substrate-based additive manufacturing process

专利摘要:
Substrate Based Additive Manufacturing Process The invention relates to a substrate based method for forming a three-dimensional object by manufacturing the additive by coating a radiation curable liquid resin comprising from 30 to 80% by weight of curable cationic compounds onto a substrate by engaging the radiation curable liquid resin with a subsequently cured layer, selectively exposing the radiation curable liquid resin layer layer to actinic radiation, thereby forming a cured layer, separating the cured layer from the substrate, and repeating the steps. enough time to construct a three-dimensional object.
公开号:BR112012014900B1
申请号:R112012014900
申请日:2010-12-16
公开日:2019-09-10
发明作者:Xu Jigeng；Dake Ken
申请人:Dsm Ip Assets Bv；
IPC主号:

专利说明:

PROCESS FOR SUBSTRATE ADDITIVE MANUFACTURING
FIELD OF THE INVENTION
The present invention relates to a process for manufacturing a substrate-based additive.
HISTORY OF THE INVENTION
Additive manufacturing processes for producing three-dimensional articles are known in the art. Additive manufacturing processes use computer aided design (CAD) data from an object to create three-dimensional parts, layer by layer. These three-dimensional pieces can be formed from liquid resins, powders, or other materials.
A non-limiting example of an additive manufacturing process is stereolithography (SL). Stereolithography is a well-known process for rapidly producing models, prototypes, molds and production parts ____________ in certain applications. SL uses an object's CAD data, in which the data is transformed into thin cross sections of a three-dimensional object. The data is loaded into a computer that controls a laser beam that traces the pattern of a cross section through a radiation curable liquid resin composition contained in a tank, solidifying a thin layer of the resin corresponding to the cross section. The solidified layer is covered with resin and the laser beam traces another cross section to harden another layer of resin at the top of the previous layer. The process is repeated layer by layer, until the three-dimensional object is completed. When initially formed, the three-dimensional object is, in general, not fully cured
2/77 and can therefore be subjected to post-cure if necessary. An example of an SL process is described in US Patent 4,575,330.
The most widely used method to create parts from a radiation-curable liquid resin is stereolithography. Stereolithography is an additive manufacturing process based on a vat. Vat-based systems consist of a large reservoir, or vat, of resin curable by liquid radiation, where imaging occurs. A vertically mobile lift platform is submerged in the tank and is used to support the solid three-dimensional object as it is constructed. In addition, a coating is present to assist in the formation of the next layer of liquid radiation curable resin. The coating is present on the surface of the liquid radiation-curable resin_ and moves across the surface of the same to assist in the formation of the next layer of liquid radiation-curable resin.
Typically, the construction process in vat-based systems is a recurring process consisting of the following repetition steps: 1) the surface of the radiation-curable liquid resin is exposed to the appropriate image radiation by tracking a desired object cross-section three-dimensional by a laser, thus forming a solid layer, 2) the mobile elevator is vertically transferred downstream, additionally below the surface of the radiation-curable liquid resin surface, 3) the coating is transferred through the surface of the radiation-curable liquid resin to assist in the formation of the next layer of liquid radiation curable resin, and 4)
3/77 the elevator is moved upstream, such that the distance between the surface of the radiation curable liquid resin and the solid layer thus formed of the three-dimensional object is equal to the desired thickness of the layer to be formed. Optionally, there may be a programmed dwell time before the steps are repeated in order to allow the liquid radiation curable resin to equilibrate such that a uniform layer thickness is ensured.
In general, there are two elements of a stereolithography process that inhibit process speed: 1) the laser beam tracing, and 2) the covering process and optional dwell time. Recently, new additive manufacturing systems have been developed with the aim of improving the speed of the process layer by layer .___
First, the tracing of the laser beam in a stereolithography process inhibits the speed of formation. The speed of the tracing step is highly dependent on the area and complexity of the cross section. More tracing must occur through a more complex cross section, larger than for a smaller, relatively simple one.
Additive manufacturing systems have been developed which do not use lasers as the source of image radiation in order to make the imaging stage less dependent on the complexity of the cross section. First, the new imaging source is a projection of a DMD (Digital Micromiror Device) or LCD (Liquid Crystal Display) projector. DMD-based systems use a special chip comprising thousands of mirrors
4/77 microscopes that correspond to the pixels of the image. When using such a system in an additive manufacturing process, an imaging time that is independent of the complexity of the cross section can be achieved. See US Patents 7052263 for an example of a system that uses this type of imaging source. In some cases, a second lighting is beneficial to improve the resolution of the image; see, for example, European Patent EP174487IB1.
Second, the covering process and optional dwell time hinder the speed of a stereolithography process. Due to the large amount of curable liquid radiation resin that is present in the vat, the coating process and residence time cannot be completely removed with current stereolithography processes and radiation curable liquid resin technology. The speed of the coating process and the residence time are largely a function of the properties of the radiation-curable liquid resin, mainly viscosity.
Systems have been developed, where imaging takes place using a vat-based system that is modified to use a sheet or film to assist in the formation of each layer. Such a technique is described, for example, in US Patent numbers 5171490, 7052263 and 7438846.
Additional manufacturing systems have been developed which are known as vat-free systems. Vessel-free systems differ from traditional vat-based systems in that the imaging step does not occur within the radiation curable liquid resin reservoir. Instead, the layer of
5/77 imaging layer, one layer at a time.
Examples of undisclosed systems, for example, in
Patents
European
EP1710625
Patents
US 6547552,
7614866,
7758799 and
7731887.
An example of a commercially available vat-free system is the ν'FLASH® system available from 3D Systems, Inc.
a common feature of these examples is that they require a step of separating the freshly cured solid layer from a separating or carrier layer, such as a film, sheet, glass, or plate. Such separation layers and carriers will be referred to collectively as substrates throughout the present patent application. In addition, each of these machines employs an upside-down construction platform, where the part is moved vertically upstream as it is constructed, rather than vertically downstream, as in a traditional stereolithography device.
Although the use of substrates in an additive manufacturing process offers several improvements over traditional vat-based systems, the use of substrates also presents several challenges. For example, the substrate-based process adds the complexity of accurately coating the substrate with radiation-curable liquid resin. In addition, increasing the speed of the process requires that the appropriate green resistance be developed in order to facilitate the proper peeling of the substrate and bonding to the previously cured layer. Finally, the adhesion of the liquid radiation curable resin to the substrate must be treated.
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Several patent applications discuss resin formulations useful in the additive manufacturing process based on a substrate. W02010 / 027931 for 3D Systems, Inc discloses a radiation-curable liquid resin comprising only radically free polymerizable compounds. The compositions of W02010 / 027931 include mixtures of (meth) acrylates and (meth) urethane acrylates. US Patent number 7358283, assigned to 3D Systems Inc., discloses all liquid radiation curable acrylate resins that are assumed to be easily released from substrates. These compositions also require a mixture of urethane (meth) acrylates and (meth) acrylates.
It is well known in the field of radiation-curable liquid resins that liquid, radiation-curable resins produce cured three-dimensional articles with the most desirable combination of mechanical properties. A radiation curable liquid resin is a radiation curable liquid resin that comprises both cationic and free radical polymerizable components and photoinitiators. It is also well known that the cationically polymerizable components of a radiation-curable liquid resin primarily contribute to the desirable combination of mechanical properties in a cured article
three-dimensional, however, components cationically polymerizable of a radiation-curable liquid resin polymerize the a slower ratio than the components polymerizable radically free. Consequently,
mechanical properties of the cured three-dimensional article develop over time after the initial curing of the hybrid, liquid, radiation-curable resin. The complexities
7/77 added to these known substrate-based additive manufacturing processes also contribute to the difficulty in formulating the radiation-curable liquid resin for substrate-based additive manufacturing processes.
Therefore, it would be desirable to develop hybrid, liquid, radiation-curable resins that are capable of forming cured three-dimensional articles that have excellent mechanical properties when cured in a substrate-based additive manufacturing process.
SUMMARY OF THE INVENTION
The first aspect gives gift invention claimed is a method for form one object three-dimensional system comprising: 1) coating a layer resin liquid
radiation curable comprising from 30 to 80% by weight, more preferably from 35 to 80% by weight, more preferably from 35 to 75% by weight, more preferably from 35 to 70% by weight of at least one compound cationically curable on a substrate;
2) contact of the radiation curable liquid resin layer with a previously cured layer;
3) selective exposure of the radiation-curable liquid resin layer to actinic radiation, provided by an actinic radiation source, thus forming a cured layer that adheres to the previously cured layer;
4) allowing a delay time to occur and after completion of the separation delay time, separating the cured layer and the substrate; and
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5) repetition of steps 1 to 4 a sufficient number of times in order to construct a three-dimensional object;
where the separation delay time is the time from the first exposure of the radiation curable liquid resin layer to actinic radiation with respect to the time that the storage shear modulus (G ¹ ) of the radiation curable liquid resin is measured upon reaching a value (G ¹ ) greater than 9.0 x 10 ⁵ Pa, preferably greater than 1.0 x 10 ⁶ Pa, more preferably greater than 2.0 x 10 ^δ Pa, as measured from the beginning of exposure to light, when the storage shear modulus (G ¹ ) of the radiation-curable liquid resin is measured on a Real-Time Dynamic-Mechanical Analyzer as the liquid-curable resin is cured with a light intensity of 50 mW / cm ² per exposure time to light of 1 second. _______________ _______________
The second aspect of the claimed invention is a three-dimensional object manufactured using the method of the first aspect of the claimed invention.
The third aspect of the claimed invention is a method for obtaining a three-dimensional object comprising:
1) coating of the radiation curable liquid resin layer comprising from 30 to 80% by weight, more preferably from 35 to 80% by weight, more preferably from 35 to 75% by weight, more preferably from 35 to 70% by weight at least one cationically curable compound on a substrate;
2) contact of the radiation curable liquid resin layer with a previously cured layer;
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3) selective exposure of the radiation-curable liquid resin layer to actinic radiation, provided by an actinic radiation source, thus forming a cured layer that adheres to the previously cured layer;
4) separation of the cured layer and the substrate; and
5) repetition of steps 1 to 4 a sufficient number of times in order to construct a three-dimensional object;
wherein the storage shear modulus (G ') of the curable liquid resin measured when reaching a value (G ¹ ) greater than about 7.5 x 10 ⁵ Pa, preferably higher
8.5
10 ⁵
Pa, more preferably greater than
9.5 x 10 ⁵
Pa, in two seconds from the beginning of the exposure when the storage shear modulus (G ¹ ) of the radiation-curable liquid resin is measured in a Real-Time Mechanical Dynamic Analyzer as the radiation-curable liquid resin is cured with a light intensity 50 mW / cm ² for a light exposure time of 1 second.
The fourth aspect of the claimed invention is a three-dimensional object manufactured using the method of the third aspect of the claimed invention.
DETAILED DESCRIPTION OF THE INVENTION
US Provisional Order number 61/287620 is incorporated herein by reference in its entirety.
The first aspect of the claimed invention is a method for making a three-dimensional object comprising:
1) coating a layer of radiation curable liquid resin comprising 30 to 80% by weight, plus
10/77 preferably from 35 to 80% by weight, more preferably from 35 to 75% by weight, more preferably from 35 to 70% by weight of at least one cationically curable compound on a substrate;
2) contact of the radiation curable liquid resin layer with a previously cured layer;
3) selective exposure of the radiation curable liquid resin layer to actinic radiation provided by an actinic radiation source, thus forming a cured layer that adheres to the previously cured layer;
4) permission for a delay time to occur and after the completion of the delay time, separation of the cured layer and the substrate; and
5) repetition of steps 1 to 4 a sufficient number of times in order to construct a three-dimensional object;
where the separation delay time is the time from the first exposure of the radiation curable liquid resin layer to actinic radiation with respect to the time that the storage shear modulus (G ¹ ) of the radiation curable liquid resin is measured upon reaching a value (G ¹ ) greater than 9.0 x 10 ⁵ Pa, preferably greater than 1.0 x 10 ⁶ Pa, more preferably greater than 2.0 x 10 ⁶ Pa, as measured from the beginning of exposure to light, when the storage shear modulus (G ¹ ) of the radiation-curable liquid resin is measured in a Real-Time Dynamic-Mechanical Analyzer as the radiation-curable liquid resin is cured with a light intensity of 50 mW / cm ² per exposure time to light of 1 second.
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A substrate is any material that provides a surface on which the radiation-curable liquid resin can be irradiated and then separated. Non-limiting examples of substrates are slabs, plastics, or flexible sheets. Flexible sheet substrates can be elastic, such as the preferred silicone film in US 7438846 for Envisiontec, or substantially non-elastic such as thin Mylar, or TPX film. Preferably, the film is not elastic to reduce any effects caused by movement during curing.
Preferably, the thickness of the substrate is about 75 to 200 microns, preferably about 90 microns to about 160 microns. In one embodiment, the substrate is coated with a material that helps release the freshly cured layer of the substrate. In an additional embodiment, the substrate is formed from layers of different materials. In one embodiment, the substrate consists of at least two layers, preferably two or three layers. A multilayer sheet allows at least one layer of contact barrier with the resin and a non-contact layer of lower or middle resin. The contact barrier layer with the resin provides good chemical resistance and release properties, while the non-contact layer with the middle or lower resin provides thermal and mechanical properties, hardness, flexural strength and / or fatigue resistance. In a three-layer modality, the bottom layer is the same as the contact layer of the resin. In another embodiment, the lower layer is different from the barrier layer of
12/77 resin contact. The contact barrier layer of the resin can be a coating layer.
