 from Rahn may also be used.

Preferably, the free radical photoinitiator is cyclohexyl phenyl ketone. More preferably, cyclohexyl phenyl ketone is 1-hydroxyphenyl ketone. Most preferably, 1-hydroxyphenyl ketone is 1-hydroxycyclohexyl phenyl ketone, for example Irgacure® 184. A free radical photoinitiator may include one free radical photoinitiator, or two or more free radical photoinitiators.

The proportion of the free radical photoinitiator in the photocurable composition of the present invention may be about 0.01-10% by weight, more preferably about 0.2-8% by weight. and most preferably about 0.5-4% wt. of the total mass of the photocurable composition. In another embodiment of the present invention, the free radical photoinitiator is present in an amount of about 1: 8, preferably 2: 5 parts by weight of the free radical photoinitiator with respect to the antimony free cationic photoinitiator.

According to the present invention, it is more preferable to use a combination of triarylsulfonium-PF ₆ and Irgacure 184, which provides better sensitivity and polymerization kinetics in radical cationic systems.

Impact Resistant Additive

The photocurable composition of the present invention may also include one or more impact resistance additives in an amount of 0-40% by weight, preferably about 0.01-40% by weight. of the total mass of the photocurable composition.

Impact enhancing additive may be particles in a shell with a core of an active and / or inactive type. For example, in one embodiment of the present invention, a shockproofing additive that can be added to the photocurable composition comprises active particles having a crosslinked elastomeric core and a shell carrying active groups. Active particles can be obtained by the method described in US Patent No. 4853434, which is incorporated herein by reference. This reference discloses active particles applicable in the creation of fiber-reinforced plastics, mounting adhesives, laminated plastics, and annealing varnishes.

The core of the active particles may consist of polysiloxane, polybutadiene, polybutadiene styrene, amino terminated polybutadiene, polybutadiene methacrylate, alkyl acrylates, polyorganosiloxane, rubber, urethane acrylate, modified polyethylene glycol, other polyurethane acrylate. In one embodiment of the present invention, the crosslinked core consists of polysiloxane. In another embodiment, the polysiloxane core consists of a cross-linked polyorganosiloxane rubber, which may include dialkylsiloxane repeating units, where the alkyl is C _1-6 alkyl. In yet another embodiment, the polysiloxane core includes dimethylsiloxane repeating units.

The shell carrying the active groups may consist of a styrene / acrylonitrile copolymer, a polyacrylonitrile, a methyl methacrylate / styrene copolymer with a carboxyl functional group, a styrene / butyl acrylate copolymer, a polystyrene, a methyl methacrylate / maleic anhydride copolymer, a copolymethyl acrylate copolymer, a polyalkyl acrylate copolymer modified vinyl esters, epoxides, polymethyl methacrylate, glycidyl methacrylate / acrylonitrile copolymer, poly (cyclohexanedimethanol-tereph Alata), a thermoplastic resin such as polycarbonate, a copolymer of methyl methacrylate / glycidyl methacrylate copolymer, methyl methacrylate / akrilonitrila / divinylbenzene.

Active shell groups may be epoxy groups, oxitan groups, ethylene unsaturated groups and / or hydroxy groups. In one embodiment of the present invention, the active groups may be oxirane, glycidyl, vinyl ester, vinyl ester, acrylate groups, and mixtures thereof.

The active particles preferably have an average diameter of about 0.01-50 microns, more preferably about 0.1-5 microns, and most preferably about 0.1 to about 3 microns. Examples of active particles that are commercially available include Albidur EP 2240 - silicone / epoxy particles in Bisphenol A / epoxy; Albidur VE 3320 - silicone / vinyl ester particles in Bisphenol / vinyl ester; and Albidur EP 5340, silicone / epoxy particles in cycloaliphatic epoxy resin (all available from Hanse Chemie).

In one embodiment of the present invention, the active particles are added to the photocurable composition in the form of a mixture of active particles and an active liquid medium containing, for example, epoxy or ethylene unsaturated groups. For example, active organosiloxane particles are dispersed in bisphenol A / glycidyl ether in the case of Albidur EP 2240, in bisphenol A / vinyl ester in the case of Albidur VE 3320 and in cycloaliphatic epoxide in the case of Albidur EP 5340.

The amount of active particles added to the photocurable composition may be different and depends on the cationically curable component and the free radical active component. The amount of active particles present in the photocurable composition may be at least about 0.5% by weight, more preferably at least about 1% by weight. and most preferably at least about 1.5% wt. of the total mass of the photocurable composition. In another embodiment of the present invention, the proportion of active particles in the composition is at most about 40% by weight, more preferably at most about 15% by weight. and most preferably at most about 10% wt. of the total mass of the photocurable composition. In yet another embodiment, the active particles are present in the range of about 0.01-40% wt., Preferably about 0.5-15% wt. and most preferably about 1-5% wt. the total weight of the photocurable composition.

Other impact resistance additives that can be added to the photocurable composition in addition to or instead of active particles include one or more hydroxyl-containing compounds. The hydroxyl-containing compound (s) has at least 1 corresponding functional group, and more preferably at least 2, and does not contain any groups that inhibit the curing reaction. The hydroxyl-containing compound may be an aliphatic or aromatic hydroxyl-containing compound. Examples include polyether polyols, polyester polyols, polybutadiene with hydroxyl and hydroxyl / epoxy functional groups, 1,4-cyclohexanedimethanol, polycaprolactone diols and triols, ethylene / butylene polyols, and polyhydroxyl functional monomers.

In one embodiment, the hydroxyl-containing compound is polytetramethylene glycol ether ("poly-THF"). Poly-THF preferably has a molecular weight of from about 250 to about 2500, and at the end may have a hydroxy, epoxy, or ethylene unsaturated group (s). Commercially available poly-THFs include Polymeg® poly-THFs, for example Polymeg® 1000, which is a linear diol with a nominal molecular weight of 1000 (Penn Specialty Chemicals). In another embodiment, the compound containing hydroxyl functional groups is a caprolactone-based oligo- or poly (ester), for example, trimethylolpropane-triether with caprolactone, such as Tone® 301 (Dow Chemical Co.) In another embodiment, the compound containing hydroxyl functional groups, is a polyester, for example k-flex 188 (from Kings Industries). When the hydroxyl-containing compound is present in the photocurable composition, its total amount that can be added to the photocurable composition is usually about 0.01-40% by weight, and preferably about 0.5-20% by weight. of the total mass of the photocurable composition.

Other optional components

The photocurable composition of the present invention may also include other components, for example, stabilizers, modifiers, anti-foam additives, leveling agents, thickeners, flame retardants, antioxidants, pigments, paints, fillers, nanofillers having an average particle size of 3-500 nanometers, as well as combinations thereof.

Stabilizers that can be added to the photocurable composition to prevent viscosity increase during use include butylated hydroxytoluene ("BHT"), 2,6-di-tert-butyl-4-hydroxytoluene, stereo-protected amines, such as benzyl dimethylamine ("BDMA") , N, N-dimethylbenzylamine, as well as boron complexes. If stabilizers are used, their amount may be from about 0.001% to about 5% wt. of the total mass of the photocurable composition.

Fillers, including inorganic or organic, powder, flocculent or fibrous materials, may also be added. Examples of inorganic fillers include mica, glass or quartz, calcium carbonate, barium sulfate, talc, glass or quartz hollow microspheres, zirconium silicate, iron oxides, glass fiber, asbestos, kieselguhr, dolomite, metal powders, titanium oxides, cellulose powder, kaolin, modified kaolin, hydrated kaolin-metal fillers, ceramics and composites. Examples of organic fillers include polymeric compounds, thermoplastics, core particles, aramid, kevlar, nylon, cross-linked polystyrene, cross-linked polymethyl methacrylate, polystyrene or polypropylene, cross-linked polyethylene in powder, cross-linked phenolic powder, cross-linked phenolic resin, a crosslinked urea resin in powder, a crosslinked melamine formaldehyde resin in powder, a crosslinked polyester resin in powder and a crosslinked epoxy resin in powder. Both inorganic and organic fillers may optionally serve as a surface that is treated with various crosslinking agents. Examples include methacryloxypropyltrimethoxysilane, β - (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ -glycidoxypropyltrimethoxysilane and methyltriethoxysilane. Mixtures of inorganic and organic fillers may also be used.

Further examples of preferred fillers include microcrystalline quartz, crystalline quartz, amorphous quartz, alkaline aluminosilicate, feldspar, wollastonite, alumina, aluminum hydroxide, glass powder, alumina trihydrate, surface treated alumina trihydrate, and alumina silicate. Each of the preferred excipients is commercially available. Most preferred filler materials are inorganic fillers such as mica, Imsil, Novasit, amorphous quartz, feldspar and alumina trihydrate. These fillers preferably transmit UV light, have a low tendency to refract or reflect incident light and provide good dimensional stability and high temperature resistance. Nanofillers such as layered clays (nanoclay), nano-lasers, whiskers of aluminum borate, barium nanosulfate (Nanofine, available from Solvay), quartz nanoparticles dispersed in UV-curable monomers (a number of Nanopox and Nanocryl materials from Nanoresins), nanoparticles can also be used. alumina dispersed in UV-curable monomers (Nanobyk by Byk Chemie).

The filler and nano filler used in the polymer composition for stereolithography in accordance with the present invention should not also prevent cationic or radical polymerization, and the filled SL composition should have a relatively low viscosity suitable for the stereolithography method. Fillers and nanofillers can be used on their own or as a mixture of two or more fillers, depending on the desired operating mode. Fillers and nanofillers used in the present invention may be neutral, acidic or basic, with some being more preferred basic. The particle size of the filler may vary depending on the practical application and the required characteristics of the resin. Particle size can vary from 50 nanometers to 50 microns. The particle size of nanofillers can vary from 3 to 500 nanometers. In order to provide a good dispersion of said nanofillers, dispersants can be used.

If fillers are present in the photocurable composition, their content is usually from about 0.5% wt. up to about 30% wt. of the total mass of the photocurable composition. The photocurable compositions of the present invention can be prepared in a known manner, for example, by pre-mixing the individual components followed by mixing the resulting premixes or by mixing all the components using standard devices, such as stirred tanks. In one embodiment of the present invention, the mixing is carried out in the absence of light and, if necessary, at slightly elevated temperatures in the range from about 30 ° C to about 60 ° C. In addition, it is preferable that the photocurable composition has a viscosity at 25 ° C. in the range of 50-1000 cP, preferably 70-700 cP.

In one embodiment, the implementation of the photocurable composition of the present invention is obtained by mixing approximately 35-80% wt. cationically curable component, approximately 15-60% wt. free radical active component, approximately 0.1-10% wt. free of antimony cationic photoinitiator, 0-10% wt. free radical photoinitiator, and 0-40% wt. shock resistance additives, where% wt. taken from the total mass of the photocurable composition. In another embodiment, the photocurable composition is obtained by mixing from about 45-70% wt. cationically curable component comprising a hydrogenated bisphenol-epoxy compound and an oxitane compound, more than 25% wt. and up to about 40% wt. free radical component comprising at least one poly (meth) acrylate having a functionality of 2, approximately 0.5-8% wt. free of antimony cationic photoinitiator, approximately 0.5-4% wt. free radical photoinitiator, and 0-40% wt., preferably approximately 0.01-40% wt. shock resistance additives, where% wt. taken from the total mass of the photocurable composition.

New photocurable compositions can be polymerized by irradiation with actinic light, for example using electron beams, X-rays, UV or visible light, the radiation wavelength range being preferably 280-650 nm. The most suitable are the rays of a HeCd laser, an argon ion or nitrogen laser, as well as lasers operating on metal pairs and NdYAG lasers. The present invention extends to all types of existing lasers or lasers under development that are to be used in a method for displaying solid objects (stereolithography), for example, semiconductor and argon ion lasers, etc., as well as non-laser based radiation. A person skilled in the art is aware that for each selected light source, it is necessary to select the appropriate photoinitiator and, if necessary, carry out sensitization. It was proved that the depth of radiation penetration into the polymerizable composition, as well as the speed of the process, is directly proportional to the absorption coefficient and concentration of the photoinitiator. In stereolithography, it is preferable to use photoinitiators that release the greatest number of particles forming free radicals or cationic particles, and which provide the greatest depth of radiation penetration into the polymerized compositions.

It is preferable that the photocurable compositions of the present invention upon radiation polymerization produce an article having a cohesive strength in 10 minutes of at least 100 MPa. It is also preferable that the photocurable composition after 1.5 hours after curing in the post-curing apparatus provide a photocurable product having at least one of the following properties:

(i) the modulus of elasticity in bending has a value in the range between 1000-2300 MPa;

(ii) the average elongation at break is at least 5%;

(iii) the tensile strength is at least 30 MPa;

(iv) the liquid photocomposition used to make the product has a viscosity of less than 500 cP;

(v) the notched Izod impact strength is at least 0.5 psi; and / or

(vi) the ash content is less than 0.05%.

Thus, a further aspect of the present invention includes a method for producing a three-dimensional antimony-free article in successive cross-sections in accordance with an article model by forming a first layer of a photocurable composition; exposing the first layer to the action of actinic radiation in a plane corresponding to a certain cross-section of the model, sufficient to cure the first layer in the displayed area; forming a second layer of the photocurable composition on top of the cured first layer; exposing the second layer to the action of actinic radiation in a plane corresponding to a certain cross-section of the model, sufficient to cure the second layer in the displayed area; and with the subsequent repetition of the two previous stages, which allows you to form such sequential layers as are required to obtain a three-dimensional antimony-free product that can be used in various fields, for example, in the space industry and in the investment casting industry, or for medical use .

In principle, any stereolithographic apparatus may be used to implement the method of the present invention. Stereolithography equipment is commercially available from various manufacturers. Table I lists examples of commercial stereolithography equipment available from 3D Systems Corp. (Valencia, Calif).

                                TABLE I INSTALLATION WAVE LENGTH (nm) SLA® 250 325 SLA® 500 351 SLA® 3500 355 SLA® 5000 355 SLA® 7000 355 Viper si2 ^TM 355 Viper pro v 355

Most preferably, the stereolithography process for producing three-dimensional article from the photocurable composition of the present invention includes the preparation of the composition surface to form a first layer, and then applying a subsequent layer on the first layer and each successive layer of the three-dimensional article using the apparatus for applying Zephyr ^TM coatings (3D Systems Corp ., Valencia, Calif) or its analogue.

It would be preferable to obtain a stable, antimony-free, photocurable composition of low viscosity, which can be cured quickly in a method for displaying solid objects using a liquid in order to obtain a medical product with high cohesive strength, impact resistance and dimensional accuracy with minimal distortion.

The present invention relates to photocurable compositions comprising a cationically curable component, a free radical active component, an antimony-free cationic photoinitiator and, optionally, a free radical photoinitiator, an impact resistance improver, and one or more other additional components. It was unexpectedly found that the combination of these components allows you to get a non-toxic photocurable composition of low viscosity, which when quickly laser cured gives a three-dimensional medical product that has an excellent balance of cohesive strength, impact resistance, elasticity, dimensional accuracy, wear resistance, increased water resistance, high color fastness, increased transparency, increased stability in the cured and uncured form, moisture resistance in the room and strength, When this term "three-dimensional medical device" refers to a product obtained by at least two cured resin composition layers. At the same time, without being bound by any particular theory, it is assumed that the antimony-free cationic photoinitiator forms active cationically curable components with different kinetics compared to antimony-based photoinitiators. During curing, the active cation-curable components formed by the antimony-free photoinitiator also act by a different curing method, which leads to less residual stress in the cured product and, thus, allows the production of a product having lower brittleness and greater impact resistance. Since the medical device is made from a non-toxic photocurable composition free of any component containing a heavy metal, the device can be used for medical purposes. Thus, the medical device may be, for example, a medical instrument, medical model and / or medical implant, fully meeting the requirements of USP 28, NF 23 for biological testing of plastics, class VI, 70 ° C.

As used herein, the term “medical instrument” refers to any physical item used in medical care and may include a catheter, stent, infusion therapy system, drug delivery system, chemotherapeutic tip, syringe, cardiovascular device, vascular access line, surgical instrument, for example an ergonomic surgical instrument, or a part of medical equipment.

As used herein, the term “medical model” refers to a three-dimensional product obtained from two-dimensional data, such as CAT (computed axial tomography) data and MRI (magnetic resonance imaging) data, which can be used for surgical planning, prosthesis development and as a training tool . Examples include models of an organ such as a liver, heart, lung, kidney, bladder, brain, eye, intestines, pancreas, and reproductive organ; bone models such as the skull, jaw, spine, rib, collarbone, scapula, humerus, radius, ulna, teeth, fingers and hands, sternum, femur, tibia and tibia; models of a joint, such as a spherical joint in the thigh and shoulder, as well as a joint in the knee and elbow; teeth; as well as tissues such as tumor, muscle, and cartilage.

As used herein, the term “medical implant” refers to an object that is made for insertion or placement within the body. Types of implants include implants suitable for replacing, repairing, supporting or modifying joints (such as described above), bones (such as described above), teeth, tissues (such as described above), and the like.

The present invention also provides a method for manufacturing a three-dimensional medical device, comprising the steps of applying a first layer of a photocurable composition of the present invention to a surface; exposing the layer from the images under the action of actinic radiation in order to form a displayed cross section, where the radiation has an intensity sufficient to cause substantial curing of the layer in the exposed areas; applying a second layer of the photocurable composition to a cross section previously exposed in the image; exposure of the second layer from the previous stage in the image under the action of actinic radiation in order to form the next displayed cross section, where the radiation has an intensity sufficient to cause substantial curing of the second layer in the exposed areas and cause adhesion to the previously exposed displayed cross section; and repeating the cycle a sufficient number of times, which allows to obtain a three-dimensional medical device.

Although the photocurable composition of the present invention is preferably used in a stereolithography method, the composition of the present invention can also be used for three-dimensional inkjet printing or other rapid prototyping methods for producing a three-dimensional product.

In the inkjet printing method, successive droplets of a photocurable composition are applied (for example, using an inkjet printhead, such as a piezoelectric inkjet printhead) to a substrate at predetermined positions, and then irradiated by exposing the droplets to electromagnetic radiation to cure the composition and obtain the desired three-dimensional product forms. Drops are applied in accordance with the required form, information about which is stored in a computer file, for example, in a CAD file. The base may include paper, fabrics, tiles, printing plates, wallpaper, plastic or paste. The photocurable composition may be irradiated in pixels, in lines, in layers and / or after several layers have been applied, and / or after all layers have been applied. The electromagnetic radiation used may be UV light, microwave radiation, visible light, laser beams, or other similar sources.