The choice of substrate is important for the integrity of the additive manufacturing process. The substrate is preferably substantially transparent in radiation, but the substrate may still be impaired by repeated exposure to radiation, for example, UV light. A substrate that rapidly decomposes in the presence of certain wavelengths of radiation, for example, UV light, must be updated. In some cases, a fresh substrate must be provided after each layer is cured.
The first step of the first aspect of the claimed invention is to coat a layer of liquid radiation curable resin on the substrate. The coating can be carried out using, for example, an engraving roller (Meyer bar), an applicator, or spraying the coating on the substrate. A thin layer of radiation curable liquid resin is desired. In one embodiment, the radiation-curable liquid resin layer is 1 to 1,000 microns thick. Preferably, the radiation curable liquid resin layer is from about 25 microns to about 250 microns in thickness, more preferably from 25 microns to 125 microns, more preferably from 25 microns to 75 microns and with a substantially uniform thickness.
The second step of the first aspect of the claimed invention is to contact the liquid radiation curable resin on the substrate with a previously cured layer. This can be accomplished by, for example, moving the substrate, thus placing it on
13/77 contact with the radiation-curable liquid resin and the previously cured layer, or by moving the previously cured layer in contact with the radiation-curable liquid resin on the substrate. For the first layer of a three-dimensional object, the radiation-curable liquid resin can be contacted with a solid construction platform such as a construction support or solid plate. It may be desirable to use a slow forming speed with a higher radiation dose in order to ensure good adhesion to the construction platform for the initial layer, as long as the cohesive strength of the part is not a problem.
The third step of the first aspect of the claimed invention is the selective exposure of the radiation curable liquid resin to actinic radiation, thus forming a cured layer that adheres to a previously cured layer. Actinic radiation can be provided from any suitable source, for example, a laser, lamp, LED or laser diode. Any appropriate wavelength of light emission that sufficiently overlaps the absorbance spectrum of the photoinitiators in the radiation curable liquid resin is suitable. Preferably, the wavelength of the light is 300 - 475 nm, preferably 340 - 400 nm, more preferably 350-375 nm, more preferably about 365 nm. Preferably, the light source is a light emitting diode (LED) or an array of LEDs.
Selective exposure can occur, for example, by moving an actinic radiation source through the entire radiation curable liquid resin and / or switching the actinic radiation source from on to off according to
14/77 the desired exposure profile. In another embodiment, actinic radiation is selectively applied by exposing the mask. In an additional embodiment, actinic radiation is applied using a projection from a DMD. In one embodiment, the actinic radiation must first pass through the substrate to reach the liquid radiation curable resin. In one embodiment, the exposure of the entire layer can occur in one step, for example, using one projection, or multiple projections that occur simultaneously. In another modality, exposure can occur gradually. For example, the exposure pattern can be moved along the surface of the radiation curable liquid resin. In this method, certain regions of the same radiation curable liquid resin layer can be exposed to actinic radiation, sometimes being significantly different, for example, greater than 15 or even greater than 30 seconds interval, depending on the size of the liquid curable resin layer by radiation to be selectively exposed. In another modality, the exhibition takes place in several stages. For example, the liquid radiation-curable resin is exposed to a first exposure and then later to a second exposure in a short period of time.
The fourth step of the first aspect of the claimed invention is to remove the radiation-curable liquid resin from the substrate for a period that exceeds the separation delay time as measured from the time of selective exposure. This step can be accomplished by moving the curing layer, moving the substrate, or both. Preferably, the substrate is flexible. A flexible substrate
15/77 allows flaking first to enter, first to leave, where the regions of the liquid radiation-curable resin that are first irradiated are generally the first to be stripped of the substrate. See WO 2010/74566 for TNO, incorporated in this document as a reference in its entirety, for the description of a device capable of peeling first in first to out.
Although a separation delay time is fixed, as detailed by the analysis of the storage shear module revealed in this document, the period of time in which the various regions of the layer are exposed or separated from the substrate is variable. The separation time is the time of selective exposure of the radiation curable liquid resin to actinic radiation in relation to the time that the cured layer and the substrate are separated. The separation time is specific for each region to be cured. In a first-to-first peeling process or a similar process in which the selective exposure of the radiation curable liquid resin layer occurs gradually, the separation time of several regions of the cured layer may not be identical. For example, certain regions of the same layer of liquid radiation curable resin can be coated, exposed, or stripped at different times when a layer is formed. In some embodiments, certain regions of a cured layer may have been separated before other regions of liquid radiation curable resin have even been coated on the substrate. The phrase separation from curable layer means that all regions of the layer
16/77 cured are separated after exposure to actinic radiation for a longer time than the separation delay time, although different regions can be separated at different times. Since the separation time is specific for each region to be cured, whether or not the separation delay time has occurred must be determined for each region of the radiation curable liquid resin being cured.
Different regions of a cured layer can have different time intervals between exposure and separation in relation to other layers. For example, a first region, Region, A, has an exposure time of Time J and a Time K of separation, and a second region, Region B, has an exposure time of Time L and a time M of separation. (Time K minus Time J) can be the same, equal, or less than (Time M minus Time L). Now, if the process Separation Delay Time is determined to be Separation Delay Time X, as determined by the shear module storage analysis method described in the present application, then both (Time K minus Time J) and (Time M minus Time L) must exceed the Separation Delay Time X. In other modalities, Region A and Region B must have the same exposure time, but different separation times.
Region means a section of a radiation-curable liquid resin that has been exposed to radiation in an amount sufficient to cause substantial curing of the radiation-curable liquid resin. Erratic radiation or insufficient radiation to cause substantial curing of the radiation curable liquid resin does not define a region.
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For example, if a first area of a radiation-curable liquid resin layer is illuminated first by a light source of sufficient intensity to cause substantial cure and a second area of radiation-curable liquid resin of the same layer is illuminated by the same or a different light source of sufficient intensity to cause substantial healing at a later time, two regions will have been created. Regions can be overlapping.
next component of the method of the first aspect of the present claimed invention is the radiation curable liquid resin. In substrate-based additive manufacturing processes, a newly cured layer of liquid curable radiation curable develops both the cohesive resistance for the previously cured layer and the adhesive resistance to the substrate as the layer solidifies. When formulating radiation-curable liquid resins for use in substrate-based additive manufacturing processes, it is important that the newly cured layer of radiation-curable liquid resins completely strip the substrate. The flaking of a freshly cured layer of the radiation curable liquid resin from the substrate is known as adhesive failure.
rapid development of good adhesive strength for the previously cured layer is important for all adhesive manufacturing applications. Cohesive strength is even more important in substrate-based adhesive manufacturing processes due to the added forces caused by the substrate peeling off the substrate.
18/77 freshly cured layer of radiation curable liquid resin (adhesive resistance). The strong adhesion of a recently cured layer of radiation curable liquid resin to the substrate can cause cohesive failure. Cohesive failure occurs when the recently cured layer of liquid curable radiation cured adheres more to the substrate than to the previously cured layer and either does not separate completely from the substrate or causes some separation between the previously cured layers. Such a cohesive failure is catastrophic for the construction of the pieces in a layered way. In summary, the construction will fail unless the curing of the liquid radiation curable resin can be controlled, such that the adhesive failure occurs before the cohesive failure for each and all layers of the construction.
In addition, a point of complication is that the cured layer must develop sufficient and proper strength so that it can be completely separated from the substrate without fracture or otherwise failing. In general, this property can be measured as the storage shear modulus (G ¹ ) of the radiation-curable liquid resin using Mechanical-Dynamic Analysis in
Real Time (RT-DMA).
However, even if the cured layer develops shear modulus in sufficient storage, it may still have developed much more adhesive strength in relation to the substrate, such that cohesive failure or incomplete flaking occurs. In general, it is desirable that a liquid curable resin is able to develop shear modulus in storage quickly and has low adhesive resistance to the substrate before stripping. Once it occurs
19/77 desquamation, it is desirable to quickly build cohesive resistance in the piece, such that cohesive failure will not occur when building subsequent layers.
The hybrid, liquid, radiation-curable resin formulations have been preferred in manufacturing additive applications that do not use a substrate, for example, for stereolithography applications. Generally, the rate of cationic polymerization in a radiation curable liquid resin is considered too slow for rapid prototyping applications, unless a sufficient amount of radically free polymerizable components is incorporated into the radiation curable liquid resin. The rate of polymerization of photoinitiated free radicals is very fast, much faster than the rate of photoinitiated cationic polymerization. This rapid polymerization is critical for green resistance and the build up of cohesive resistance required for rapid prototyping applications. However, free radical polymerizable components suffer from high polymerization shrinkage, oxygen inhibition and very weak mechanical properties after curing. Despite these deficiencies in the radically free polymerizable components, a radiation curable liquid resin without radically free polymerizable components will generate very slow curing for use in rapid prototyping applications.
In addition, free radical polymerizable components generally develop less adhesive resistance to the substrate than cationically curable components. Consequently, previous attempts at
20/77 formulation of radiation-curable liquid resins for use in substrate-based additive manufacturing processes resulted in compositions with a radically free base. Such compositions generally contain a mixture of various urethane (meth) acrylates and / or (meth) acrylates. See US Patent Number 7358283 and WO 2010/027931, both for 3D Systems, Inc. Urethane (meth) acrylates are widely known to be mostly incompatible with cationically cured systems. Please see Vabrik et al., Journal of Applied Polymer Science, Vol. 68, 111-119 (1998); (2) US 4,920,156 (It should be understood, of course, by those skilled in the art that when such nitrogen-containing compounds are used with photoinitiators, only minor amounts of compounds containing basic organic nitrogen can be used so as not to interfere with the reaction polymerization). ___
Due to the slower cure of hybrid, liquid, radiation-curable resins it is much more difficult to develop a sufficiently high storage shear module as the amount of cationically curable components increases. In addition, hybrid resin curing systems have an increased adhesive strength compared to the substrate than radiation-curable liquid resins composed of curable components with total free radicals. Therefore, the ideal scenario in curing a hybrid, liquid, radiation-curable resin in a substrate-based additive manufacturing process is to rapidly develop green strength, cohesive strength or strength in volume, while presenting a cure rate initially slow us
21/77 cationically curable components in order not to develop too much adhesive resistance.
After desquamation, the cationically curable components must cure quickly so that the three-dimensional object can develop sufficient green resistance, so that the cohesive failure does not occur in the underlying layers. The period of time after flaking is thus important for the success of the additive manufacturing process and must be combined with the curing and adhesion properties of the radiation-curable liquid resin.
Various methods of making substrates from additives are known. Each of these methods is of varying complexity and presents different challenges for the formulator of a radiation-curable liquid resin.
US7438846 for Envisiontec teaches the benefit of a highly elastic substrate, such as a substrate made of silicone or latex, in order to facilitate the separation of the cured resin and the substrate, facilitating a combination of shear and peeling effects (Column
3, 11.16-22). In this mechanism, the substrate is separated from the cured resin layer by movement in the vertical direction of the elevator that holds the piece. This patent also describes the importance of a horizontal component of the force, with the angle changing during the separation process (col. 3, 11. 42-54 and figures 3B and 3C).
US 7731887 for 3D Systems reveals a mechanism that separates the cured layer from the substrate by a shear process (col. 14, 1.65 to col. 15, 1.5). The mechanism, revealed in that patent, uses mainly non-elastic substrates, for example PTFE (col. 12 11, 33-48). THE
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US patent 7614866 to 3D Systems discloses a similar method of manufacturing a substrate-based additive. The cured resin is separated from the substrate mainly by a shearing action, however the lift platform can be placed in order to facilitate removal (col. 25 1.31 to col. 26 1.21 and figures 62 and 63). In addition, it is indicated that the elevator or substrate can be twisted to facilitate removal of the substrate.
WO 2010/74566 for TNO teaches an additive manufacturing process, where imaging and flaking occur simultaneously. In other words, imaging a location on the radiation curable liquid resin layer occurs while a different location on the same layer, now freshly cured, is separated from the substrate. The peeling angle is constant throughout the
construction. In according to first aspect of this invention claimed, resin liquid curable by radiation is able to achieve a value (G ¹ ) greater than about
9.0 x 10 ⁵ Pa, preferably greater than 1.0 x 10 ⁶ Pa, more preferably greater than 2.0 x 10 ⁶ Pa, when the storage shear modulus (G ¹ ) of the radiation curable liquid resin is measured in a Real-Time Mechanical-Dynamic Analyzer with an 8 mm plate and a 0.10 mm sample slit, in which the said shear modulus in storage (G ¹ ) is measured as the liquid resin curable by radiation being cured with a light intensity of 50 mW / cm ² for an exposure time of 1 second. In one embodiment, the shear module in storage is measured at an ambient temperature from breaking
23/77 to 23 ° C and a relative humidity percentage of 25 to 35%.
When obtaining the said value of shear modulus in storage by time of curable liquid delay, capable of developing sufficient initial resistance in one if a resin reaches this storage process with enough to be stripped part. The inventors have found that, not being able to shear modulus value in three-dimensional basis that the present cationically delayed properties on the substrate will be less desirable claimed.
curable, slower separation times, produce articles that
In the process, component ratio is generally more difficult for a radiation curable liquid resin
Ltiva ^ __ for example, more than 30% by weight of cationically curable components achieve a shear modulus in storage high enough to allow complete flaking in the separation delay time.
According to the present claimed method, the freshly cured layer must be separated from the substrate after the separation delay time. The freshly cured layer does not necessarily need to be stripped exactly at the separation delay time. Instead, the separation delay time must occur some time before the separation occurs. In addition, the inventors have found that if the cured layer and substrate are not separated by a certain upper time limit, then construction will fail. The attempt to separate the substrate and the
24/77 cured layer after the upper time limit will result in cohesive failure between the previously cured layers, lack of cohesion from the recently cured layer to the previously cured layer, and / or only partial separation of the cured layer from the substrate. In one embodiment, that upper timeout is 30 seconds, preferably 25 seconds, more preferably 20 seconds, more preferably 18 seconds, more preferably 15 seconds, more preferably 10 seconds, more preferably 6 seconds.