Alternatively, a photocurable composition of the present invention can be applied to a powder. The powder can be distributed as a thin layer on the base, and the photocurable composition is sprayed onto the powder in the required positions in the desired plane. The sample can then be cured by exposing the photocurable composition to UV light. Then, on top of the first layer, a further layer of powder can be applied, after which the method is repeated to create a three-dimensional product. The remaining uncured powder can be removed after manufacturing a three-dimensional product. After removal of the uncured powder, final curing of the three-dimensional article by high temperature and / or radiation can be carried out. As a result, the photocurable composition fully combines with the powder.

In another embodiment of the present invention, the powder comprises an active component that can either react with the photocurable composition, or the photocurable composition facilitates the reaction of said active ingredient with itself. The powder may contain organometallic polymers, oligomers or monomers. Examples include polyacrylic acid, copolymer (acrylonitrile / butadiene, poly (allylamine), polyacrylic resins with functional acrylate groups, polybutadiene, butadiene with functional epoxy groups, poly (glycidyl (meth) acrylate), poly-THF, polycaprolacton diols, HEMA, polymers HEMA, HEMA, maleic anhydride, such as styrene-maleic anhydride, polyvinyl butyral, polyvinyl alcohol, poly (4-vinyl phenol), copolymers / mixtures of these compounds, as well as any of these compounds having epoxy, vinyl ester, acrylate / methacrylate at the end th, hydroxy, amino or vinyl groups. Additionally, the powder may comprise organic or inorganic filler, a pigment, nanoparticles, a dye and / or a surfactant.

In one embodiment, a three-dimensional article made from a photocurable composition of the present invention is used as a casting model for investment casting. In investment casting, a removable casting model made from the photocurable composition of the present invention is used to make a mold in which parts can be cast. The mold is created around the casting model in a known manner, the details of which differ depending on the type of metal that will be cast into the mold. Typically, using ferroalloy casting as an illustration of the investment casting method, the casting model is coated, namely, immersed in a refractory slurry, for example, in an aqueous ceramic slip dried from excess water, resulting in a coating that is then plastered with fine ceramic sand. This stage is usually repeated several times (usually 10-20 layers) after the first coating has dried. Then the casting model is placed in an open metal container, which is filled with a coarse suspension of ceramic molding material, which then hardens. Then the casting model, placed in ceramics, is sent to the furnace or autoclave, where the casting model is melted or burned out from the mold obtained. When the casting model is removed, a cavity is formed in the mold corresponding to the shape and dimensions of the finished part, however, the casting model (and therefore the cavity) may be slightly larger to compensate for shrinkage or machining of the part that is made in the subsequent casting operation. The molten metal enters the mold cavity and hardens upon cooling. After hardening, the ceramic mold is removed to remove the finished part. Although metal casting is primarily considered, any liquid material capable of hardening, such as plastic or ceramic compositions, can be cast in the same way.

Since the photocurable composition of the present invention does not contain antimony, sensitive alloys can be cast in molds made using a stereolithographically obtained casting model. In addition, complex casting models can be precisely made. Finally, it was found that casting models have a low ash content (<0.05%) and also retain their accuracy and rigidity over time, making them ideal for casting active metals.

Other applications in which the photocurable composition of the present invention can be used include a binder material, a coating, for example a photographic image coating, such as a photoresistive coating, or a coating for optical fibers, an insulator for LEDs, or paints, dyes or varnishes, or any other application is preferred , a method or method wherein the storage stable photocurable composition has stable curing mechanical properties.

EXAMPLES A

The general procedure for manufacturing three-dimensional products using stereolithographic equipment is as follows. The photocurable composition is placed in a bath designed for use with stereolithography equipment at approximately 30 ° C. The surface of the composition, either completely or in accordance with a previously defined plane, is irradiated with a UV / visible light source in such a way that the layer of the required thickness is cured and the irradiated area solidifies. A new layer of the photocurable composition is formed on the cured layer. A new layer is likewise irradiated over the entire surface or in a previously defined plane. The freshly cured layer adheres to the lower cured layer. The step of forming the layer and the step of irradiation is repeated until an untreated model consisting of a plurality of cured layers is obtained.

The term "raw model" means a three-dimensional product, originally formed by a stereolithographic method of applying and photocuring layers, where the layers are usually not fully cured. This allows successive layers to adhere better to each other during subsequent curing.

“Cohesive strength” is a generic term for the mechanical characteristics of an unprocessed model, including modulus, stress, strength, hardness and adhesion of adjacent layers. For example, cohesive strength can be estimated by measuring bending modulus (ASTM D 790). A product having low cohesive strength may deform under its own weight, or may settle or collapse during cure.

Next, the untreated model is washed in tripropylene glycol monomethyl ether ("TPM"), then rinsed with water and dried with compressed air. The dried untreated model is then finally cured using UV radiation in a post-curing apparatus ("PCA") for approximately 60-90 minutes. The term "post-cure" means a method for subsequent curing of the unprocessed model, allowing fully harden partially cured layers. The unprocessed model can be completely cured by heating, exposure to actinic radiation, or using both methods.

Tables A-II-VI list the components of each photocurable composition labeled as Examples A1-A23 and Comparative Example A1. The numerical values in Tables A II-A VI refer to the mass. the percentage of each component taken from the total mass of the photocurable composition. Table A VII provides additional trademark identification information in Tables A II-A VI.

TABLE A II Component Example A1
(% wt.) Example A2
(% wt.) Example A3
(% wt.) Example A4
(% wt.) Example A5
(% wt.) Uvacure 1500 3,995 3,995 3,995 3,995 7,895 Epalloy 5000 49 49 49 49 45 UVR-6000 OXT-101 fifteen fifteen fifteen fifteen OHT-121 fifteen CN 2301 5 fifteen 5 CN 2302 10.0 10.0 15.0 10.1 Ebecryl 3605 10 10 10 SR 833S 5 10 10 Irgacure 184 2 2 2 2 2 UVI 6992 5 5 5 5 5 Stabilizer 0.005 0.005 0.005 0.005 0.005 Total% wt. one hundred 10.0 one hundred one hundred one hundred

TABLE A III Component Example A 6 (% wt.) Example A7 (% wt.) Example A8 (% wt.) Example A 9 (% wt.) Example A10 (% wt.) Uvacure 1500 7,895 3,995 3,995 3,895 Epalloy 5000 45 49 49 49 52,895 Limonene Dioxide fifteen Limonene Monoxide fifteen OHT-10 fifteen fifteen OHT-221 fifteen CN 2301 5 5 5 5 CN 2302 10.1 10 10 10 Ebecryl 3605 10 10 10 SR 833S 15.1 20.1 Irgacure 184 2 2 2 2 2 UVI 6992 5 5 5 5 5 Stabilizer 0.005 0.005 0.005 0.005 0.005 Total% wt. one hundred one hundred one hundred one hundred one hundred

TABLE A IV Component Example All (% wt.) Example A12 (% wt.) Example A13 (% wt.) Example A14 (% wt.) Example A15 (% wt.) Uvacure 1500 7,895 eleven Epalloy 5000 52,895 45 17 thirty DCA 28 UVR-6000 fifteen fifteen 24 OXT-101 fifteen fifteen CN 2301 5 CN 2302 6 10.1 twenty 26 26 Ebecryl 3605 10 thirty 24 Cyclomer A 400 13 SR 833S 19.1 5 10 Irgacure 184 2 2 2 2 2 UVI 6992 5 5 5 5 5 Stabilizer 0.005 0.005 Total% wt. one hundred one hundred one hundred one hundred one hundred

TABLE A V Component Example A16 (% wt.) Example A17 (% wt.) Example A18 (% wt.) Example A19 (% wt.) Example A20 (% wt.) Uvacure 1500 8 3,895 Epalloy 5000 28 32 40 28 49 UVR-6000 fifteen twenty fifteen fifteen CN 2301 CN 2302 26 26 fifteen 15.1 15.1 Ebecryl 3605 24 24.9 Ebecryl 3700 Cyclomer A 400 twenty 10 10 SR 833S 5 Tone 301 fifteen E1 10 Irgacure 184 2 2 2 2 2 UVI 6992 5 5 5 5 5 Stabilizer Total% wt. one hundred one hundred one hundred one hundred one hundred Ebecryl 3605 UCB Surface Specialties Partially Acrylated Bisphenol A-Epoxy Ebecryl 3700 UCB Surface Specialties Bisphenol-A-Epoxy diacrylate SR 833S
SR-399 Sartomer Co. Inc.
Sartomer Co. Inc. Tricyclodecandimethanol diacrylate Dipentaerythritol pentaacrylate Cyclomer A 400 Daicel Chemical Industries, Ltd. 3,4-epoxy-cyclohexylmethyl-acrylate E1 Perstorp Specialty Chemicals Hyperbranched Epoxy Tone 301 Dow Chemical Co. Trifunctional Polyol Dianol 320 Seppic Propoxylated Bisphenol A Heloxy 48 Resolution Performance Products Triglycidyl ether Heloxy 107 Resolution Performance Products Diglycidyl ether cyclohexendimethanol Heloxy 84 Resolution Performance Products Aliphatic triol polyglycidyl ether Irgacure 184 Ciba Specialty Chemicals 1-hydroxycyclohexyl phenylketone UVI 6992 Dow Chemical Co. Mixed arylsulfonium hexafluorophosphates

Examples A1-A23 and Comparative Example A1 were prepared by combining the components and mixing them at room temperature until the mixture became homogeneous.

TABLE A VI Component Example A21 (% wt.) Example A22 (% wt.) Example A23 (% wt.) Comparative Example A1 (% wt.) Uvacure 1500 3,895 7,895 35 Epalloy 5000 49 45 52,895 He1oxy 48 16 He1oxy 107 13,2 He1oxy 84 8 UVR-6000 fifteen OXT-101 fifteen fifteen CN 2301 5 CN 2302 15.1 10.1 Ebecryl 3605 10 5 Ebecryl 3700 6.3 Cyclomer A400 10 SR 399 6 SR 833S 20.1 Dianol 320 8 Irgacure 184 2 2 2 2 UVI 6992 5 5 5 5.5 Stabilizer 0.005 0.005 0.005 0.01 Total% wt. one hundred one hundred one hundred one hundred

TABLE A VII Component Source Chemical Name Uvacure 1500 UCB Surface Specialties 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexane-carboxylate Epalloy 5000 CVC Specia1ty Chemicals Inc. Epoxidized Hydrogenated Bisphenol A UVR-6000 Dow Chemical Co. 3-ethyl-3-hydroxymethyl-1-hydroxytane DCA Asahi Denka Co. Ltd. 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexane-carboxylate Cyclomer A400 Daicel Chemical Industries, Ltd. 3,4-epoxy-cyclohexylmethyl-acrylate OXT-101 Toagosei Co. Ltd. 3-ethyl-3-hydroxymethyl-1-hydroxytane OXT-121 Toagosei Co. Ltd. 1,4-bis [3-ethyl-3-hydroxytanylmethoxy) methyl] benzene OXT-221 Toagosei Co. Ltd. Bis [1-ethyl-3-hydroxytanylmethyl] ether CN 2301 Sartomer Co. Inc. Hyperbranched Polyester Acrylate Oligomer CN 2302 Sartomer Co. Inc. Hyperbranched Polyester Acrylate Oligomer Ebecryl 3605 UCB Surface Specialties Partially Acrylated Bisphenol A-Epoxy Ebecryl 3700 UCB Surface Specialties Bisphenol-A-Epoxy diacrylate SR 833S Sartomer Co. Inc. Tricyclodecandimethanol diacrylate Cyclomer A 400 Daicel Chemical Industries, Ltd. 3,4-epoxy-cyclohexylmethyl-acrylate E1 Perstorp Specialty Chemicals Hyperbranched Epoxy Tone 301 Dow Chemical Co. Trifunctional Polyol Dianol 320 Seppic Propoxylated Bisphenol A Heloxy 48 Resolution Performance Products Triglycidyl ether Heloxy 107 Resolution Performance Products Diglycidyl ether cyclohexendimethanol Heloxy 84 Resolution Performance Products Aliphatic triol polyglycidyl ether Irgacure 184 Ciba Specia1ty Chemicals 1-hydroxycyclohexyl phenylketone UVI 6992 Dow Chemical Co. Mixed arylsulfonium hexafluorophosphates

Examples A1-A23 and Comparative Example A1 were prepared by combining the components and mixing them at room temperature until the mixture became a homogeneous photocurable composition. As shown below in Table A VIII, the photocurable compositions of the present invention have a viscosity suitable for photolithography.

TABLE A VIII Photo curing composition Viscosity at 25 ° C
(cp) Example A1 555 Example A2 465 Example A3 285 Example A4 410 Example A5 700 Example A7 565 Example A9 260 Example A10 325 Example A11 280 Example A12 460 Example A20 182 Example A21 200 Example A22 460

Then, three-dimensional products were made from photocurable compositions on a stereolithographic installation. Examples A1-A20 and Comparative Example A1 were prepared on an SLA350 machine, and Examples A21-A23 were prepared on an SLA7000 machine. Products having a layer thickness of 0.1 m were manufactured using a penetration depth in the range of about 4.8-7.3 mils and a critical energy in the range of about 6.3-25.5 mJ / cm ² . All products made from the photocurable compositions of the present invention had a cohesive strength in the range of about 137-1337 MPa in 10 minutes and 243-1900 MPa in 60 minutes. In comparison, a product made from a commercially available resin according to Comparative Example A1 had a cohesive strength of 25 MPa in 10 minutes, which did not increase with time. However, when the resin according to Comparative Example A1 was prepared using an antimony-based cationic photoinitiator instead of the antimony-free photoinitiator, the resulting product had a cohesive strength of 50 MPa in 10 minutes, which then increased to 150 MPa after 60 minutes. Thus, replacing an antimony-based cationic photoinitiator with an antimony-free cationic photoinitiator in commercially available photo-curable resins will not allow a high-quality resin to be obtained due to its low cohesive strength. The cohesive strengths of the products are shown in Table A IX below.

TABLE A IX Photo curing composition Cohesive strength in 10 minutes (MPa) Cohesive strength in 60 minutes (MPa) Example A1 137 243 Example A2 182 330 Example A3 776 938 Example A4 1090 1309 Example A5 140 220 Example A9 286 361 Example A10 1337 1604 Example A11 458 565 Example A12 137 243 Example A13 330 Example A18 585 Example A19 1022 1198 Example A20 353 737 Example A21 737 Example A23 1190 1598 Comparative Example A1 25 25 Comparative Example A1 with Antimony-Based Photo Initiator fifty 150

The mechanical properties of the products were evaluated using a United Testing Systems dynamometer. The specifications of the United Testing Systems dynamometer are as follows:

Test speed 5 mm / min

Preload 0.05 kg

Test speed 5 mm / min

500 lbs maximum load

1 inch strain gauge

"Pre-test speed" is the speed at which a three-dimensional product is tightly pulled before the test.

"Preload" is the amount of force that is applied to a three-dimensional product (at a pre-test speed) before the start of the test.

"Test speed" is the speed at which a three-dimensional product is torn during the test method.

“Maximum Load” is the maximum amount of force that the United Testing Systems dynamometer can use to test the sample.

A "strain gauge" is a device that captures a three-dimensional product between two teeth with a distance between the teeth of one inch. The spring on the strain gauge measures the distance that a three-dimensional product is elongated. The results are shown below in Tables A X-A XIV:

TABLE A X Indicator (1.5 hours in a PCA heater) Example A1 Example A2 Example A3 Bending Strength (psi) 8604 7791 8097 Flexural modulus (10 ³ psi) 315 278 279 Tensile Strength (psi) 5314 4810 5366 Tensile modulus (10 ³ psi) 266 233 253 Elongation at break (%) 22.7 19,2 19.0 Notched Izod Average Impact Strength (ft lb / in) 0.81 0.79 0.68

TABLE A XI Indicator (1.5 hours in a PCA heater) Example A4 Example A5 Example A9 Bending Strength (psi) 7442 8267 8842 Flexural modulus (10 ³ psi) 249 261 286 Tensile Strength (psi) 5500 5189 6235 Tensile modulus (10 ³ psi) 257 241 313 Elongation at break (%) 16.1 8.7 7.6 Notched Izod Average Impact Strength (ft lb / in) 0.67 0.55 0.78

TABLE A XII Indicator (1.5 hours in a PCA heater) Example A10 Example A11 Example A12 Bending Strength (psi) 10,000 9027 Flexural modulus (10 ³ psi) 347 315 285 Tensile Strength (psi) 6418 5990 Tensile modulus (10 ³ psi) 323 306 268 Elongation at break (%) 10 10.9 twenty Notched Izod Average Impact Strength (ft lb / in) 0.70 0.78 0.81

TABLE A XIII Indicator (1.5 hours in a PCA heater) Example A13 Example A16 Example A17 Bending Strength (psi) 241 Tensile Strength (psi) 6382 6236 4061 Tensile modulus (10 ³ psi) 309 340 123 Elongation at break (%) 3,5 3-6 14.1

TABLE A XIV Indicator (1.5 hours in a PCA heater) Example A19 Example A20 Bending Strength (psi) Flexural modulus (10 ³ psi) 156 289 Tensile Strength (psi) 6418 Tensile modulus (10 ³ psi) 323 Elongation at break (%) 10 5.5 Notched Izod Average Impact Strength (ft lb / in) 0.70 0.60

The low viscosity of the photocurable composition of the present invention allows the manufacture of cured products with a minimum change over time of the mechanical properties and strain rate, high dimensional accuracy and cohesive strength, as well as excellent mechanical strength, high temperature resistance, moisture resistance and water resistance. Therefore, the cured product is suitable for use as a three-dimensional product, such as, for example, an experienced product for use as mechanical parts.

Although the implementation and use of various embodiments of the present invention have been described in detail above, it should be understood that the present invention provides many applicable inventive ideas that can be implemented in a wide variety of specific contexts. The specific embodiments described herein are merely illustrative of specific methods for implementing and using the present invention and in no way limit the scope of the invention.

EXAMPLES B

Tables B II-B V list the components of each photocurable composition labeled Examples B2, B3, B5-B26 and Comparative Examples B1 and B4. The numbers in Tables B II-B V refer to the masses. the percentage of each component taken from the total mass of the photocurable composition. Table B VI provides trademark identification information for the components of Tables B II-B V.