The inventors surprisingly discovered, hybrid radiation-curable liquid resins that comprise a sufficient amount of cationically curable components to allow the formation of three-dimensional objects, with excellent mechanical properties and being --- capable ---- of successfully constructing three-dimensional objects, in a substrate-based additive manufacturing process according to the first aspect of the claimed invention. In the embodiments, the radiation curable liquid resins comprise a cationic polymerizable component, a cationic photoinitiator, a free radical polymerizable component, and a free radical photoinitiator. Those skilled in the art realize that this patent application reveals the various content ranges of these four components in combination with one another, and that the combination of any of these ranges cited separately does not result in a new invention not disclosed in this document when the components are combined in the aforementioned ranges.
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The liquid curable radiation resins used in the process of the invention comprise at least 30% by weight, preferably from 30 to 80% by weight, more preferably at least 35% by weight, more preferably 35 to 80% by weight, more preferably from 35 to 75% by weight, more preferably 35 to 70% by weight of at least one cationically curable compound. In another embodiment, the radiation-curable liquid resin comprises at least 40% by weight, more preferably from 40% to 80% by weight, more preferably from 40% to 75% by weight, more preferably from 40% to 70% by weight. weight of at least one cationically polymerizable compound.
According to one embodiment, the radiation-curable liquid resins of the present invention comprise at least one cationically polymerizable component, i.e., one that undergoes polymerization initiated by ____ cations, or in the presence of acid generators. The components cationically monomers, oligomers, and / or aliphatic, arylaliphatic, heterocyclic fraction (fractions) Polymerizable cyclic ether compounds can be polymers, and can contain aromatic, cycloaliphatic, and any combination thereof. Suitable groups may comprise cyclic ether groups as side groups or groups that form part of an alicyclic or heterocyclic ring system.
The polymerizable cationic component is selected from the group consisting of cyclic ether compounds, cyclic acetal compounds, cyclic thioether compounds, spiro-orthoester compounds, lactone compounds
26/77 cyclic, and vinyl ether compounds, and any combination thereof.
Examples of cationically polymerizable components include, epoxy compounds such as cyclic ether compounds and oxetanes, cyclic lactone compounds, cyclic acetal compounds, cyclic thioether compounds, spiro orthoester compounds, vinyl ester compounds.
Specific examples of cationically polymerizable components include bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, bisphenol diglycidyl ether
A brominated, brominated diglycidyl bisphenol ether, bisphenol diglycidyl ether Bisphenol diglycidyl diglycidyl ether
Brominated, novolac epoxy resins, hydrogenated bisphenol A, ether
Hydrogenated F, hydrogenated bisphenol S diglycidyl ether, 3,4-epoxycyclohexylmethyl1-3 ¹ , 4 ¹ epoxycyclohexanecarboxylate, 2- (3,4-epoxycyclohexyl-5,5spiro-3,4-epoxy) -cyclohexane-1,4-dioxane , bi (3,4 epoxycyclohexylmethyl) adipate, vinylcyclohexane oxide, 4vinilepoxiciclohexano, vinylcyclohexene dioxide, limonene oxide, limonene dioxide, bi (3,4-epoxy-6metilciclohexilmetil) adipate, ^{3,4-epoxy-6-1} metilciclohexil3 , 4'-epoxy-6'-meetylcyclohexanecarboxylate, 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexane modified ε-caprolactone, 3,4-epoxycyclohexylmethyl-3 ¹ , 4'epoxycyclohexane carboxylates, 3-epoxycyclohexyl carboxylates, trimethyl carboxylates, carboxylates. , 4epoxiciclohexeilmetil ^1-3 ' , 4'-O-epoxiciclohexano βmetil valerolactone-modified biciclohexil ^{1-3,3-epoxide,} bi (3,4 epoxycyclohexyl) with a binding -O-, -S-, -SO-, - S0 ₂ 27/77
C (CH ₃ ) ₂ , -CBr ₂ , -C (CBr ₃ ) ₃ -, -C (CF ₃ ) ₂ -, -C (CC1 ₃ ) ₃ or -CH (C ₆ H ₅ ), dicyclopentadiene diepoxide, ethylene glycol di (3,4epoxycyclohexylmethyl), ethylene bi (3,4epoxycyclohexanocarboxylate), epoxyhexahydrodioctyl phthalate, epoxyhexahydro-2-ethylhexyl phthalate, 1,4-butanediol diglycidyl ether, 1,6-hexanidyl ether, diglycidyl glycol, ether; triglycidyl glycerol ether, triglycidyl trimethylpropane ether, diglycidyl polyethylene glycol ether, diglycidyl polypropylene glycol ether, polyether polyol polyglycidyl ethers obtained by adding one or more alkylene oxides to aliphatic polyhydric alcohols, such as, ethylene glycol, propylene glycol of long chain aliphatic dibasic acids, monoglycidyl ethers of higher aliphatic alcohols, phenol monoglycidyl ethers, cresol, butyl phenol, or polyether alcohols obtained from these higher compounds, oil by addition of epoxy oxidized soybean glycidyl esters, alkylene to epoxybutyl stearic acid, epoxyoctyl stearic acid, epoxidized cottonseed oil, epoxidated polybutadiene, 1,4-bi [3-ethyl3-oxetanyl methoxy) methyl] benzene,
3-ethyl-3hydroxymethyloxetane,
3-ethyl-3- (3hydroxypropyl) oxymethyloxetane,
3-ethyl-3- (4hydroxybutyl) oxymethyloxetane,
3-ethyl-3- (5hydroxypentyl) oxymethyloxetane, 3-ethyl-3-phenoxymethyloxetane, bi ((1-ethyl (3-oxetanyl)) methyl) ether, 3-ethyl-3- ((2ethylhexyloxy) methyl) oxetane, 3 -ethyl ((triethoxysilylpropoxymethyl) oxetane, 3- (met) -alyloxymethyl3-ethyloxetane, (3-ethyl-3-oxetanylmethoxy) methylbenzene, 428/77 fluor- [1- (3-ethyl-3-oxetanylmethoxy) methyl] benzene,
4-methoxy [1- (3-ethyl3-oxetanylmethoxy) ethyl] phenyl, ether (3-ethyl-3-isobutoxymethyl, ether (3-ethyl-32-ethylhexyl), ether (3-ethyl-3-ethylethylene glycol), ether (3-ethyl -3dicyclopentadiene, (3-ethyl-3dicyclopentenyloxyethyl ether, (3-ethyl-3oxetanylmethyl) dicyclopentenyl ether, (3-ethyl-3-tetrahydrofurfuryl ether, ether (3-ethyl-32-hydroxyethyl, ether (3-ethyl-32-hydroxypropyl). Examples of polyfunctional materials that are cationically polymerizable include dendritic polymers, such as, dendrimers, linear polymers;
hyper-fused polymers, star-branched polymers hypo-graft polymers with epoxy or oxetane functional groups. Dendritic polymers can contain one type of polymerizable functional group or different types of polymerizable functional groups, for example, epoxy resin and the polymerizable cationic component is at least one selected from the group consisting of cycloaliphatic epoxy and an oxetane. In a specific embodiment, the polymerizable cationic component is an oxetane, for example, an oxetane containing 2 or more oxetane groups. In another specific modality, the polymeric cationic component is an epoxy
29/77 cycloaliphatic, for example, a cycloaliphatic epoxy with 2 or more than 2 epoxide groups.
In one embodiment, the epoxide is 3,4epoxycyclohexylmethyl-3 ', 4-epoxycyclohexane carboxylate (available as CELLOXIDE ™ 2021P from Daicel Chemical, or as CYRACURE ™ UVR-6105 from Dow Chemical), hydrogenated bisphenol A-epichlorohydrin-based epoxy resin (available as EPONEX ™ 1510 from Hexion), 1,4-cyclohexanedimethanol diglycidyl ether (available as HELOXY ™ 107 from Hexion), a mixture of dicyclohexyl and nanosilicate diepoxide (available as NANOPOX ™) and any combination thereof.
The inventors have surprisingly found that the addition of epoxidized polybutadiene to a hybrid, radiation-curable liquid resin can significantly improve the flaking properties of a recently cured resin from a support substrate. Depending on the type and classification of epoxidized polybutadiene materials and the concentration of any acrylate in the composition, the addition of about 5 to about 20% by weight, preferably from about 5 to about 10% by weight, of epoxidated polybutadiene leads to a composition with good film formation and rapid build-up of resistance. Such compositions have improved the peeling properties of various types of support substrates such as, for example, Mylar (i.e., polyester), TPX (i.e., PMP), glass sheets or glass plates. Suitable examples of epoxidized polybutadiene for use in the present claimed invention are Epolead® PB3600, available from Daicel Cheical and Poly bd® 600E available from Sartomer.
30/77
The above cationically polymerizable compounds can be used alone or in combination of two or more of these.
According to one embodiment, the polymerizable component of the liquid radiation-curable resin is polymerizable by both free radical polymerization and cationic polymerization. An example of such a polymerizable component is a vinyloxy compound, for example, one selected from the group consisting of bi (4-vinyloxybutyl) isophthalate, tri (4-vinyloxybutyl) trimellitate and combinations thereof. Other examples of such a polymerizable component include those containing an acrylate and an epoxy group, or an acrylate and an oxetane group, in the same molecule.
In the embodiments of the invention, the liquid radiation-curable resin used in the process of the "invention" also includes a cationic photoinitiator. According to one embodiment, the radiation-curable liquid resin includes a cationic photoinitiator. The cationic photoinitiator generates photoacids after irradiation of light. They generate Bronsted or Lewis acids when irradiated. Any suitable cationic photoinitiator can be used, for example, those selected from the group consisting of onium salts, halon salts, iodosyl salts, selenium salts, sulfonium salts, sulfoxonium salts, diazonium salts, metallocene salts, salts isoquinoline, phosphonium salts, arsenic salts, tropilium salts, dialkylphenacylsulfonium salts, thiopiryl salts, diaryl iodonium salts, triaryl sulfonium salts, antimonate salts
ferrocenes, compounds
in
31/77 di (cyclopentadienyliron) arene and pyridinium salts, in addition to any combination thereof. Onium salts, for example, iodonium salts, sulfonium salts and ferrocenes have the advantage of being thermally stable. Thus, any residual photoinitiator does not continue to cure after the removal of irradiated light. Cationic photoinitiators have the advantage of not being sensitive to oxygen in the atmosphere.
The embodiments of the invention comprise a liquid radiation-curable resin including at least one cationic photoinitiator, where the cationic photoinitiator is selected from the group consisting of aromatic diazonium salts, aromatic sulfonium salts, aromatic iodonium salts, metallocene-based compounds, aromatic phosphonium salts and aluminum silanol complexes, in addition to any combination thereof. In one embodiment, the cationic photoinitiator is selected from the group consisting of sulfonium salts, aromatic iodonium salts and metallocene-based compounds in addition to any combination thereof. In another embodiment, the cationic photoinitiator is selected from the group consisting of triarylsulfonium salts, diaryliodonium salts and metallocene-based compounds in addition to any combination thereof.
In a particular embodiment, the cationic photoinitiator has an anion selected from the group consisting of BF ₄ ', AsF ₆ ', SbF ₆ ', PF ₆ ', B (C ₆ F ₅ ) ₄ ·, perfluoralkylsulfonates, perfluoralkylphosphates and carborane anions.
In one embodiment, the cationic photoinitiator presents a cation selected from the group consisting of
32/77 aromatic sulfonium salts, aromatic iodonium salts and metallocene-based compounds with at least one anion selected from the group consisting of SbF ₆ ', PF ₆ , B (C ₆ F ₅ ) ₄ ·, perfluoralkylsulfonates, perfluoralkylphosphates and (CHgBuCle) '.
In a specific embodiment, the cationic photoinitiator is a cationic photoinitiator based on the sulfonium salt selected from the group consisting of 4- (4benzoylphenylthio) phenyldiphenylsulfonium hexafluorantimonate, 4 - (4-benzoylphenylthioxyphenyloxyphenyloxyphenyloxy)) 4- (4-benzoylphenylthio) phenyl bi (4-fluorophenyl) sulfonium, 4- - (4-benzoylphenylthio) phenyl bi (4-chlorophenyl) sulfonium, 4- [4- (3-chlorobenzoyl) phenylthio] phenyl ___ bij4-fluorphenyl) 4 - (4-benzoylphenylthio) phenyl bi (4methylphenyl) sulfonium, 4 - (. 4benzoylphenylthio) phenyl bi (4-hydroxyethylphenyl) sulfonium, 4- (4- (4hydroxyethyloxybenzyl) phenylphenyl] phenylbenzyl (4) 4- (4- (4- (4hydroxyethyloxybenzoyl) phenylthio] phenyldiphenylsulfonium hexafluorantimonate, 4- (4- (4 (hydroxyethyloxybenzyl) phenylthio] phenyl bi (4hydroxyethyloxyphenyl) sulfonium, hexafluor 4- [4 (benzoylphenylthio) phenyl bi (4-methoxyethoxyphenyl) sulfonium, 4- [4- (3methoxybenzoyl) phenylthio] phenyldiphenylsulfonium, hexafluorantimonate hexon
4- [4- (333/77 methoxycarbonylbenzoyl) phenylthio] phenyldiphenylsulfonium, 4- [4- (2-hydroxymethylbenzoyl) phenylthio] phenyldiphenylsulfonium, 4- [4- (4-methylbenzoyl) phenylthio] phenyl bi (4fluorfen) hexyl sulfonium, 4- [4- (4-phenylthio] phenyl bi (4-fluorophenyl) sulfonium, 4- [4- (4-fluorobenzoyl) phenylthio] phenyl bi (4-fluorophenyl) phenyl bi (4-fluorophenyl) sulfonate, 4- [4-hexafluorantimonate - (2methoxycarbonylbenzoyl) phenylthio] phenyl bi (4fluorfenyl) sulfonium, bi [4 (diphenylsulfonium) phenyl] bihexafluorphosphate, bi [4- (diphenylsulfonium) phenyl] bi tetrafluorborate, bi [4 - (diphenylsulfonium) sulfide ] tetracis (pentafluorfenil) borate, diphenyl-4- (phenylthio) phenylsulfonium hexafluorphosphate, diphenyl-4- (phenylthio) phenylsulfonium, diphenyl-4 (phenylthio) phenylsulfonium tetracis (pentafluorphenylsulfonate, hexylphenylsulfonate, hexylphenylsulfonate, hexane triphenylsulfonium, triphen ilsulfonium tetracis (pentafluorfenyl) borate, bi [4- (di (4- (2-hydroxyethoxy)) phenylsulfonium) phenyl] bihexafluorphosphate, bi [4- (di (4- (2 (hydroxyethoxy)) phenylsulfonium) phenyl] bi tetrafluorborate , and tetracis (pentafluorfenyl) borate bi [4- (di (4- (2 (hydroxyethoxy)) phenylsulfonium) phenyl] sulfate, and any combination thereof.