TABLE B II Component Comparative example B1 (% wt.) Example B2
(% wt.) Example B3
(% wt.) Comparative Example B4
(% wt.) Example B5
(% wt.) Uvacure 1500 56.96 56.96 48.9 Epalloy 5000 48.9 48.9 OXT 101 fifteen fifteen fifteen CN 2301 5 5 5 SR 833S 20.1 20.1 20.1 CN120 eighteen eighteen Albidur EP 2240 3 3 four four four Polymeg 1000 fifteen fifteen UVI 6976 4.95 5 UVI 6992 4.95 5 5 Irgacure 184 2 2 2 2 2 Stabilizers 0,095 0,095 Total% wt. one hundred one hundred one hundred one hundred one hundred

TABLE III Component Example B6 (% wt.) Example B7 (% wt.) Example B8 (% wt.) Example B9 (% wt.) Example B10 (% wt.) Example B11 (% wt.) Example B12 (% wt.) Example B13 (% wt.) Epalloy 5000 25.62 21.86 35 27.9 20.1 38.41 45.24 47.4 OXT-101 5.8 12.3 OHT-212 7.7 8.16 CN 2301 2.59 2.72 2.6 2.59 2 SR 833S 10,4 10.9 10,4 10,4 10 7.8 2.6 Albidur EP 2240 2 2.2 2 2 2 2 Cyclohexane-dimethanol 5 UVI 6992 2.59 2.7 2.6 2,51 2,4 2.59 3.28 5.3 Irgacure 184 one one one one one one 1,04 Epoxide wt.% 27.4 23.7 33,4 29th 23,2 40,4 45.24 47.3 Occitan wt.% 7.7 8.16 0 5.8 13.3 0 0 0 Acrylate wt.% 13 13.6 13 13 13,4 7.8 2.6 0

TABLE IV Component Example B 14 (% wt.) Example B 15 (% wt.) Example B 16 (% wt.) Example B 17 (% wt.) Example B18 (% wt.) Example B19 (% wt.) Uvacure 5000 1.9 1.9 3.66 1.96 3,995 3,995 Epalloy 5000 23.5 23.5 23.9874 24,5176 49 49 OXT 101 7.2 12,1188 6.8 7.35 fifteen fifteen CN 2302 7.2 7.2 4.9 CN 2301 9.36 fifteen fifteen SR 833S 5,0376 2.45 10 Ebecryl 3605 4.9 10 UVI6992 2,4 2,4 1,59 2.45 5 5 Irgacure 184 0.96 0.96 0.04 0.98 2 2 Stabilizers 0.0024 0.0024 0.0026 0.0024 0.005 0.005 Epoxide wt.% 25,4 25,4 29.04 26.46 52,995 52,995 Occitan wt.% 7.2 12,1188 6.8 7.35 fifteen fifteen Acrylate wt.% 12 7.2 9.36 11.78 24.04 25 Dendritic acrylate wt.% 7.2 7.2 9.36 4.9 fifteen fifteen

TABLE IN V Component Example B20 (% wt.) Example B21 (% wt.) Example B22 (% wt.) Example B23 (% wt.) Example B24 (% wt.) Example B25 (% wt.) Example B26 (% wt.) Uvacure 5000 1,96735 Epalloy 5000 25.97 25,4 26.45 32.6 27,516 19.7 24 OXT 101 7.95 7.8 7.5 7.77 7.77 7.5 CN 2302 7.95 CN 2301 2.5 SR 833S 13 12.65 7.77 20.72 20.72 10.5 Albidur EP 2240 2 2 UVI 6992 2.65 2.6 2.5 2.59 2.59 2.59 2.5 Irgacure 184 1.06 one 1,5 1.13 one 1,03 one Stabilizers 0.00265 Epoxide wt.% 28.6 27.4 26.45 32.6 27,454 19.7 26.5 Occitan wt.% 7.95 7.8 7.5 7.77 0 7.77 7.5 Acrylate wt.% 7.95 13 12.95 7.7715 20.72 20.72 13.5 Dendritic acrylate wt.% 7.95 0 2.5 0 0 0 . 2.5

TABLE VI Component Source Chemical Name Uvacure 1500 UCB Surface Specialties 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexane-carboxylate Epalloy 5000 CVC Specialty Chemicals Inc. Hydrogenated Epoxidized Bisphenol A Albidur EP 2240 Hanse chemie Silicone-Epoxy Particles in Bisphenol A / Epoxy OXT-101 Toagosei Co. Ltd. 3-ethyl-3-hydroxymethyl-1-hydroxytane OXT-212 Toagosei Co. Ltd. 3-Ethyl-3- [2-ethylhexyloxy methyl] oxytane Polymeg 1000 Penn specialty chemicals Polytetramethylene glycol ether (m.v. 1000) Cyclohexane dimethanol Sigma aldrich CN 2301 Sartomer. Co. Inc. Hyperbranched Polyester Acrylate Oligomer CN 2302 Sartomer Co. Inc. Hyperbranched Polyester Acrylate Oligomer Ebecryl 3605 UCB Surface Specialties Partially Acrylic Bisphenol A / Epoxy SR 833S Sartomer Co. Inc. Tricyclodecandimethanol diacrylate CN 120 Sartomer Co. Inc. Bisphenol A Epoxy Acrylate Irgacure 184 Ciba Specialty Chemicals 1-hydroxycyclohexylphenylketone UVI 6992
UVI-6956 Dow Chemical Co.
Dow Chemical Co. Mixed arylsulfonium hexafluorophosphates
A mixture of triarylsulfonium hexafluoroantimonate salts in propylene carbonate

The viscosity of several photocurable compositions was determined at 25 ° or 30 ° C using a Brookfield viscometer; the corresponding results are shown in Table B VII:

TABLE B VII Photo curing composition Viscosity (cP) Example B3 215 (at 30 ° C) Example B6 155 (at 30 ° C) Example B7 150 (at 30 ° C) Example B8 600 (at 30 ° C) Example B9 280 (at 30 ° C) Example B10 125 (at 30 ° C) Example B11 650 (at 30 ° C) Example B12 820 (at 30 ° C) Example B13 890 (at 30 ° C) Example B14 285 (at 25 ° C) Example B16 510 (at 25 ° C) Example B17 465 (at 25 ° C) Example B18 760 (at 325 ° C) Example B19 410 (at 25 ° C) Example B20 500 (at 25 ° C) Example B21 465 (at 25 ° C) Example B22 555 (at 25 ° C) Example B24 520 (at 25 ° C) Example B25 185 (at 25 ° C) Example B26 330 (at 25 ° C)

Then, on stereolithographic installations of 3D Systems SLA 350 or 7000, or using silicone molds, test models were made from photocurable compositions. When using silicone molds, the liquid resin was cast in a mold and cured by actinic radiation for 1 hour. Comparative Examples B1 and B4, as well as Examples B2, B3, B5, B11 and B14-B26 were prepared on the SLA 350, and Examples B3 and B6-B13 were prepared on the SLA 7000. The photosensitivity in Examples B3 and B6-B13 was defined on the SLA 7000 installation.

Photosensitivity was determined on “window glasses” by measuring the thickness of a layer of single-layer test samples produced at different laser energies. Then, the layer thickness was set aside depending on the logarithm of the applied irradiation energy, as a result of which a working curve was constructed. Then, in order to determine the penetration depth, the slope of the curve was determined (D _p , in miles). The energy value (E _c , in mJ / cm ² ), or the point at which the working curve passes through the X axis was also determined. E _c represents the energy at which material thickens, as described by P. Jacobs, Rapid Prototyping and Manufacturing, Soc. Of Manufacturing Engineers, 1992, p. 270, which is incorporated herein by reference.

Cohesive strength was determined by measuring the modulus of elasticity in bending, with a deflection of 1 mm, 10 and 60 minutes after the models were made. Glass transition temperature (T _g ) was determined using dynamic mechanical analysis. Water resistance was determined by immersing the model in water at room temperature, followed by determination after 1 week of the stored bending elastic modulus.

Other physical properties of fully cured test models (post-cure in a PCA heating chamber for 90 minutes) were determined according to the following ASTM and ISO standard procedures, which are incorporated herein by reference:

ASTM Standard ISO Standard Tensile properties
(elongation at break, strength, modulus) D 638 527 Bending properties
(maximum strength, module) D 790 178 Notched Izod Impact Strength (Impact Strength) D 256 n / a Impact and bending impact strength
(fracture toughness, stress intensity factor) n / a 13586

TABLE B VIII Indicator Comparative Example B1 Example B2 Example
IN 3 Comparative Example B4 Example B5 Cohesive strength in 10 minutes (MPa) 220 25 1113 1669 fifty Cohesive strength in 60 minutes (MPa) 440 26 1553 1831 52 D _P (mil) 5.14 5.48 5.44 E _C (mJ / cm ² ) 8.84 10.37 12.07 Tensile modulus (MPa) 2188 2339 2242 Elongation at break (%) 10 12 3,5 Tensile Strength (MPa) 45 46 thirty Flexural modulus (MPa) 2098 2063 2160 Bending Strength (MPa) 67 66 fifty Notched Izod Impact Strength (ft lb / in) 0.95 0.54 0.52 T _g (° C) 55 69 70 Water resistance (%) 76 80 80 DSC exothermic peak (° C) 313 213 315

TABLE B IX Indicator Example B3 Example B6 Example B7 Example B8 Example B9 Example B10 Example B11 Example B12 Example B13 D _P (mil) 5.22 5.22 2.21 4,50 4.65 4,52 4.94 3.16 3.00 E _C (mJ / cm ² ) 18.64 28.1 19.03 14.56 16.14 15.94 9.09 57.46 68.88 E ₄ (mJ / cm ² ) 40,082 60,488 116,753 35,427 38,081 38,653 20,42 203,835 261.008 E ₁₁ (mJ / cm ² ) 153,074 231,390 2791,805 168,030 171.106 182,072 84,172 1868 2686.091 Tensile modulus (MPa) 1515 452 136 1100 1430 2260 900 1250 1270 Elongation at break (%) 2.91 8.1 30.6 2.6 2,8 2,8 1.3 2.5 3.1 Tensile Strength (MPa) 27.8 9.9 12.3 18.5 27.0 39.3 1,0 20.7 21.4 Flexural modulus (MPa) 1522 300 77 632 1124 1580 730 1020 1240 Bending Strength (MPa) 43.3 13.9 7.2 23.9 40.6 52.1 17.1 29.7 41.5

TABLE B X Indicator Example B3 Example B11 Example B14 Example B15 Example B6 Example B17 Example B18 Example B19 Cohesive strength in 10 min (MPa) 1190 fifteen 776 * * 182 576 1090 Cohesive strength in 60 min (MPa) 1598 26 938 * * 330 691 1309 D _P (mil) 5.55 5.55 7.28 8.27 4.69 4.86 6.08 6.50 E _C (mJ / cm ² ) 10.22 12,43 25.46 41.46 7.14 6.31 12.23 13.91 E ₄ (mJ / cm ² ) 21.01 25.56 44.10 67.25 16.75 14.37 23.61 25.74 E ₁₁ (mJ / cm ² ) 74.15 90.21 115.4 156.8 74.52 60.67 74.67 75.56 Tensile modulus (MPa) 2188 740 1744 620 1606 1503 1772 Elongation at break (%) 10 8.1 19 7.6 19,2 9.8 15.1 Tensile Strength (MPa) 45 15.6 37 13 33 31 38 Flexural modulus (MPa) 2098 634 1923 800 1916 2234 1717 Bending Strength (MPa) 67 19 56 21 54 64 51 Notched Izod Impact Strength (ft lb / in) 0.95 0.68 0.4 0.79 0.70 0.67 * Material too soft to measure.

TABLE B XI Indicator Example B20 Example B21 Example B22 Example B23 Example B24 Example B25 Example B26 Cohesive strength in 10 min (MPa) 423 1120 1343 734 443 1903 1104 Cohesive strength in 60 min (MPa) 581 1322 1353 899 551 2150 1265 D _P (mil) 7.51 5.09 5.65 5.79 7.49 5.66 5.71 E _C (mJ / cm ² ) 28.87 7.07 5.69 8.13 9.9 5.71 10.16 E ₄ (mJ / cm ² ) 49.18 15,51 11.55 16.22 16.89 11.58 20.47 E ₁₁ (mJ / cm ² ) 125 61.37 39.87 54.35 43 39.87 69.75 Tensile modulus (MPa) 1344 1344 1590 2578 2220 Elongation at break (%) 18.9 25.1 5,0 6.7 9.0 Tensile Strength (MPa) 22 28 34.2 53 45.1 Flexural modulus (MPa) 1627 1669 1613 2260 2000 Bending Strength (MPa) 47 45 49 75 62.7 Notched Izod Impact Strength (ft lb / in) 1.06 0.78 0.41 0.39 0.61

Comparative Example B1 (identical to the commercially available photocurable composition) and Example B2 above demonstrate that simply replacing an antimony-based cationic photoinitiator with an antimony-free photoinitiator does not allow a product having sufficient cohesive strength. In addition, Example B3 demonstrates the increased impact resistance that is achieved with cured products made from the photocurable composition of the present invention compared to Comparative Example B4. In addition, Examples B3 and B5 demonstrate that the photocurable compositions of the present invention are much more stable since the exothermic peak of the DCC (showing the thermal stability of the mixture) for these compositions is much higher than the corresponding exothermic peak for the compound containing antimony (i.e., Comparative Example B4 )

EXAMPLES C

Table C II lists the components of the photocurable composition according to the present invention, designated as Example C1. The numerical values in Table C II refer to the masses. the percentage of each component taken from the total mass of the photocurable composition. Table C III provides trademark identification information for the components of Table C II.

TABLE C II Component Example C1 (% wt.) Epalloy 5000 52.9 OXT-101 fifteen CN 2301 5 SR 833S 20.1 UVI 6992 5 Irgacure 184 2

TABLE C III Component Source Chemical name Epalloy 5000 CVC Specia1ty Chemicals Inc. Hydrogenated Epoxidized Bisphenol A OXT-101 Toagosei Co. Ltd. 3-ethyl-3-hydroxymethyl-1-hydroxytane CN 2301 Sartomer Co. Inc. Hyperbranched Polyester Acrylate Oligomer SR 833S Sartomer Co. Inc. Tricyclodecandimethanol diacrylate Irgacure 184 Ciba Specia1ty Chemicals 1-hydroxycyclohexyl-phenylketone UVI 6992 Dow Chemical Co. Mixed arylsulfonium hexafluorophosphates

The viscosity of the photocurable composition and the commercially available acrylate-containing photocurable composition (hereinafter referred to as “Comparative Example C”) was determined at 30 ° C. using a Brookfield viscometer. Test models were made from the photocurable compositions of Example C 1 and Comparative Example C on a SLA 7000 stereolithographic apparatus. Before the mechanical test, the test models were kept for 3-5 days at 23 ° C, in 50% humidity.

The photosensitivity of the photocurable compositions was determined as described in Examples B of the present description.

Other physical properties of fully cured test models were determined in accordance with the ISO standards described in Examples B.

TABLE C IV Indicator Example C1 Comparative Example C Viscosity at 30 ° C (cP) 205 1090 D _p (mil) 6.10 6.3 E _c (mJ / cm ² ) 13.95 4.3 Tensile modulus (MPa) 2000 1045 Elongation at break (%) 4.2 6.0 Tensile Strength (MPa) 35.5 26.5 Flexural modulus (MPa) 2080 1160 Bending Strength (MPa) 75 52 Impact and notch impact strength, G _1C (J / m ² ) 915 417 Impact strength with notch and bending, K _1C (MPa / m ^1/2 ) 1.55 0.75 Bending heat resistance at 0.45 MPa (° C) 47.6 50,4 Twisting strain (mm) 0.186 1,776

The above results demonstrate that the viscosity in Example C1 is much lower than in Comparative Example C (similar to a commercially available acrylate-containing photocurable composition). In addition, the results demonstrate increased impact resistance of a test model made from the photocurable composition of Example C1 compared to Comparative Example C. Therefore, the test model of Example C1 is much less fragile than the test model of Comparative Example. Finally, the accuracy of the test model made of the photocurable composition of Example C1 is significantly higher than that of the test model made of the photocurable composition of Comparative Example C, which is demonstrated by a ten-fold reduction in twisting strain.

EXAMPLES D

The compounds of Examples D were prepared by mixing the components with a stirrer at room temperature until a homogeneous composition was obtained. The physical characteristics of the resulting compositions are described below.

Test samples were prepared using one of the SLA350 (examples D5-D13) or SLA7000 (examples D1-D4, D32-D37) manufactured by 3D Systems or cured in molds at room temperature in a UV oven for 1 h 30 min (examples D14-D31).

After fabrication at SLA plants, the samples were purified using isopropanol, dried and post-cured in a 3D Systems (PCA) post-cure apparatus for 1 h 30 min to ensure complete cure of the resin. Before mechanical testing, test samples were kept for 3-5 days at 23 ° C, in 50% humidity.

The mechanical test of fully cured parts is carried out according to ISO or ASTM standards. Examples D1-D4, D32-D37 were tested according to ISO standards. Examples D5-D13 were tested according to ASTM standards.

The viscosity of liquid mixtures was determined at 25 ° C or 30 ° C using a Brookfield viscometer (MPa · s):

TABLE D I Examples Viscosity at 30 ° C Examples Viscosity at 30 ° C Examples Viscosity at 25 ° C D1 60 D24 170 D5 280 D2 150 D25 160 D6 285 D3 80 D26 155 D7 230 D4 160 D27 150 D8 270 D14 145 D28 170 D9 270 D15 130 D29 155 D10 200 D16 145 D30 155 D11 250 D17 one hundred D31 165 D12 245 D18 one hundred D32 350 D13 310 D19 210 D33 570 D20 130 D34 120 D21 110 D35 230 D22 90 D36 70 D23 70 D37 145