In another embodiment, the cationic photoinitiator is an aromatic iodonium salt based on the cationic photoinitiator selected from the group consisting of diphenyliodonium hexafluorphosphate, hexafluorantimonate of
34/77
tetracis (pentafluorfenil) borate bi (dodecylphenyl) iodonium, of
themselves.
cationic
(chlorophenyl) diphenylsulfonium chlorine [S- (phenyl) thianthrene], S-
thiantrene,
35/77 [4- [(2-hydroxytetradecyl) oxy] phenyl] phenyliodonium, (4methylphenyl) [4- [[2- [[[[3 (trifluoromethyl) phenyl] amino] carbonyl] oxy] tetradecyl] oxy] phenyl l ] iodonium, bi (4-dodecylphenyl) iodonium, [4- (1methylethyl) phenyl] (4-methylphenyl) iodonium, and any combination thereof.
In an illustrative embodiment, the radiation-curable liquid resin includes a cationic photoinitiator selected from the group consisting of SbF ₆ ~, triarylsulfonium borate, tetracis (pentafluorfenyl) tris (4- (4-acetylphenyl) thiophenyl) sulfonate, diaryliodonium borate , iodonium [4- (1-methylethyl) phenyl] (4-methylphenyl) tetracis (pentafluorfenyl) borate, and any combination thereof. A non-nucleophile anion serves as the counterion. Examples of such ions include BF ₄ AsF ₆ ', SbF ₆ ', PF ₆ ', B (C _fi Fg) 4 ~, perfluoralkylsulfonates, perfluoralkyl phosphates and carborane anions, such as, (CH ₆ BnC16)'.
Examples of cationic photoinitiators useful for curing at 300-475 nm, particularly at 365 nm UV light, without sensitizer include 4- [4- (3-chlorobenzoyl) phenylthio] phenyl bi (4-fluorophenyl) sulfonium, tetracis (pentafluorfenyl) borate hexafluorantimonate 4- [4- (3-chlorobenzoyl) phenylthio] phenyl bi (4-fluorophenyl) sulfonium, and tetracis (pentafluorphenyl) borate of tri (4- (4acetylphenyl) thiophenyl) sulfonium (GSID4480-1 also known as IRGACURE® PAG 2 90) da Ciba used in some exemplary compositions.
In some embodiments, it is desirable for the liquid radiation curable resin to include a photosensitizer. The term photosensitizer is used to refer to
36/77 any substance that either increases the polymerization rate of the photoinitiator or switches the wavelength at which the polymerization occurs, see G. Odian's book, Principies of Polymerization, 3 ^to Ed., 1991, page 222. Examples of Photosensitizers include those selected from the group consisting of methanones, xanthenones and pyrenemethanols, anthracenes, pyrene, perylene, quinones, xanthones, thioxanthones, benzoyl esters, benzophenones and any combination thereof. Specific examples of photosensitizers include those selected from the group consisting of [4- [(4-methylphenyl) thio] phenyl] phenyl-methanone, isopropyl-9H-thioxanthen-9-one, 1-pyrenemethanol, 9 (hydroxymethyl) anthracene, 9, 10-dietoxianthracene, 9,10-dimethoxy anthracene, 9,10-dipropoxy anthracene, 9,10-dibutyloxy anthracene, 9-anthracenomethanol acetate, 2-ethyl9,10-dimethoxy anthracene, 2-methyl-9,10-dimethoxy anthracene, 2t-butyl-9,10- dimethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene and 2-methyl-9,10-diethoxyanthracene, anthracene, anthraquinones, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tertbutylanthraquinone, 1-chloroanthraquinone, 2-amylanthraquinone, thioxanthanthione, xoxanthanthione anoxanthone , 2,4 diethyloxanthone, 1-chloro-4-propoxyoxanthone, methylbenzoyl formate, methyl-2-benzoyl benzoate, 4-benzyl-4'-methyl diphenyl sulfide, 4,4'-bi (diethylamino) benzophenone, and any combination the same.
In addition, photosensitizers are useful in combination with photoinitiators in curing with LED light sources emitting in the 300-475 nm wavelength range. Examples of suitable photosensitizers
37/77 include: anthraquinones, such as, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tertbutylanthraquinone, 1-chloroanthraquinone, and 2-amylanthraquinone, thioxanthones and xanthones, such as, isopropyl thioxanthone, 2-chlorotioxanthone, 2,4-diethyloxythone, 2,4-diethyloxythone, and 4propoxyoxanthone, methyl benzoyl format, (Darocur MBF from Ciba), methyl-2-benzoyl benzoate (Chivacure OMB from
Chitec), 4-benzoyl-4'-methyl diphenyl sulfide (Chivacure
Chitec BMS), 4,4'-bi (diethylamino) benzophenone (Chivacure
Chitec EMK).
In one embodiment, the otosensitizer is a fluorone, for example, 5,7-diiodo-3-butoxy-6-fluorone, 5,7-iodo-3-hydroxy-6-fluorone, 9-cyano-5,7-di iodine-3-hydroxy6-fluorone, or a photosensitizer is:
and any combination thereof.
The radiation-curable liquid resin can include any suitable amount of the photosensitizer, for example, in certain embodiments, in an amount of up to about 10% by weight of the composition, in certain embodiments, up to about 5% by weight of the composition, in
38/77 include:
4-methyl benzophenones, benzophenone, dimethoxybenzophenone such as,
2,4,6-trimethyl
Additional 1-hydroxyphenyl modalities from about 0.05% to about 2% by weight of the composition.
When photosensitizers are used, other photoinitiators absorbing at shorter wavelengths can be used. Examples of such photoinitiators benzophenone, benzophenone, and ketones, such as 1-hydroxycyclohexyl phenyl ketone, phenyl (1-hydroxyisopropyl) ketone, 2-hydroxy-1- [4- (2hydroxyethoxy) phenyl] -2-methyl-l-propanone and 4isopropylphenyl (1-hydroxyisopropyl) ketone, benzyl dimethyl ketal, and oligo- [2-hydroxy-2-methyl-1- [4- (1methylvinyl) phenyl] propanone] (Esacure KIP 150 from Lamberti). These photoinitiators when used in combination with a photosensitizer are suitable for use with LED light sources that emit at wavelengths between about 100 nm to about 300 nm.
LED light sources that emit visible light are also known. LED light sources that emit light at wavelengths greater than about 400 nm, for example, from about 475 nm to about 900 nm, examples of suitable photoinitiators include: camphorquinone, 4,4'-bi (diethylamino) benzophenone (Chivacure EMK de Chitec), 4.4 ¹ -bi (N, N'-dimethylamino) benzophenone (Michler's ketone), bi (2,4,6-trimethylbenzoyl) -phenylphosphine (Irgacure 819 or BAPO da Ciba), metallocenes, such as bi (eta 5-2-4cyclopentadien-l-yl) bi [2,6-diflúor-3- (1H-pyrrol-l-yl) phenyl] titanium (Irgacure 784 da Ciba) , and photoinitiators
39/77 visible light from Spectra Group Limited, Inc. such as, HNu 470, H-Nu-535, H-Nu-635, H-Nu-Blue-640, and H-Nu-Blue-660.
A photosensitizer or co-initiator can be used to improve the activity of the cationic photoinitiator. It is used either to increase the polymerization rate of the photoinitiator or to switch the wavelength at which the polymerization takes place. The sensitizer used in combination with the cationic photoinitiator mentioned above is not particularly limited. Various compounds can be used as photosensitizers, including heterocyclic hydrocarbons and fused ring aromatic hydrocarbons, organic dyes, and aromatic ketones. Examples of sensitizers include compounds disclosed by J.V. Crivello in Advances in Polymer Science, 62, 1 (1984), and by J.V. Crivello and K. Dietliker, Photoinitiators for Cationic Polymerization in Chemistry & technology of UV & EB formulation for coatings, inks & paints. Volume III, Photoinitiators for free radical and cationic polymerization, by K. Dietliker; [Ed. by P.K.T. Oldring], SIT A Technology Ltd, London, 1991. Specific examples include polycyclic aromatic hydrocarbons and their derivatives, such as anthracene, pyrene, perylene and their derivatives, thioxanthones, ahhydroxyalkylphenones, acridine orange 4-benzoyl-4 'methyldiphenyl sulfide and benzoflavin.
There are several cationic photoinitiators known and technically proven to be appropriate.
They include, for example, onium salts with weak nucleophilic anions. Examples are halon salts, iodosyl salts or sulfonium salts, such as
40/77 described in the published European Patent Application EP 153904 and WO 98/28663, sulfoxonium salts, as described, for example, in the published European Patent Applications EP 35969, 44274, 54509, and 164314, or diazonium salts, such as described, for example, in US Patent Nos. 3,708,296 and 5,002,856. All eight of the above disclosures are hereby incorporated by reference in their entirety. Other cationic photoinitiators are metallocene salts, as described, for example, in European Patent Applications EP 94914 and 94915, which are both incorporated herein by reference in their entirety.
A survey of other current onium salt initiators and / or metallocene salts can be found at UV Curing, Science and Technology, (Editor S. P. Pappas,
Technology Marketing Corp., 642 Westover Road, Stamford,
Technology of
UV & EB
Formula tion for Coatings, Inks &
Paints, Vol.
(edited by PKT Oldring).
Suitable photoinitiators of the cationic ferrocene type include, for example, salt compounds as disclosed in Chinese Patent Number CN 101190931:
41/77 in which the MXn anion is selected from BF ₄ ,
PF _S ,
SbF ₆ , and Ar is a fused ring or polycyclic arene.
Other illustrative photoinitiators of the cationic ferrocene type include, for example, (η6hexafluorphs fact, specifically [cyclopentadiene-Fe-N-butylcarbazole] hexafluror-phosphate (C4-CFS PF6) and [cyclopentadiene-Fe-N-octyl-carbol] hexafluorophosphate (C8-CFS
PF6), bearing C4 and C8 alkyl chains, respectively, on the nitrogen atom (see Polymer Eng.
& Science (2009), 49 (3), 613-618); ferrocenium dication salts, for example, bi (ποιο lopentadienyl) iron] biphenyl hexafluorphosphate cyclopentadien-iron-biphenyl hexafluorphosphate as disclosed in Chinese J.
Chem. Engnrng (2008), 16 (5), 819-822 and Polymer Bulltn (2005), 53 (5-6), 323-331; cyclopentadienyl-Fe-carbazole hexafluorphosphate ([Cp-Fecarbazol] + PF6-), cyclopentadienyl-FeN-ethylcarbazole hexafluorphosphate ([Cp-Fe-N-ethylcarbazole] + PF6-) and hexafluorphosphonate-cyclopentadine [amine-cyclopentinone] -Fe-aminonaphthalene] + PF6-) as disclosed in J Photochem. & Photobiology, A: Chemistry (2007), 187 (2-3), 389-394 and Polymer Intnl (2005). 54 (9), 1251-1255; alkoxy substituted ferrocene salts, for example, [cyclopentadien-Fe-anisol] PF6, [cyclopentadien-Fe-diphenylether] PF6, [cyclopentadien-Fe-diphenylether] BF4, and [cyclopentadien-Fe-dietoxide ] PF6 as disclosed in Chinese J. of Chem Engnrng (2006), 14 (6), 806-809; tetrafluorborates of
42/77 cyclopentadiene-iron-arene, for example, cyclopentadiene-iron-naphthalene tetrafluorborate, salt ([Cp-Fe-Naph) BF4), as disclosed in Imaging Science J (2003), 51 (4), 247253; ferrocenyl tetrafluorborate ([Cp-Fe-CP] BF4), as disclosed in Ganguang Kexue Yu Guang Huaxue (2003), 21 (1), 46-52; [CpFe (q6-tol)] BF4, as revealed in Ganguang Kexue Yu Guang Huaxue (2002), 20 (3), 177-184, ferrocene salts (ηβ-α-naphthoxybenzene) (q5-cyclopentadienyl) iron hexafluorophosphate (NOFC -1) and (η6-β-naphthoxybenzene) (q5-cyclopentadienyl) iron hexafluorophosphate (NOFC-2), as disclosed in J. of Photoenergy (2009), Article ID 981065; (q6-diphenyl-methane) (q5-cyclopentadienyl) iron hexafluorphosphate and (q6-benzenophenone) (q5-cyclopenta-dienyl) iron hexafluorphosphate as disclosed in Progress in Organic Coatings (2009), 65 (2), 251-256; [CpFe (q6isopropyl-benzene)] PF6, as disclosed in Chem. Comm. (1999), (17), 1631-1632 and any of their combinations.
Suitable cationic photoinitiators of the onion type include, for example, iodonium and sulfonium salts, as disclosed in Japanese Patent JP 2006151852. Other illustrative photoinitiators include, for example, onium salts, such as diaryliodonium salts, triarilsulfonium salts , aryl-diazonium salts, ferrocenium salts, diarylsulfoxonium salts, diaryliodoxonium salts, triaryl-sulfoxonium salts, dialkylphenancyl-sulfonium salts, dialkylhydroxyphenylsulfonium salts, phenacyl-triarylphosphonium salts and phenacyl-triaryl phosphonic salts and phenacyl compounds disclosed in US Patent Numbers 5,639,413; 5,705,116; 5,494,618; 6,593,388 and Chemistry of Materials
43/77 (2002), 14 (11), 4858-4866; aromatic salts of sulfonium or iodonium, as disclosed in US Patent Application number 2008/0292993; diaryl- or triaryl- or dialkylphenacylsulfonium salts, as disclosed in US2008260960 and J. Poly. Sci., Part A (2005), 43 (21), 5217; diphenyl iodonium hexafluorophosphate (Ph2I + PF ₆ '), as disclosed in Macromolecules (2008), 41 (10), 3468-3471; onium salts using onion salts using less toxic anions to replace, for example, SbF ₆ '. Anions are mentioned: B (C ₆ F ₅ ) ₄ ', Ga (C ₆ F ₅ ) ₄ ' and perfluoralkyl fluorophosphate, PFnRf (6-n) -, as revealed in Nettowaku Porima (2007), 28 (3 ), 101-108; photoactive allyl ammonium salt (BPEA) containing benzophenone fraction in the structure, as disclosed in Eur J Polymer (2002), 38 (9), 1845-1850, 1- (4-hydroxy-3-methylphenyl) tetrahydrothiophene hexafluorantimonate, as disclosed in Polymer (1997), 38 (7), 1719-1723; and any combination of these.
Illustrative cationic photoinitiators of the iodonium type include, for example, diaryliodonium salts having counter ions similar to hexafluror phosphate and others, such as, for example, (4-n-pentadecyloxy-phenyl) phenylidonium hexafluorantimonate, as disclosed in US2006041032; diphenyliodonium hexafluorophosphate, as disclosed in US4394403 and Macromolecules (2008), 41 (2), 295-297; diphenyliodonium ions as disclosed in Polymer (1993), 34 (2), 426-8; diphenyliodonium salt with boron tetrafluoride (Ph2I + BF4-), as disclosed in Yingyong Huaxue (1990), 7 (3), 54-56; SR-1012, a diaryldiodonium salt, as disclosed in Nuclear Inst. & Methods in Physics Res., B (2007), 264 (2), 318-322; salts
44/77 diaryliodonium, for example, 4,4'-di-tbutyldiphenyl-iodonium hexafluorarsenate, as disclosed in J Polymr Sei, Polymr Chem Edition (1978), 16 (10), 2441-2451; Diaryllium salts containing metal complex halide anions, such as diphenyliodonium fluorborate, as disclosed in
J Polymr Sci., Poly Sympos (1976), 56, 383-95;
any
Illustrative sulfonium-type cationic photoinitiators include,
UVI 6992 (sulfonium salt) described in the formula:
JP2007126612; compounds for example such as
Patent
Japanese where RI-2 = F; R3 = isopropyl; R4 = Η, X = PF6, as disclosed in Japanese Patent JP10101718; salts
for example • nZ ^s of the formula:
as described in US Patent No. 6,054,501; sulfon (acyloxyphenyl) salts of type R ₃ -xS + R3x A ', where A' is a non-nucleophilic anion, such as AsF ₆ ', and R3 may be the phenyl group shown below:
45/77
as described in US Patent No. 5,159,088; alkyldiaryl sulfonium salts 9,10-dithiophenoxyanthracene, for example, ethylphenyl hexafluoranthimonate (9-thiophenoxy anthracenyl-10) sulfonium, and the like, as disclosed in US Patent No. 4,760,013; etc.; triphenylsulfonium hexafluorophosphate salt, as disclosed in US Patent No. 4,245,029; S, S-dimethyl-S- (3,5-dimethyl-2-hydroxyphenyl) sulfonium salts, as disclosed in J Poly Sei., Part A (2003), 41 (16), 2570-2587; anthracene-bound sulfonium salts, as disclosed in J Photochem% Photobiology, A: Chemistry (2003), 159 (2), 161-171; triarylsulfonium salts, as disclosed in J. Photopolymer Science & Tech. (2000), 13 (1), 117-118 and J Poly Science, Part A (2008), 46 (11), 3820-29; S-aryl-S, S-cycloalkylsulfonium salts, as disclosed in J Macromol Sei, Part A (2006), 43 (9), 1339-1353; dialkylphenacylsulfonium salts, as disclosed in UV & EB Tech Expo & Conf, May 2-5, 2 004, 55-69 and ACS Symp Ser (2003), 847, 219-230; dialkyl (4hydroxyphenyl) sulfonium salts and their dialkyl (2hydroxyphenyl) sulfonium isomeric salts, as disclosed in ACS 224th Natnl Meeting, 18-22 August 2002, POLY-726; dodecyl hexafluorophosphate (4-hydroxy-3,5dimethylphenyl) methylsulfonium and similar alkyl analogues other than dodecyl. Tetrahydro-1- (4-hydroxy-3,5-dimethylphenyl) thiophene hexafluorphosphate and tetrahydro-1- (2-hydroxy-3,5-dimethylphenyl) thiophene hexafluorphosphate, as
46/77 disclosed in ACS Polymer Preprints (2002), 43 (2), 918-919;
photoinitiators with the general structure Ar 'S + CH ₃ (C12H25) SbF ₆ , where Ar' is phenacyl (1), 2-indanonyl (II), 4 methoxyphenacyl (III), 2-naphthylmethyl (IV), 1-antroylmethyl ( V) or 1-pyrenoylmethyl (VI), as revealed in J Polymr
Sci, Part A (2000), 38 (9), 1433-1442; Triarylsulfonium Ar ₃ S + MXn salts with metal complex halide anions, such as BF ₄ ', AsF ₆ , PF ₆ and SbF ₆ , as revealed in J Polymr Sei, Part A (1996), 34 (16) , 32313253; dialkylphenacylsulfonium and dialkyl (4hydroxyphenyl) sulfonium salts, as disclosed in
as described in J. Polymr. Sci., Polymr Chem Edition (1979), 17 (4), 977-99; aromatic sulfonium salts, for example with PF6- anion, for example, UVI6970, as disclosed in JP 2000239648; and any combination thereof.
Suitable cationic photoinitiators of the pyridinium type include, for example, Netoxy-2-methylpyridinium hexafluorphosphate (EMP + PF6-), as disclosed in Turkish J Chemistry (1993), 17 (1), 44-49; charge transfer complexes of pyridinium salts and aromatic electron donors (hexamethyl-benzene and 1,2,4-trimethoxybenzene), as revealed in Polymer (1994), 35 (11),
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2428-31, hexafluorophosphate of N, ^{N'-4,4-diethoxy-1-azobis} (pyridinium) (DEAP), as disclosed in Macromolecular Rapid Comm (2008), 29 (11) 892-896; and any combination of these.
Other suitable cationic photoinitiators include, for example, acylgermanium-based photoinitiator, in the presence of onium salts, for example, benzoyltrimethylgerman (BTG) and onium salts, such as diphenyl-iodonium hexafluorphosphate (Ph2I + PF6-) or N-hexafluorphosphate -ethoxy-2-methyl pyridinium (EMP + PF6), as disclosed in Macromolecules (2008), 41 (18) 67146718; Di-Ph diselenide (DPDS), as disclosed in Macromolecular Symposia (2006), 240, 186-193; N-phenacyl-N, N-dimethyl-anilinium hexafluorantimonate (PDA + SbF ₆ -), as disclosed in Macromol Rapid Comm. (2002), 23 (9), 567-570; synergistic mixtures of: diaryliodonium hexafluor-antimonate (IA) with tetracis (pentafluorfenyl) tolylcumyl-iodonium borate (IB), and cumenocyclopentadienylfer (II) hexafluorophosphate with IA and IB, as revealed in Designated Monomers and Polymers (2007), 10 (4), 327-345; diazonium salts, for example, 4 (hexyloxy) -diazonium salts substituted with complex anions, as revealed in ACS Symp Series (2003), 847, 202-212; 5-arylthiantrene salts, as disclosed in J Poly Sei., Part A (2002), 40 (20), 3465-3480; and any combination of these.
Other suitable cationic photoinitiators include, for example, triarylsulfonium salts, such as, triarylsulfonium borates modified by long wavelength UV absorption. Illustrative examples of such
48/77 modified borates include, for example, SP-300 available from Denka, tri (4- (4acetylphenyl) thiophenyl) sulfonium (GSID4480-1) tetracis (pentafluorfenyl) available from Ciba / BASF, and those photoinitiators disclosed in W01999028295 ; W02004029037; W02009057600; US6368769 W02009047105; W02009047151; W02009047152; US 20090208872; and US7611817.
Preferred cationic photoinitiators include a mixture of: bi [4diphenylsulfonophenyl] bihexafluorantimonate sulfide; thiophenoxyphenylsulfonium hexafluorantimonate (available as Chivacure 1176 from Chitec); tri (4- (4acetylphenyl) thiophenyl) sulfonium tetracis (pentafluorfenyl) borate (GSID4480-1 available from Ciba / BASF), tri (4- (4acetylphenyl) thiophenyl) sulfonium, iodonium, [4- (1methylethi1) phenyl] hexafluorantimonate (4-methylphenyl1) - ________________ tetracis (pentafluorfenyl) borate, (available as Rhodorsil 2074 from Rhodia), 4- [4- (2-chlorobenzoyl) phenylthio] phenyl bi (4-fluorphenyl) sulfonium (such as SP-172) and SP -300 (both available at Adeka).
The radiation-curable liquid resin can include any suitable amount of the cationic photoinitiator, for example, in certain embodiments, in an amount of up to about 20% by weight of the composition, in other embodiments from about 0.5% to about 10% by weight of the composition, and in another embodiment from about 1 to about 5% by weight of the composition. In one embodiment, the above ranges are particularly suitable for use with epoxy monomers.
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According to an embodiment of the invention, the components comprising at least one component polymerizable by free radicals, i.e., a component that passes through components polymerizable by free radicals are monomers, oligomers, and / or polymers, which are monofunctional or polyfunctional materials, i.e. yes, they have 1, 2,
3, 4, 5, 6, 7, 8, 9, 10, 20, 30, 40,
50,
100, or more functional groups that can polymerize with free radicals, aromatics (s), polyfunctional materials include dendritic polymers, such as, dendritic polymers, linear dendritic polymers ~ hyper-fused polymers, star-branched polymers and hyper-graft polymers; see US 2009/0093564 A1. Dendritic polymers can contain one type of polymerizable functional group or different types of methacrylate functional groups.
Examples of free radical polymerizable components include acrylates and methacrylates, such as, isobornyl (meth) acrylate, bornyl (meth) acrylate, tricyclodecanyl (meth) acrylate, dicyclopentanyl (meth) acrylate, (dicyclopentenyl methilate), (meth) cyclohexyl acrylate, (meth) benzyl acrylate, (meth) 4-butylcyclohexyl acrylate, acryloyl morpholine, (meth) acrylic acid, (meth) 2-hydroxyethyl acrylate,
50/77 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, (meth) methyl acrylate, (meth) ethyl acrylate, (meth) propyl acrylate, (meth) isopropyl acrylate, (meth) butyl acrylate, (meth) amyl acrylate, (meth) isobutyl acrylate, (meth) tbutyl acrylate, (meth) acrylate (meth) acrylate (meth) acrylate (meth) pentyl, isoamyl, heptyl acrylate, of isooctyl,
(met) acrylate in nonila, (met) acrylate in isodecyl, (met) acrylate in undecila, (met) acrylate stearyl,
(meth) caprolactone acrylate, (meth) hexyl acrylate, (meth) octyl acrylate, (meth) 2-ethylhexyl acrylate, (meth) decyl acrylate, (meth) tridecyl acrylate, (meth) acrylate lauryl, isostearyl (meth) acrylate, tetrahydrofurfuryl, (butoxyethyl) methilate, (et) ethoxydiethylene glycol acrylate, (meth) benzyl acrylate, (meth) acrylate
(meth) polyethylene mono glycol acrylate, (meth) mono olipropylene acrylate, (meth) methoxyethylene glycol acrylate, (meth) ethoxyethyl acrylate, (meth) methoxypolyethylene glycol acrylate, (meth) methoxy polypropylene glycol acrylate, (meth) ) diacetone acrylamide, (meth) beta-carboxyethyl acrylate, (meth) phthalic acid acrylate, (meth) dimethylaminoethyl acrylate, (meth) diethylaminoethyl acrylate, (meth) butylcarbamethyl acrylate, (meth) n-acrylamide isopropyl, fluorinated (meth) acrylate, 7-amino-3,7-dimethyloctyl (meth) acrylate.