The raw materials used in Examples D are described in table DII

TABLE D II Trademark Source Chemical Name Uvacure 1500 Cytec 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexanecarboxylate Epalloy 5000 CVC Chemicals Hydrogenated Bisphenol A Diglycidyl Ether OXT-101 Toagosei 3-ethyl-3-hydroxymethyloxytane Gri1oniteF-713 EMS Primid Polytetrahydrofurandiglycidyl ether polyBD 605E Sartomer Co. Epoxidized polybutadiene with terminal hydroxyl (mv approx. 1300) k-flex 188 King industries Polyester-based polyol Terathane 1000 Invista Polytetramethylene ether glycol (MW approximately 1000) Terathane 250 Invista Polytetramethylene ether glycol (MW approximately 250) Acclaim 12200 Bayer Polyester Based Polyol (MW approximately 11200) Diethylene glycol Sigma-alldrich CN 2301 Sartomer Co. Hyperbranched Polyester Acrylate Oligomer CN 2302 Sartomer Co. Hyperbranched Polyester Acrylate Oligomer SR 833S Sartomer Co. Tricyclodecandimethanol diacrylate CN 131 Sartomer Co. Aromatic monoacrylate SR 306 Sartomer Co. Tripropylene glycol triacrylate SR 399 Sartomer Co. Dipentaerythritol pentacrylate SR 495 Sartomer Co. Caprolactone acrylate Nanopox a610 Nano resins Quartz nanoparticles modified with cycloaliphatic epoxy resin Nanobyk-3601 Byk chemie Alumina Nanoparticles Dispersed in Tripropylene Glycol Diacrylate Nanofine Solvay Barium Sulfate Nanoparticles UVI 6976 Dow chemicals company Mixture of PhS- (C ₆ H ₄ ) -S ⁺ Ph ₂ SbF ₆ ^- and Ph ₂ S ⁺ - (C ₆ H ₄ ) -S- (C ₆ H ₄ ) -S ⁺ Ph ₂ (SbF ₆ ^- ) ₂ UVI 6992 Dow chemicals company Mixture of PhS- (C ₆ H ₄ ) -S ⁺ -Ph ₂ РF ₆ ^- and Ph ₂ S ⁺ - (C ₆ H ₄ ) -S- (C ₆ H ₄ ) -S ⁺ Ph ₂ (РF ₆ ^- ) ₂ Esacure 1064 Lamberti Mixture of PhS- (C ₆ H ₄ ) -S ⁺ -Ph ₂ РF ₆ ^- and Ph ₂ S ⁺ - (C ₆ H ₄ ) -S- (C ₆ H ₄ ) -S ⁺ Ph ₂ (РF ₆ ^- ) ₂ Irgacure 184 Ciba Specia1ty Chemicals 1-hydroxycyclohexylphenylketone Irganox 1035 Ciba Antioxidant and thermal stabilizer

TABLE D III Example D1 D2 D3 D4 Epalloy 5000 48 38 Uvacure 1500 48 38 Oxt-101 fifteen fifteen fifteen fifteen SR 833 thirty thirty thirty thirty terathane 1000 10 10 Irgacure 184 2 2 2 2 Esacure 1064 5 5 5 5

TABLE D IV Example D5 D6 D7 D8 D9 D10 D11 D12 D13 Epalloy 5000 fifty fifty fifty 60 58 47 fifty fifty fifty Oxt-101 fifteen fifteen fifteen eighteen 17 eighteen fifteen 10 fifteen SR 833 twenty eighteen 28 fifteen eighteen 28 twenty 28 twenty CN 2302 3 5 CN 2301 5 5 CN 131 8 k-flex 188 5 Irgacure 184 2 2 2 2 2 2 2 2 2 UVI 6992 5 5 5 5 5 5 5 5 5

TABLE D V Example D1 D2 D3 D4 D _p Mil 5.79 5.91 5.78 4,52 E _c mJ / cm ² 10.89 12.36 14.34 17.15 E ₄ mJ / cm ² 21.73 24.32 28.63 41.55 E ₁₁ mJ / cm ² 72.80 79.48 96 195.45 Tensile modulus (MPa) MPa 2090 2375 2159 383 Elongation at break (%) % 3.06 3.2 3.9 18.9 Tensile Strength (MPa) MPa 39 46 45 16 Flexural modulus (MPa) MPa 1970 1960 2280 300 Bending Strength (MPa) MPa 61 83 94 21 Fracture Toughness (G _1C ) J / m ² 0.38 0.61 1,143 0.51 Voltage Intensity Factor (K _1C ) MPa√m 63 158 501 752 The deformation temperature during heating at 0.45 MPa ° C 55.2 50,2 54.5 38,2 T _g (DMA) ° C 71.1 63.5 61 52.6

TABLE D VI Example D5 D6 D7 D8 D9 D10 D11 D12 D13 D _p Mil n / a n / a 6.82 6.34 5.98 6.63 n / a n / a n / a E _c mJ / cm ² n / a n / a 6.41 8.45 5.86 7.38 n / a n / a n / a E ₄ mJ / cm ² n / a n / a 11.53 15.88 11,4 13.5 n / a n / a n / a E ₁₁ mJ / cm ² n / a n / a 32.17 47.92 36.87 38.77 n / a n / a n / a Tensile modulus (MPa) MPa 2565 2455 2420 2186 2303 2358 2372 2241 2392 Elongation at break (%) % 8.4 6.6 11,4 10.7 6.1 11.2 6.5 8.3 10.3 Tensile Strength (MPa) MPa 55 52 52 46 47 51 48 48 fifty Flexural modulus (MPa) MPa 2000 2400 2360 1930 2100 2100 2490 2160 2460 Bending Strength (MPa) MPa 69 79 80 69 74 71 82 75 80 Notched Izod Impact Strength Foot lb / in 0.61 0.62 0.71 1,0 0.80 0.73 0.78 0.79 0.85

TABLE D VII Example D14 D15 D16 D17 D18 Uvacure 1500 59,4 53.46 53.46 45.45 45.45 OXT-101 fifteen fifteen SR 399 17 15.3 15.3 13 13 SR 495 10 8.5 SR 306 10 8.5 Terathane 250 eighteen 16,2 16,2 13.77 13.77 Irgacure 184 2,3 2.07 2.07 1.76 1.76 UVI 6976 3,1 2.79 2.79 2,37 2,37 Irganox 1035 0.2 0.18 0.18 0.15 0.15

TABLE D VIII Example D19 D20 D21 D22 D23 Uvacure 1500 59,4 53.46 53.46 45.45 45.45 OXT-101 fifteen fifteen SR 399 17 15.3 15.3 13 13 SR 495 10 8.5 SR 306 10 8.5 Terathane 250 eighteen 16,2 16,2 13.77 13.77 Irgacure 184 2,3 2.07 2.07 1.76 1.76 Esacure 1064 3,1 2.79 2.79 2,37 2,37 Irganox 1035 0.2 0.18 0.18 0.15 0.15

The transparency of samples D14-D23 was evaluated by measuring the total transmittance (the ratio of the total amount of light passing through the material to the amount of incident light, which decreases as a result of reflection and transmission). The measurements were performed on a Haze Guard plus nephelometer (BYK Gardner) on disk samples (thickness 0.004 mm, ϕ 40 mm). The highest transparency is determined by the highest transparency value.

TABLE D IX Example D14 D15 D16 D17 D18 transparency 87.1 91.1 90.8 90.8 90.5

TABLE D X Example D19 D20 D21 D22 D23 transparency 82.3 88.7 86 86.8 84.5

TABLE D XI Example D24 D25 D26 D27 Epalloy 5000 43 38 33 28 Oxt-101 fifteen fifteen fifteen fifteen SR 833 thirty thirty thirty thirty Nanopox a610 5 10 fifteen twenty Irgacure 184 2 2 2 2 Esacure 1064 5 5 5 5

TABLE D XII Example D28 D29 D30 D31 Epalloy 5000 48 48 48 47 Oxt-101 fifteen fifteen fifteen fifteen SR833 29.5 28 26 thirty Nanobyk 3601 0.5 2 four Nanofine one Irgacure 184 2 2 2 2 Esacure 1064 5 5 5 5

TABLE D XIII Example D24 D25 D26 D27 D _p Mil 5.81 5.57 5.84 5.56 E _c mJ / cm ² 11.65 10.67 11.54 10.82 E ₄ mJ / cm ² 23,20 21.87 22.90 22.21 E ₁₁ mJ / cm ² 77.49 76.78 75.93 78.16 Tensile modulus (MPa) MPa 1540 1570 1730 2210 Elongation at break (%) % 3 3,1 2.9 2.9 Tensile Strength (MPa) MPa 28 thirty 31 39 Flexural modulus (MPa) MPa 1240 1665 1760 2050 Bending Strength (MPa) MPa fifty 64 60 63 Fracture Toughness (G _1C ) J / m ² 0.64 0.55 0.70 0.40 Voltage Intensity Factor (K _1C ) MPa√m 280 162 232 70 The deformation temperature during heating at 0.45 MPa ° C 45.4 45.6 45.6 48.8

TABLE D XIV Example D28 D29 D30 D31 D _p Mil 6.29 6.22 5.67 6.39 E _c mJ / cm ² 13.83 15.69 15.28 15.3 E ₄ mJ / cm ² 26.13 29.85 30.95 28.60 E ₁₁ mJ / cm ² 79.55 92.00 106.49 85.49 Tensile modulus (MPa) MPa 2380 2170 1340 1940 Elongation at break (%) % 2.9 3.0 3.0 2,3 Tensile Strength (MPa) MPa 45 42 26 31 Flexural modulus (MPa) MPa 2135 1720 1000 1380 Bending Strength (MPa) MPa 68 48 31 39 Fracture Toughness (G _1C ) J / m ² 1,151 1,186 0.551 0.77 Voltage Intensity Factor (K _1C ) MPa√m 539 695 260 330 Deformation temperature during heating at 1.80 MPa ° C 43,4 41.7 39 41.7

EXAMPLE E

Test samples of composition B6 were made on SLA350 and maintained at 23 ° C, in 50-60% humidity. The impact values given are averaged and obtained from approximately 10 samples.

The table below shows the change in impact strength over more than 5 months. This is a huge achievement because it is known that currently commercially available SL resins allow the manufacture of parts that are cured in the dark for a long time, while losing impact strength for several weeks after their manufacture.