Examples of components polymerizable by polyfunctional free radicals include those with (meth) acryloyl groups, such as trimethylolpropane tri (meth) acrylate, pentaerythritol (meth) acrylate,
51/77 ethylene glycol di (met) acrylate, diglycidyl ether di (meth) acrylate, dicyclopentadiene di (meth) acrylate dimethanol, [2- [1, l-dimethyl-2 [(1-oxoalyl acrylate) ) oxy] ethyl] -5-ethyl-1,3-dioxan-5-yl] methyl;
3,9-bi (1,1-l-dimethyl-2-hydroxyethyl) di (meth) acrylate 2,4,8,10-tetraoxaspiro [5.5] undecane, dipentaerythritol monohydroxy (meth) acrylate, tri (meth) acrylate of propoxylated trimethylolpropane, neopentyl propoxylated glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, di (meth) acrylate
1,4-butanediol, di (meth) acrylate
1,6-hexanediol, neopentyl glycol di (meth) acrylate, polybutanediol di (meth) acrylate, tripropylene glycol di (meth) acrylate, glycerol tri (meth) acrylate, mono and phosphoric acid di (meth) acrylates , C ₇ -C ₂ o alkyl di (meth) acrylates, pentaerythritol tri (meth) acrylate di (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate , di (dimethyl) tricyclodecane di (meth) acrylate and alkoxylated versions (for example, ethoxylated and / or propoxylated) of any of the preceding monomers and also di (meth) acrylate of a diol which is an ethylene oxide or propylene oxide adduct for bisphenol A, diol di (meth) acrylate which is an ethylene oxide or propylene oxide adduct for hydrogenated bisphenol A, epoxy (meth) acrylate which is a (meth) acrylate adduct for diglycidyl ether, diacrylate ether polybisphenol A polyoxyalkylated and triethylene glycol divinyl ether and hydroxyethyl acrylate adducts.
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According to one embodiment, the polyfunctional (meth) acrylates of the polyfunctional component can include all methacryloyl groups, all acryloyl groups, or any combination of methacryloyl and acryloyl groups. In one embodiment, the free radical polymerizable component is selected from the group consisting of diglycidyl bisphenol A ether (meth) acrylate; bisphenol A ethoxylated or propoxylated di (meth) acrylate or bisphenol F, dicyclopentadiene di (meth) acrylate dimethanol, [2- [1,1dimethyl-2 - [(1-oxoalyl) oxy] ethyl] -5-ethyl acrylate -l, 3-dioxan-5yl] methyl, monohydroxy dipentaerythritol (meth) acrylate, dipentaerythritol hexa (meth) acrylate, propoxylated tri (meth) acrylate propane acrylate and propoxylated di (meth) acrylate and any combination thereof .
In another embodiment, the free radical polymerizable component is selected from the group consisting of diglycidyl bisphenol A ether diacrylate; dicyclopentadiene diacrylate dimethanol, [2- [1,1-l-dimethyl-2 [(1-oxoalyl) oxy] ethyl] -5-ethyl-1,3-dioxan-5-yl] methyl acrylate, dipentaerythritol monohydroxy pentaacrylate, triacrylate propoxylated trimethylolpropane and propoxylated neopentyl glycol diacrylate and any combination thereof.
In specific embodiments, the photocurable resin compositions for the manufacture of additives of the invention include one or more of diglycidyl bisphenol A ether di (meth) acrylates, dicyclopentadiene di (meth) acrylate dimethanol, dipentaerythritol monohydroxy (meth) acrylate, tri ( met) propoxylated trimethylolpropane acrylate and / or neopentyl glycol di (meth) crylate
53/77 propoxylated, and more specifically one or more among diglycidyl bisphenol A ether diacrylate, dimethanol dicyclopentadiene diacrylate, dipentaerythritol monohydroxy dipentaacrylate, propoxylated trimethylolpropane triacrylate and / or glycated neopentyl propylate diacrylate.
The liquid radiation curable resin can include any suitable amount of the free radial polymerizable component, for example, in certain embodiments, in an amount of up to about 60% by weight of the composition, in certain embodiments, up to about 50% by weight composition. In additional embodiments of about 15% to about 50% by weight of the composition, in other embodiments of about 15 to about 40% by weight of the composition.
____Radiation-curable liquid resin — can_include a free radical photoinitiator. Typically, free radical photoinitiators are divided into those that form radicals by cleavage, known as Norrish Type I and those that form radicals by hydrogen abstraction, known as Norrish Type II. Norrish Type II photoinitiators require a hydrogen donor, which serves as the source of free radicals. Since the onset is based on a bimolecular reaction, Norrish Type II photoinitiators are generally slower than Norrish Type I photoinitiators which are based on the unimolecular formation of radicals. On the other hand, Norrish Type II photoinitiators have better optical absorption properties in the spectroscopic region near UV. The photolysis of aromatic ketones, such as,
54/77 benzophenone, thioxanthones, benzyl and quinones, in the presence of hydrogen donors, such as alcohols, amines or thiols, lead to the formation of a radical produced from a carbonyl compound (radical of the cetyl type) and other radical derivatives from the donor of hydrogen. The photopolymerization of vinyl monomers is usually initiated by the radicals produced from the hydrogen donor. Cetyl radicals are generally not reactive towards vinyl monomers, due to the steric impediment and displacement of an unpaired electron.
In order to successfully formulate a liquid curable resin composition useful for the claimed process, it is necessary to review the wavelength sensitivity of the photoinitiator (s) present in the composition to determine whether they will be activated by the
According to one embodiment, the radiation-curable liquid resin includes at least one free radical photoinitiator, for example, those selected from the group consisting of: benzoylphosphine oxides, aryl ketones, benzophenons, hydroxylated ketones, 1-hydroxyphenyl ketones, ketones, metallocenes and combinations thereof.
In one embodiment, the radiation-curable liquid resin includes at least one free radical photoinitiator selected from the group consisting of: 2,4,6-trimethylbenzoyl diphenylphosphine, and 2,4,6-trimethylbenzoyl phenyl, ethoxy phosphine oxide, oxide bi (2,4,6-trimethylbenzoyl) -phenylphosphine, 2-methyl-1- [4 (methylthio) phenyl] -2-morpholinopropanone-1,2-benzyl-2 (dimethylamino) -1- [4- (4-morpholinyl ) phenyl] -1-butanone, 255/77 dimethylamino-2- (4-methylbenzyl) -1- (4-morpholin-4-yl-phenyl) butan-l-one, 4-benzoyl-4'-methyl sulfide biphenyl, 4,4'bi (diethylamino) benzophenone, and 4,4'-bi (N, N ¹ -dimethylamino) benzophenone (Michler's ketone), benzophenone, 4-methyl benzophenone, 2,4,6-trimethyl benzophenone, dimethoxybenzophenone, 1-hydroxycyclohexyl phenyl ketone, (1hydroxyisopropyl) phenyl ketone, 2-hydroxy-1- [4- (2hydroxyethoxy) phenyl] -2-methyl-l-propanone, 4-isopropylphenyl (1-hydroxyisopropyl) ketone, oligo- [ 2-hydroxy-2-methyl-1- [4 (1-methylvinyl) phenyl] propanone], camphorquinone, 4,4'bi (diethylamino) benzophenon a, benzyl dimethyl ketal, bi (eta 5-2-4-cyclopentadien-1-yl) bi [2,6-difluoro-3- (ΙΗ-pyrrol-1yl) phenyl] titanium and a combination thereof.
For LED light sources emitting in the 300-475 nm wavelength range, especially those emitting at 3 65 nm, 390 nm, or 3 95 nm, examples of suitable free radical photoinitiators absorbing in this area include: benzoylphosphine oxides , such as, for example, 2,4,6-trimethylbenzoyl diphenylphosphine oxide (Lucirin TPO from BASF) and 2,4,6-trimethylbenzoyl phenyl, ethoxy phosphine oxide (Lucirin TPO-L from BASF), bi ( 2,4,6-trimethylbenzoyl) -phenylphosphine (Irgacure 819 or BAPO da Ciba), 2-methyl-l- [4- (methylthio) phenyl] -2morpholinopropanone-1 (Irgacure 907 from Ciba), 2-benzyl-2 ( dimethylamino) -1- [4- (4-morpholinyl) phenyl] -1-butanone (Irgacure 369 da Ciba), 2-dimethyl amino-2- (4-methyl-benzyl) 1- (4-morpholin-4-yl -phenyl) -butan-l-one (Irgacure 379 from Ciba), 4-benzoyl-4 ^1- methyl diphenyl sulfide (Chitacure BMS from Chitec), 4,4'-bi (diethylamino) benzophenone (Chivacure EMK from Chitec) , and 4,4'-bi (N, N'-dimethylamino) benzophenone
56/77 (Michler ketone). Their mixtures are also appropriate.
together with photoinitiators in curing with LED light sources that emit in this wavelength range. Examples of suitable photosensitizers include: anthraquinones, such as 2-methylanthraquinone,
2 ethylanthraquinone, t-butylanthraquinone,
1chloroanthraquinone, and 2-amylanthraquinone, thioxanthones xanthones, such as isopropyl thioxanthone,
2c1orot ioxanthone,
2,4-diethylthioxanthone l-chloro-4propoxythoxanthone, methyl benzoyl formate (Darocur MBF de Ciba), methyl benzoate methyl-2-benzoyl (Chivacure
Chitec OMB), 4-benzoyl-4'-methyl diphenyl sulfide (Chivacure BMS de
Chitec),
4,4'-bi (diethylamino) benzophenone (Chivacure EMK de
Chitec).
It is possible that UV LED light sources are designed to emit light at shorter wavelengths. For LED light sources emitting a wave between about 100 and about 300 using a photosensitizer with nm lengths, a photoinitiator is desirable.
When photosensitizers, such as those previously listed are present in the formulation, other absorption photoinitiators at shorter wavelengths can be used. Examples of such photoinitiators include: benzophenones, such as, benzophenone, 4-methyl benzophenone, 2,4,6-trimethyl benzophenone, and dimethoxybenzophenone, and 1-hydroxyphenyl ketones, such as 1-hydroxycyclohexyl phenyl ketone, phenyl (1hydroxyisopropyl) ketone ,
2-hydroxy-1- [4- (257/77 hydroxyethoxy) phenyl] -2-methyl-1-propanone and 4isopropylphenyl (1-hydroxyisopropyl) ketone, benzyl dimethyl ketal, and oligo- [2-hydroxy-2-methyl- 1- [4- (1-methylvinyl) phenyl] propanone] (Esacure KIP 150 by Lamberti).
LED light sources can also be designed to emit visible light. For LED light sources emitting light at wavelengths from about 4 75 nm to about 900 nm, examples of suitable photoinitiators include: camphorquinone, 4.4 ^1- bi (diethylamino) benzophenone (Chivacure EMK de Chitec), 4, 4'-bi (N, N'-dimethylamino) benzophenone (Michler's ketone), bi (2,4,6-trimethylbenzoyl) phenylphosphine oxide (Irgacure 819 or BAPO da Ciba), metallocenes, such as, bi (eta 5 -2-4-cyclopentadien-l-yl) bi [2,6difluoro-3- (lH-pyrrol-l-yl) phenyl] titanium (Iribaacure 784 from Ciba), and visible light photoinitiators from Spectra Group Limited, Inc such as, H-Nu 470, H-Nu-535, H-Nu-635, HNu-Blue-640, and H-Nu-Blue-660.
In an embodiment of the claimed invention, the light emitted by the LED is UVA radiation, which is radiation with a wavelength between about 320 and about 400 nm. In an embodiment of the claimed invention, the light emitted by the LED is UVB radiation, which is radiation with a wavelength between about 280 and about 320 nm. In one embodiment of the instant invention claimed, the light emitted by the LED is UVC radiation, which is radiation with a wavelength between about 100 and about 280 nm.
The embodiments of the invention include up to about 0.5% by weight of a free radical photoinitiator with properties that slow the cure of the cationic resin. The
58/77 inventors have surprisingly found that the incorporation of up to about 0.5% by weight of such a component can delay the curing of the radiation-curable liquid cationic resin enough to allow the improvement of the substrate flaking. Generally, free radical photoinitiators that delay cationic curing are not used in radiation-curable liquid hybrid resins since rapid cationic curing is desirable. A specifically preferred example of such a free radical photoinitiator is bi (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (Irgacure 819 or BAPO da Ciba). In one embodiment, the free radical photoinitiator that partially inhibits cure is present in an amount of about 0.05 to about 0.25% by weight.
The radiation-curable liquid resin can include any suitable amount of the free radical initiator, for example, in certain embodiments, in an amount of up to about 15% by weight of the composition, in certain embodiments of up to about 10% by weight of the composition , and in other embodiments from about 2% to about 8%, by weight of the composition.
According to one embodiment, the radiation curable liquid resin composition may further include a chain transfer agent, particularly a chain transfer agent for a cationic monomer. The chain transfer agent has a functional group containing active hydrogen. Examples of the active hydrogen-containing active group include an amino group, an amide group, a hydroxyl group, a sulfo group and a thiol group. In one embodiment, the transfer agent
59/77 chain ends the propagation of one type of polymerization, that is, both cationic and free radical polymerization, and initiates a different type of polymerization, that is, both free radical and cationic polymerization. According to one embodiment, chain transfer to a different monomer is a preferred mechanism. In the embodiments, chain transfer tends to produce branched or cross-linked molecules. Thus, chain transfer offers a way to control the molecular weight distribution, crosslink density, thermal properties and / or mechanical properties of the cured resin composition.
Any suitable chain transfer agent can be employed. For example, the chain transfer agent for a cationic polymerizable component is a hydroxyl-containing compound, such as a compound containing 2 or more than 2 hydroxyl groups. In one embodiment, the chain transfer agent is selected from the group consisting of a polyether polyol, polyester polyol, polycarbonate polyol, ethoxylated or propoxylated aliphatic or aromatic compounds having hydroxyl groups, dendritic polyols, hyper-molten polyols. An example of a polyether polyol is a polyether polyol comprising an alkoxy ether group of the formula [(CH ₂ ) _n O] mz θπι which n can be 1 to 6 and M can be 1 to 100.