TABLE E 5 days 30 days 159 days Notched Izod Impact Strength Foot lb /
inch 0.93 0.91 0.92

EXAMPLES F

Suitable compositions for jet ejection are shown in Table F1. These compounds have a viscosity of 10-12 cP at 70 ° C and provide stable jet ejection when using the SPECTRA NOVAJET device; they have acceptable sensitivity and good jet ejection characteristics. More detailed information regarding the compositions for jet ejection can be found in the application WO 03/09947 A1, the contents of which are incorporated herein by reference. Preferably, the composition for inkjet ejection is a fully curable composition for inkjet ejection having a viscosity of less than 30 cP at a temperature within the range of 15-180 ° C, more preferably at a temperature of 15-100 ° C, for example 60-80 ° C, where said composition includes:

(A) at least one active resin of low viscosity selected from the group consisting of compositions containing an oxytane ring, cycloaliphatic epoxies, tetrahydrofurans, hexahydropropanes and monofunctional (meth) acrylates, wherein said resin preferably has a molecular weight of not more than 300 Dalton, for example 250 Daltons or less, and preferably a viscosity in said temperature range of less than 30 cP, for example 5-15 cP;

(B) at least one higher viscosity active resin selected from the group consisting of epoxy resins, compounds containing an oxitan ring, and acrylates, said resin increasing the viscosity of the low viscosity resin and enhancing the jet ejection of the composition, while the resin is higher viscosity has a viscosity two times higher than the low viscosity resin in the above temperature range, and the functionality is greater than or equal to 2;

(C) optionally at least one curable impact-resistant additive having a functionality of preferably at least 2, such as a polymer / oligomer with hydroxyl, epoxy, acrylate or other active functional groups (for example, obtained by introducing functional groups in poly (tetrahydrofuran), polycaprolactone, diolpolycarbonate or dendritic polyol;

(D) at least one initiator for the polymerization of resins, and

(E) optionally at least one stabilizer for delaying the curing of the resins of the composition; where the low viscosity resin is less reactive than the higher viscosity resin and acts as a diluent for the higher viscosity resin before curing and at least partially during curing, and where at least 30% of components A and B are cationic curable resins.

The compositions can be ejected from the piezoelectric printheads under the control of a computer program, forming a multilayer product, for example a three-dimensional product, in which adjacent droplets merge and homogenously cure together.

TABLE F1 F1 F2 F3 F4 UV1500 fifty 51.5 fifty 47 UVR6000 45 46 45 43 UVI6976 5 2.5 UVI6992 5 10

The cure rate of the jet-ejected compositions F1-F4 was measured (Table F1), the results are shown in Diagram F:

DIAGRAM F

Time / s means cure time in seconds: 50 s for 2.5% UVI6976, 40 s for 5% UVI6976, 75 s for 5% UVI6992, 40 s for 5% UVI6992.

An aging test was performed at 60 ° C. A number of compositions were subjected to this test (Table F2). As shown in the present description, compositions containing PF ₆ salts are more stable than compositions containing SbF ₆ salts, while having similar curing rates.

TABLE F2 F5 F6 F7 F8 F9 F10 F11 F12 F13 UV1500 95 fifty UVR6105 95 fifty fifty 95 90 UVR6107 95 UVR6128 95 UVR6000 45 45 45 UVR6976 5 5 5 5 5 5 UVR6992 5 5 10

TABLE F3 Composition Initial viscosity (MPa * s) 1 week later at 60 ° C (MPa * s) F5 220 900 F6 160 5100 F7 290 410 F8 fifty Body F9 fifty Body F10 25 85 F11 128 138 F12 205 225 F13 590 650

Claims (25)

1. Non-toxic photocurable composition for a three-dimensional product containing
(a) 35-80% by weight of a cationically curable component that contains an oxetane compound;
(b) 15-60 wt.% free radical component containing poly (meth) acrylate, which is not dipentaerythritol hexaacrylate;
(c) 0.1-10 wt.% antimony-free cationic photoinitiator;
(d) 0.01-10% by weight of a free radical photoinitiator; and
(e) 0.01-40 wt.% one or more impact resistance additives, where wt.% is taken from the total mass of the photocurable composition. 2. The photocurable composition of claim 1, wherein the free radical active component is poly (meth) acrylate. 3. The photocurable composition of claim 2, wherein the poly (meth) acrylate comprises a bifunctional acrylate compound. 4. The photocurable composition according to any one of claims 1 to 3, wherein the free radical active component further comprises a compound with functional epoxy groups. 5. The photocurable composition according to any one of claims 1 to 3, wherein the cationically curable component further comprises a hydrogenated epoxy-containing bisphenol compound. 6. The photocurable composition according to any one of claims 1 to 3, wherein the antimony-free cationic photoinitiator is triarylsulfonium hexafluorophosphate. 7. The photocurable composition according to any one of claims 1 to 3, wherein the photocurable composition comprises 0.01-40 wt.% Of one or more impact resistance additives. 8. The photocurable composition according to claim 7, wherein the impact resistance enhancer is particles consisting of a polysiloxane core and a shell that contains active groups. 9. The photocurable composition according to any one of claims 1 to 3 or 8, wherein the photocurable composition has a viscosity in the range of 50-1000 mPa · s (cP). 10. A curable composition having at least one characteristic selected from a tensile strength with a value of at least 30 MPa, a bending modulus in the range of about 1000-2300 MPa, or an average elongation at break with a value of at least 5% obtained by curing under the action of actinic radiation and optionally by heating a non-toxic photocurable composition for a three-dimensional product containing
(a) 35-80% by weight of a cationically curable component that contains an oxetane compound;
(b) 15-60 wt.% free radical active component, which is not dipentaerythritol hexaacrylate containing
(i) at least one poly (meth) acrylate compound and optionally
(ii) at least one dendritic acrylate polymer compound;
(c) 0.1-10 wt.% antimony-free cationic photoinitiator;
(d) 0.01-10% by weight of a free radical photoinitiator;
(e) 0.01-40 wt.% one or more impact resistance additives, where wt.% is taken from the total mass of the photocurable composition. 11. The curable composition of claim 10, wherein the poly (meth) acrylate is, or at least includes, a bifunctional acrylate compound. 12. Curable composition according to claim 10 or 11, where the free radical active component further comprises a compound with functional epoxy groups. 13. The curable composition of claim 10 or 11, wherein the cationically curable component further comprises a hydrogenated epoxy-containing bisphenol compound. 14. Curable composition according to claim 10 or 11, where the photocurable composition comprises 0.01-40 wt.% One or more additives that increase impact resistance. 15. A method of obtaining a non-toxic photocurable composition, comprising mixing the following components:
(a) 35-80% by weight of a cationically curable component that contains an oxetane compound;
(b) 15-60 wt.% free radical active component, which is not dipentaerythritol hexaacrylate containing
(i) at least one poly (meth) acrylate compound and optionally
(ii) at least one dendritic acrylate polymer compound;
(c) 0.1-10 wt.% antimony-free cationic photoinitiator;
(d) 0.01-10% by weight of a free radical photoinitiator; and optional
(e) 0.01-40 wt.% one or more impact resistance additives, where wt.% is taken from the total mass of the photocurable composition. 16. A method of obtaining a three-dimensional product free of antimony, including
(a) forming a first layer of a photocurable composition according to any one of claims 1 to 9 on a surface;
(b) exposing the first layer under the action of actinic radiation from the images to form a displayed cross section, where the radiation has an intensity sufficient to cause substantial curing of the first layer in the exposed areas;
(c) the formation of the second layer of the composition according to claim 1 on a previously exposed to the displayed cross-sectional radiation;
(d) exposure of the second layer of step (c) under the action of actinic radiation from the images in order to form the next displayed cross section, where the radiation has an intensity sufficient to cause substantial curing of the second layer in the exposed areas, as well as to cause adhesion of the second layer to a previously displayed transverse cross section exposed to radiation; and
(e) repeating steps (c) and (d) a sufficient number of times to obtain a three-dimensional product. 17. The method according to clause 16, where the photocurable composition comprises 0.01-40 wt.% One or more additives that increase impact resistance. 18. The method according to clause 16 or 17, where the photocurable composition has a viscosity in the range of 50-1000 MPa · s (cP). 19. A three-dimensional antimony-free medical device made in accordance with the method of any one of claims 16-18. 20. The three-dimensional medical device according to claim 19, wherein the medical device is a medical instrument, medical model or medical implant that fully complies with the requirements of USP 28, NF 23 for biological testing of plastics, class VI, 70 ° C. 21. A three-dimensional antimony-free product made according to the method of any one of claims 16-18. 22. A method for producing a three-dimensional antimony-free product using inkjet printing, comprising the following steps:
(a) sequentially applying drops of the photocurable composition according to any one of claims 1 to 9 to specific positions on a substrate, in accordance with the desired shape stored in a computer file;
(b) exposing droplets when exposed to electromagnetic radiation to cure droplets in exposed areas;
(c) repeating steps (a) and (b) a sufficient number of times, which allows the manufacture of a three-dimensional product. 23. The method according to item 22, where the substrate includes paper, fabrics, tiles, printing plates, wallpaper, plastic, powder, paste, or a liquid or already partially cured active resin. 24. The method according to item 22 or 23, where the photocurable composition is exposed when exposed to electromagnetic radiation in pixels, in lines, in layers, after several layers have been applied and / or after all layers have been applied. 25. The method according to item 22 or 23, where the used electromagnetic radiation is UV light, microwave radiation, visible light or laser beams.