A specific example of a chain transfer agent is polytetrahydrofuran, such as TERATHANE ™.
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The radiation curable liquid resin composition can include any suitable amount of the chain transfer agent, for example, in certain embodiments, in an amount of up to about 50% by weight of the composition, in certain embodiments, of up to about 30 % by weight of the composition, and in certain other embodiments from about 3% to about 20% by weight of the composition, in other embodiments from about 5 to about 15% by weight.
The radiation-curable liquid resin composition of the present invention may further include one or more additives selected from the group consisting of bubble breakers, antioxidants, surfactants, acid scrubbers, pigments, dyes, thickeners, flame retardants, silane coupling, core-coating particle impact absorbers, soluble polymers and block polymers, organic, inorganic, organic-inorganic hybrid fibers with dimensions ranging from 8 nanometers to about 50 microns.
Stabilizers are often added to the compositions in order to prevent viscosity formation, for example, viscosity formation during use in a solid imaging process. In one embodiment, the stabilizers include those described in US Patent No. 5,665,792, the full disclosure of which is incorporated herein by reference.
Stabilizers of this type are usually hydrocarbon carboxylic acid salts of the metal group
IA and IIA.
In other modalities, these salts are sodium bicarbonate,
61/77 potassium bicarbonate and rubidium carbonate. Rubidium carbonate is preferred for formulations of this invention with recommended amounts ranging from 0.0015-0.005% by weight of the composition. Alternative stabilizers include polyvinylpyrrolidones and polyacrylonitriles. Other possible additives include dyes, pigments, fillers (for example, silica particles, preferably cylindrical or spherical, talc, powdered glass, alumina, alumina hydrate, magnesium oxide, magnesium hydroxide, barium sulfate, sulfate calcium, calcium carbonate, magnesium carbonate, mineral silicate, diatomaceous earth, sandy silica, silica powder, titanium oxide, aluminum powder, bronze powder, zinc powder, copper powder, lead powder, gold, silver powder, glass fibers, titanic acid, potassium whisker, carbon whisker, sapphire whisker, beryllium _, ___ carbide io whisker, silicon nitride whisker, glass microspheres, hollow glass microspheres, metalloxides and whisker potassium titanate) , antioxidants, wetting agents, photosensitizers for the free radical photoiniciator, chain transfer agents, leveling agents, defoaming agents, surfactants and the like.
According to a curable modality for the polymerizable components, such that the desired photosensitivity is obtained, choosing an appropriate ratio of the initiators and / or polymerizable components. The ratio of components and initiators affects photosensitivity, cure speed, degree of cure, crosslink density,
62/77 thermal properties (for example, _Tg ), and / or mechanical properties (for example, tensile strength, storage module, loss module) of the radiation-curable liquid resin composition or cured article.
Therefore, in one embodiment, the weight ratio of the cationic photoinitiator to the free radical photoinitiator (CPI / RPI) is about 0.1 to about 2.0, preferably between about 0.1 to about 1.0, and more preferably from about 0.2 to about 0.8.
According to one embodiment, the radiation curable liquid resin composition has a weight ratio of the cationic polymerizable component to free radical polymerizable component (CPC / RPC) from about 0.8 to about 4.5, from , about 1.0 to about 4.0, and more preferably about 1.0 to about 3.5.
The fourth aspect of the claimed invention is a three-dimensional object manufactured using the method of the first aspect of the claimed invention.
The third aspect of the claimed invention is a method of forming a three-dimensional object comprising:
1) coating a layer of radiation curable liquid resin comprising 30 to 80% by weight, more preferably from 35 to 80% by weight, more preferably from 35 to 75% by weight, more preferably from 35 to 70% by weight of at least one cationically curable compound on a substrate;
2) contact of the radiation curable liquid resin layer with a previously cured layer;
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3) selective exposure of the radiation curable liquid resin layer to actinic radiation provided by an actinic radiation source, thus forming a cured layer that adheres to the previously cured layer;
4) separation of the cured layer and the substrate; and
5) repetition of steps 1 to 4 a sufficient number of times in order to construct a three-dimensional object;
where the shear modulus in storage is measured when reaching a higher value (G ¹ )
7.5 x 10 ⁵ Pa, preferably higher
8.5
10 ⁵
Pa, more preferably greater than
9.5 x 10 ⁵
Pa in 2 seconds at light, when the shear module in storage of the curable liquid resin for at a
Mechanical Analyzer
Dynamic of
Real time according to the radiation-curable liquid resin is cured with a light intensity of 50 mW / cm ² for a light exposure time of 1 second.
The fourth aspect of the claimed invention is a three-dimensional object manufactured using the method of the third aspect of the claimed invention.
The following examples further illustrate illustrative modalities of the invention, however, obviously, they should not be interpreted as limiting the scope of the invention.
Examples
Dynamic Mechanical Analysis in Real Time (RT-DMA)
The real-time dynamic-mechanical analysis (RT-DMA), including the shear modulus (G ') in storage is performed under laboratory conditions (20-23 ° C and
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25-35¾ relative humidity), in compositions undergoing curing and employing a StressTech Rheometer (Reologicia Instruments AB, Sweden) with an 8 mm plate, a 0.1 mm gap, and modified to include a light bulb source. mercury (OMNICURE 2000 Series available from EXFO), equipped with a 365 nm interference filter (also available from EXFO) placed in the light path and a liquid-filled light guide for transmitting light from the source to the rheometer. The 365 nm interference filter produces the spectral output shown in figure 1. The samples are evaluated under the following parameters: 10 s of equilibration time, 10 Hz frequency, 50 mW / cm ² of light intensity by the IL 1400 radiometer with XRL140B detector (International Light, Newburyport, MA); 1 second exposure that starts in 2 seconds from the beginning of data collection; Smoothing FFT of curves; G ¹ taken in 2.5, 2.7, 3, 4 and 6 seconds, from the beginning of the data collection using the monitoring software for data analysis.
Figure 2 shows a schematic diagram of the RT-DMA apparatus. The liquid radiation-curable resin (1) is placed on a plate (2). The amount of liquid resin used should be approximately the amount shown in the figure. The plan is a quartz plate that is sold with the StressTech Rheometer. The 8 mm plate (3) is positioned with a 0.1 mm gap (4) between the plate and the plane. The interval is adjusted using the software that comes with the StressTech Rheometer. Light (5) is provided on the plane (2). See Robert W. Johnson's Dynamic Mechanical Analysis of UV-Curable Coatings While Curing
65/77 available at http://reologicainstruments.com/PDF%20files/BobJohnsonUVpa per.pdf. and incorporated into this document as a reference, in its entirety for more information regarding the RT-DMA.
Separation Time Tester
A tester, as shown in figure 3, is used to measure the separation time. The test apparatus comprises a reciprocating transport (18) of four rollers (19, 19 ', 19 and 19') and a 365 nm LED light (32). The LED light corresponds to Nichia Co.'s Model NCSU033A with a focused 1mm spot light projected onto the resin surface. A flexible sheet substrate, transparent to radiation (6) made of 100 micron thick TPX is positioned on the device and placed as instructed. An elevator (14) is stationary in the x and y directions and mobile in the z direction. The system comprises an advance application roller (19 ') and a drag application roller (19) for application of a layer of radiation-curable liquid resin (10). The application rollers are grooved cylinders (Meyer bars) capable of applying a substantially uniform layer of liquid radiation-curable resin (10) on the substrate (6). The system also comprises an advance guide roller (19) and a drag guide roller (19 '). The guide rollers propel the substrate (6) in and out of the appropriate position, thereby separating the freshly cured layer (10 ') from the substrate.
When the device moves in a first direction (73), the feed application roller (19 ') applies
66/77 a substantially uniform layer of liquid radiation-curable resin (10) on the substrate (6). The radiation-curable liquid resin on the substrate is then driven to contact a previously cured layer (14) or the construction surface of the elevator. The LED (32) then passes under the part (5), curing the radiation curable liquid resin (10), thus creating a recently cured layer (10 ') of radiation curable liquid resin. The drag guide roller (19 ') then acts to strip the substrate of the newly cured layer of radiation curable liquid resin, moving the substrate (6) out of the newly cured layer (10 ¹ ) that adhered to the previously cured layer (14 ). The elevator (14) then moves upstream, by the thickness of a layer, typically 50 microns. The transport direction is then i:
and —the process is repeated.
The speed of the reciprocating transport is adjustable. The linear distance from the light source to the center of the trailing peeling roller is 5.5 cm. Guide rollers (19 'and 19) are 1 cm in diameter. Therefore, a construction time of 10 mm / s is equivalent to a separation time of five and a half seconds
Examples 1-18 and Comparative Examples 1 and 2
Several radiation curable liquid resins have been tested according to the invention. Information related to the components of liquid radiation curable resins can be obtained in Table 1. The compositions, properly, can be obtained in Table 2, Table 3 and Table 4. The quantity of each component is listed as
67/77 percentage by weight of the total composition. Examples are referred to as Ex., While comparative examples, which are not considered as examples of the invention, are designated as (Comp.).
TABLE 1
Commercial name Function in Formula Chemical Description Provider CD 406 Free radical polymerizable component Cyclohexyl diacrylate Sartomer Celloxide2021P Polymerizable cationic component Epoxycyclohexylmethyl-3 ', 4'epoxycyclohexane Daicel chemical Chivacure BMS Photosensitizer 4-Benzoyl-4'methyldiphenyl thioether Chitec DG-0049 Pigment Violet pigment in monomer Desotech DPHA Component Hexaacrylate Sigmafree radical polymerisation dipentaerythritol Aldrich Ebecryl3700 Polymerizable cationic component Bisphenol ether diacrylateDiglycidyl Cytec EpoleadPB3600 Polymerizable cationic component 1,3-Butadiene, homopolymer, epoxized, cyclized DaicelChemical Eponox 1510 Polymerizable cationic component Hydrogenated diglycidyl bisphenol A ether Hexion lrgacure184 Free radical photoinitiator α-Hydroxycyclohexyl phenyl ketone BASF lrgacure819 Free radical photoinitiator Bi (2,4,6-trimethylbenzoyl) phenylphosphine oxide BASF lrgacure PAG 290 Cationic photoinitiator Tetracis(pentafluorfenil) tri (4- (4acetylphenyl) thiophenyl) sulfonium borate BBASF Longnox 10 Ant i ox i dant e Neopentanotetrail 3,5-di-tbutil-4hydroxyhydrocinamate Longchem C&S Int.
68/77
NK Ester1 A-DOG Free radical polymerizable component [2- [1,1dimethyl-2 - [(1oxoalyl) oxy] ethyl] -5-ethyl1,3dioxan-5-yl] methyl acrylate Kowa OXT-101 Polymerizable cationic component 3-Ethyl-3-(hydroxymethyl i1) oxetane Toagosei PVP Acid scrubber Polyvinyl pyrrolidone Sigma Aldrich RhodorsilPI 2074 Cationic photoinitiator Tetracis(pentafluorfenil) 4-isopropylphenyl borate) (4methylphenyl) iodonium RRhodia Rubidium Carbonate Acid scrubber Rubidium carbonate Sigma Aldrich SR399J Free radical cationic component Dipentaerythritol monohydroxy pentaacrylate Sartomer Terathane1000 Chain transfer agent poly THF polyol Invest
TABLE 2
Ex. 1 Ex.2 Ex. 3 Ex. 4 Ex.5 Ex. 6 Ex. 7 IrgacurePAG 290 RhodorsilPI 2074 2.00 2.00 2.00 2.00 2.00 2.00 2.00 IR-184 3.00 3.00 4.30 3.80 3.80 3.80 3.80 Irgacure819 0.10 ChivacureBMS 2.00 2.00 1.50 2.00 2.00 2.00 2.00 Rubidium carbonate 0.01 CD 406 7.00 7.00
69/77
SR399J 10.00 8.00 9.87 9.97 DPHA 19.28 19.94 NK Ester 8.10 A-DOG EB3700 25.00 25.00 35.007.58 20.63 21.98 Celloxide 36.00 40.07 40.37 3 37.27 38.54 45.46 42.06 2021P Terathane 25.00 20.93 9.00 17.35 17.94 8.80 8.14 1000 OXT-101 7.11 7.24 6.70 Longnox 10 0.10 0.20 0.20 0.20 0.20 PVP0.01 0.02 DG-0049 0.50 Epon 1510 Epolead 3.16 PB3600 Total 100.01 100.00 100.00 100.00 100.0 100.0 100.0
TABLE 3
Ex. 8 Ex. 9 Ex. 10 Ex. 11 Ex. 12 Ex. 13 Ex. 14 Irgacure 1.41 0.98 1.93 1.00 PAG 290 Rhodorsil 2.00 2.00 2.00 PI 2074 IR-184 3.80 3.80 3.80 6.00 6.00 6.00 6.00
ΊΖ / ΊΊ
Irgacure819 Chivacure 2.00 2.00 2.00 BMS Carbonate rubidium CD 406 SR399J DPHA 14.00 9.03 9.82 6.59 7.02 6.07 4.00 NK Ester 20.06 20.00 20.00 20.00 20.00 20.00 20.00 A-DOG EB3700 Celloxide 45.00 45.00 45.00 45.84 45.84 45.84 45.84 2021P Terathane 12.94 9, 93 17.18 10.19 10.19 10.19 13.19 1000 OXT-101 0.00 8.049.17 9.17 9.17 9.17 Longnox 10 0.20 0.20 0.20 0.50 0.50 0.50 0.50 PVP 0.01 0.01 0.01 0.01 DG-0049 0.30 0.30 0.30 0.30 Epon 1510 Epolead 0.00 0.00PB3600 Total 100.0 100.0 100.0 100.0 100.0 100.0 100.0
71/77
TABLE 4
Ex. 15 Ex. 16 Ex. 17 Ex. 18 Comp. 1 Comp. 2 Irgacure PAG 290 0.75 0.55 1.00 1.50 Rhodorsil PI 2074 2.00 2.00 IR-184 6.00 6.00 6.00 6.00 6.00 3.80 Irgacure 819 Chivacure BMS 1.00 2.00 Carbonaterubidium CD 4 06SR399J 6.24 5.74 4.94 10.00 DPHA 4.00 4.00 NK Ester A-DOG 20.00 20.00 15.57 15.57 15.57EB370024.70 Celloxide 2021P 45.84 45.84 38.66 Terathane 1000 13.44 13.64 7.49 OXT-101 9.17 9.17 15.70 15.70 15.70 6.16 Longnox 10 0.50 0.50 1.00 1.00 0.50 0.20 PVP 0.01 0.01
72/77
DG-0049 0.30 0.30 0.20 0.20 Epon 1510 54.30 54.30 54.30Epolead5.00 PB3600 Total 100.0 100.0 100.0 100.0 100.0 100.0
The operating speed of the test apparatus described above has been adjusted to 5 mm / s, from a forming speed of 10 mm / s, increased to the fastest possible separation delay time for the hybrid curing resins of the invention , which allows the successful formation of test pieces. The test was carried out at an ambient temperature between 20 and 25 ° C and a humidity between 20 and 40% RH. The LED light (NCSU033A, Nichia) was centered on a 1 mm focus area projected onto the resin surface. The LED light was powered by a 3.65 V / 100 mA direct current output from a Programmable Power Supply (Model number PSS-3203; GW Instek). The TPX Opulent sheet (X-88BMT4; single layer film, both sides matte; 100 micron thick, Mitsui Chemicals America, Inc, was used as substrate. The storage shear module (G ¹ ) was recorded according to the procedure described above The storage shear modulus values are listed in Pa. The fastest permissible separation delay time was determined by dividing the distance from illumination to flaking (55 mm) by the maximum formation speed. are shown in Table 5, Table 6 and Table 7.
TABLE 5
73/77
Example Ex. 1 Ex.2 Ex.3 Ex. 4 Ex.5 Ex.6 Ex.7 G '0.5 s after light on (Pa) 2923 39670 2103 15580 56050 1170 114 G '0.7 s after light on (Pa 77770 322400 112400 250200 420500 19520 26230 G '1.0 s after light on (Pa 440500 1057000 697900 1131000 1720000 336200 278300 G '2.0 s after light on (Pa 1118000 2423000 2109000 3500000 3394000 1378000 957200 G '4.0 s after light on (Pa 939500 3033000 3094000 4675000 5029000 2197000 1465000 Speed information 15 20 20 20 20 10 10 maximum(mm / s) Faster separation delay time(s) 3.7 2.8 2.8 2.8 2.8 5.5 5.5
TABLE 6
Example Ex. 8 Ex. 9 Ex.10 Ex.ll Ex.12 Ex.13 Ex. 14 G '0.5 s after light on (Pa) 11230 1616 2958 7612 18810 14320 9884 G '0.7 s after light on (Pa 194400 140200 83283 248100 195100 203300 123000
74/77
G '1.0 s after light on (Pa 912800 696400 501267 1068000 742500 819600 555100 G '2.0 S after light on (Pa 2809000 2241000 1690333 2781000 1726000 2012000 1400000 G '4.0 s after light on (Pa 3980000 3610000 2208000 3940000 2305000 2802000 1968000 Speed inmaximum formation(mm / s) 15 15 20 20 25 20 30 Faster separation delay time(s) 3.7 3.7 2.8 2.8 2.2 2.8 1.8
TABLE 7
Example Ex. 15 Ex. 16 Ex.17 Ex. 18 Comp. 1 Comp. 2 G '0.5 s afterlight on (Pa) 4732 880 809 2140 449 709 G '0.7 s afterlight on (Pa 124600 131200 44920 33620 21440 3454 G '1.0 s afterlight on (Pa 490700 653500 360000 270900 219400 117600 G '2.0 s afterlight on (Pa 1146000 1780000 1099000 866900 697800 685700 G '4.0 s afterlight on (Pa 1533000 2331000 1565000 1261000 1014000 1178000 Speed inmaximum formation(mm / s) 30 20 20 25 20failed 10 failed
75/77
Faster separation delay time (s) 1.8 2.8 2.8 2.2 AT AT
Discussion of Results
Each of Examples 1-18 is capable of achieving a G 'value greater than 9.0 x 10 ⁵ Pa by the fastest measured separation delay time. Some data interpolation is necessary to determine the G 'in the fastest separation delay time since the G' values were recorded only at the indicated intervals. Comparative Example 1 was included to demonstrate a resin that is unable to form at a speed of 20 mm / s. A forming speed of 20 mm / s is equivalent to a minimum separation delay time of 3 seconds on the Separation Time Tester. Comparative example 1 is unable to achieve a G 'value greater than 9.0 x 10 ⁵ Pa for 2.75 seconds, and fails to form at 20 mm / s. Comparative Example 1 was not tested at a forming speed of less than 20 mm / s. Comparative Example 2 failed to achieve a forming speed of 10 mm / s. The cured layer did not separate sufficiently from the substrate and adhered to the previous layer. The comparative examples are unable to obtain a G 'value of 7.5 x 10 ⁵ Pa in 2 seconds after the light has been turned on in contrast to the examples of the invention which are able to obtain that value.
All references, including publications, patent applications, and patents, cited herein are incorporated into this document as a reference, just as if each reference had been cited
76/77 individually and specifically to be incorporated as a reference and had been established in this document in its entirety.
The use of the terms a, o and one, one and similar references in the context of the description of the invention (especially in the context of the claims that follow) should be interpreted to cover both the singular and the plural, unless otherwise stated in this document or clearly contradicted by the context. The terms comprising, having, including and containing must be interpreted as open terms (that is, meaning including, but not limited to), unless otherwise stated. The citation of the ranges of values in this document is merely intended to serve as an abbreviated method of individual reference to each separate value within that range, unless otherwise indicated in this document and each separate value is incorporated into the descriptive report as if cited individually in this document. All methods described in this document may be performed in any appropriate order, unless otherwise indicated or clearly contradicted by the context. The use of any and all examples, or exemplary language (for example, as) provided herein, is intended merely to better illustrate the invention and does not present a limitation on the scope of the invention, unless otherwise claimed. No language in the specification should be interpreted as indicating any element not claimed as essential to the practice of the invention.
77/77
Preferred embodiments of that invention are described herein, including the best way known to the inventors for carrying out the invention. Variations in preferred embodiments can be made clear to those skilled in the art when reading the preceding description. The inventors expect those skilled in the art to employ such variations as appropriate, and the inventors intend for the invention to be practiced in a manner other than that specifically described herein. Consequently, this invention includes all modifications and equivalents to the matter cited in the appended claims as permitted by applicable law. In addition, any combination of the elements described above in all possible variations is encompassed by the invention, unless otherwise indicated or document.
Although the invention has been described in detail and with reference to the specific modalities thereof, it will be clear to one skilled in the art that various modifications can be made without departing from the spirit and scope of the invention.

权利要求:
Claims (5)
[1]
1) coating a layer of radiation curable liquid resin comprising 35 to 70% by weight of at least one cationically curable compound on a substrate;
1) coating a layer of liquid radiation curable resin comprising 30 to 80% by weight of at least one cationically curable compound on a substrate;
1. Method for forming a three-dimensional object, characterized by the fact that it comprises:
[2]
2) contact of the radiation curable liquid resin layer with a previously cured layer;
2. Method, according to claim 1, characterized by the fact that the shear modulus in storage of the radiation-curable liquid resin is measured at an ambient temperature of 20 to 23 ° C and a relative humidity of 25% to 35% .
2/5
2) contact of the radiation curable liquid resin layer with a previously cured layer;
[3]
3) selective exposure of the radiation-curable liquid resin layer to actinic radiation, provided by an actinic radiation source, thus forming a cured layer that adheres to the previously cured layer;
3/5 mW / cm ² and the actinic radiation source have the same spectral output.
9. Method, according with The claim 1, characterized by the fact that the source of actinic radiation it consists of one or more LEDs. 10. Method, according with The claim 1, characterized by the fact that one or May s LEDs emit light in a length of wave left r from 340 at 400 nm. 11. Method, according with The claim 1, characterized by fact that O delay time in separation does not exceed 15 seconds. 12. Method, according with The claim 1,
characterized by the fact that the radiation-curable liquid resin additionally comprises: from about 0.5 to about 10% by weight of at least one cationic photoinitiator, from 15 to 40% by weight of at least one component free radical polymerisation; and from about 1 to about 10% by weight of at least one free radical photoinitiator.
13. Method according to the claim
12, characterized by the fact that at least one cationic photoinitiator comprises a triaryl sulfonium salt.
14. Method according to claim
13, characterized by the fact that the triaryl sulfonium salt is a tetrakis (pentafluorfenil) triaryl sulfonium borate.
15. Method, according to claim
14, characterized by the fact that triaryl sulfonium tetrakis (pentafluorfenyl) borate is tris (4- (4acetylphenyl) thiophenyl) tetrakis (pentafluorfenyl) borate).
Petition 870190058269, of 06/24/2019, p. 9/11
3. Method, according to claim 1, characterized by the fact that the Dynamic Mechanical Analyzer in Real Time is configured with an 8 mm plate and a sample interval of 0.10 mm.
3) selective exposure of the radiation-curable liquid resin layer to actinic radiation, provided by an actinic radiation source, thus forming a cured layer that adheres to the previously cured layer;
[4]
4) separation of the cured layer and the substrate; and
4/5
16. Method according to claim 1, characterized in that the liquid radiation curable resin comprises more than one free radical photoinitiator.
17. Method according to claim 16, characterized in that a free radical photoinitiator is bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide and is present in an amount less than 0.5 by weight of the resin liquid curable by radiation.
18. Method, according with The claim 1, characterized by fact of whatthe substrate is substantially not elastic. 19. Method, according with The claim 1, characterized by the fact that the substrate is less than 250 microns thick. 20. Method, according with The claim 1,
characterized by the fact that the amount of cationically polymerizable compounds is from about 40% by weight to about 60% by weight.
21. Method according to claim 1, characterized in that a cationically polymerizable component is an epoxidated polybutadiene, present in an amount of about 5% by weight to about 20% by weight.
22. Method according to claim 1, characterized in that the layer of liquid radiation curable resin is about 25 microns to about 250 microns thick.
23. Method, according to claim 1, characterized by the fact that actinic radiation must
Petition 870190058269, of 06/24/2019, p. 11/10
5/5 traverse the substrate to reach the radiation-curable liquid resin.
24. Method for forming a three-dimensional object, characterized by the fact that it comprises:
4. Method according to claim 1, characterized by the fact that the storage shear module of the radiation-cured liquid resin is measured at a frequency of 10 Hz and an equilibrium time of 10 seconds.
5. Method, according to claim 1, characterized by the fact that the cured layer does not adhere to the substrate and adheres to the previously cured layer.
6. Method according to claim 1, characterized by the fact that the radiation-curable liquid resin is able to achieve a shear modulus in storage greater than about 7.5 x 10 ⁵ in 2.0 seconds after exposure the light start when measured on a Dynamic Mechanical Analyzer in Real Time.
7. Method, according to claim 1, characterized by the fact that the light intensity of 50 mW / cm ² has a spectral output with a peak at about 365 nm.
8. Method, according to claim 1, characterized by the fact that the light intensity of 50
Petition 870190058269, of 06/24/2019, p. 11/11
4) allowing a delay time to occur and after completion of the separation delay time, separating the cured layer and the substrate; and
5) repetition of steps 1 to 4 a sufficient number of times in order to construct a three-dimensional object;
where the separation delay time is the time from the first exposure of the radiation curable liquid resin layer to actinic radiation with respect to the time that the storage shear modulus (G ') of the radiation curable liquid resin is measured at achieve a value (G ') greater than 9.0 x 10 ⁵ Pa, as measured from the beginning of exposure to light, when the storage shear modulus (G') of the radiation-curable liquid resin is measured on a Dynamic Mechanical Analyzer of Real Time according to the radiation-curable liquid resin is cured with a light intensity of 50 mW / cm ² for a light exposure time of 1 second.
Petition 870190058269, of 06/24/2019, p. 7/11
[5]
5) repetition of steps 1 to 4 a sufficient number of times in order to construct a three-dimensional object;
where the storage shear modulus (G ') of the liquid radiation curable resin is measured when reaching a value (G') greater than 9.5 x 10 ⁵ Pa, in 2 seconds from the beginning of the exposure to light, when the storage shear modulus (G ') of the radiation-curable liquid resin is measured in a Dynamic Mechanical Analyzer in Real Time as the radiation-curable liquid resin is cured with a light intensity of 50 mW / cm ² for a period of 1 second light exposure.

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法律状态:
2019-04-24| B06T| Formal requirements before examination [chapter 6.20 patent gazette]|

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2019-08-06| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2019-09-10| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 16/12/2010, OBSERVADAS AS CONDICOES LEGAIS. (CO) 20 (VINTE) ANOS CONTADOS A PARTIR DE 16/12/2010, OBSERVADAS AS CONDICOES LEGAIS |

优先权:

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申请号 | 申请日 | 专利标题

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US28762009P| true| 2009-12-17|2009-12-17|

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PCT/US2010/060722|WO2011084578A1|2009-12-17|2010-12-16|Substrate-based additive fabrication process|

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