JP2022070865A - LIQUID HYBRID UV/vis RAY CURABLE RESIN COMPOSITION FOR ADDITION MOLDING - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a liquid radiation curable composition that is suitable for hybrid (specifically, cation and free radical) polymerization when treated by an addition molding device using a source of actinic radiation having a peak spectrum intensity in a UV/vis region, and to provide a method for forming a three-dimensional component by an addition molding process using the source of actinic radiation having a peak spectrum intensity in the UV/vis region, using the liquid radiation curable composition that is suitable for hybrid polymerization, and a component cured by the same.

SOLUTION: A liquid UV/vis ray curable composition for addition molding contains a cationic curable component that enables cationic polymerization and further contains a cyclic aliphatic epoxy component and an oxetane component, a free radical curable component that enables free radical polymerization, and a photoinitiation package further containing a cationic photoinitiator, a vinyl ether diluent monomer and a free radical photoinitiator, and has specific photocurable physical properties.

SELECTED DRAWING: Figure 11

COPYRIGHT: (C)2022,JPO&INPIT

Description

Detailed description of the invention

[Technical field]
The present invention relates to a liquid composition for an addition shaping process that is hybrid curable in the UV or visible spectral range.

[Cross-reference of related applications]
This application claims priority under US Provisional Patent Application No. 62/172489, filed June 8, 2015, which is incorporated by reference in its entirety as if fully specified herein. do.

[background]
[001] Additional modeling processes for manufacturing 3D objects are well known. In the additive modeling process, three-dimensional parts are constructed using computer-aided design (CAD) data of the object. The three-dimensional component can be formed from liquid resin, powder, or other material.

[002] A well-known example of, but not limited to, additive modeling processes is stereolithography (SL). Stereolithography is the process for rapidly manufacturing models, prototypes, patterns, and manufactured parts for a particular application. SL uses CAD data of an object and converts this data into a thin cross-section of a three-dimensional object. By loading the data into a computer, the laser that traces the pattern of the cross section is controlled via the liquid radiation curable resin composition contained in the bat to solidify the thin layer of resin corresponding to the cross section. The solidified layer is recoated with resin and the other cross-sections are traced with a laser to cure the other resin layer on top of the previous layer. This process is repeated layer by layer until the 3D object is completed. At the time of initial formation, the 3D object is generally not completely cured and is called a "green model". Although not required, the green model may be post-cured to improve the mechanical properties of the finished part. Examples of SL processes are described, for example, in US Pat. No. 4,575,330.

[003] Lasers have traditionally functioned as the optimal source of radiation for additive modeling processes such as stereolithography. The use of gas lasers to cure liquid radiation curable resin compositions is well known. The delivery of laser energy in a stereolithography system can be a continuous wave (CW) or a Q-switched pulse. CW lasers provide continuous laser energy and can be used in high speed scanning processes. Historically, several types of lasers have traditionally been used for stereolithography with peak spectral outputs in the wavelength range of 193 nm to 355 nm, but there are others with other wavelengths. The light emitted by the laser is monochromatic. That is, a significant proportion of the total spectral output is in a very narrow wavelength range. Laser-based additive manufacturing systems in the industry have become the predominant ones operating at a peak spectral output of 355 nm.

[004] However, laser-based systems, especially those operating at peak spectral outputs at or near 355 nm, are not without their drawbacks. The significant power output of such a laser-based system can damage the resin as it can generate excessive heat at the point of irradiation. In addition, lasers of any wavelength require point-by-point scanning on the resin surface, requiring a process that can be time consuming, especially if the cross-sectional pattern to be cured is large or complex. Also, 355 nm laser-based systems are expensive and involve high maintenance costs and energy consumption.

[005] In order to eliminate some of the shortcomings associated with laser-based systems, image projection techniques are beginning to be used as chemical sources in other additive modeling systems. An example of this is the liquid crystal display (LCD), a technique well known in other industries such as the manufacture of televisions and computer monitors. Other examples, but not limited to, were developed by Texas Instruments and are referred to as Digital Light Processing (DLP®). The DLP system uses a pixel-equivalent micromirror known as a digital micromirror device (DMD) controlled by and immobilized on a microchip to selectively transmit light from an input source and deliver that light to the desired output. Project with a pattern or mask. DLP technology was developed for use in image projection systems as an alternative display system to LCD-based technology. The particularly good image sharpness, brightness, and uniformity associated with DLP systems are very useful for additive modeling where image resolution and accuracy are important. This is because the boundaries of the three-dimensional object produced by curing are finally defined by the boundaries of the projected light. In addition, image projection systems such as LCDs and DLPs offer theoretical speed advantages in that the entire cross-sectional layer can be exposed and cured simultaneously. Moreover, in that respect, the required cure time in a laser-based system is said to be directly proportional to the complexity of the cross section scanned, whereas the image projection system is cross section independent. That is, the exposure time of a given layer does not change as the shape complexity of any given layer increases. Therefore, it is particularly suitable when the component produced by the additional molding has a complicated and detailed geometry.

[006] DLPs and LCDs provide a way to process the light emitted from an existing light source into a more desirable pattern, rather than an alternative method of producing the light itself. Therefore, a coupled input light source is still needed. The light input to the image projection system can be from any light source, including traditional lamps and even lasers, but more generally the input light is collimated from one or more light emitting diodes (LEDs).

[007] An LED is a semiconductor device that generates light by utilizing an electroluminescence phenomenon. Currently, LED light sources for additive modeling systems generally emit light at wavelengths of 300-475 nm, with typical peak spectral outputs of 365 nm, 375 nm, 395 nm, 401 nm, 405 nm, and 420 nm. For a more detailed discussion of LED light sources, see the textbook "Light-Emitting Diodes", E.I. Fred Schubert, 2nd Edition, (Copyright) E.I. See Fred Schubert 2006, Cambridge University Press. LEDs offer the advantage of operating theoretically near peak efficiency over a longer duration than other light sources. In addition, it is typically more energy efficient and cheaper to maintain, resulting in lower initial and ongoing ownership costs than laser-based optical systems.

[008] Therefore, in various additive modeling systems, the following optical configuration examples, but not limited to, are: (1) laser only, (2) laser / DLP, (3) LED only, (4) LED. / DLP, or (5) one of the LEDs / LCD is used. Systems that do not utilize DLP technology can also incorporate other collimating or focusing lenses / mirrors to selectively direct light onto the liquid resin.

[009] Recently, newer additive modeling systems, regardless of optical configuration, have begun to frequently utilize light sources that emit radiation at wavelengths longer than the traditional 355 nm output. Other systems are shifting towards choosing a light source that emits light with a wider spectral output distribution instead of a monochromatic light source. Therefore, such newer systems incorporating laser / DLP, LED, LED / DLP, or LED / LCD-based optical configurations are more common with longer wavelength peak spectral outputs. It is starting to work with a wider spectral distribution than it was. The wavelength used there is changed to 355 nm and shifted in the direction of the visible spectrum, and some even have a peak spectral output within the visible range. Such longer wavelengths (ie, 375 nm to 500 nm) have traditionally been referred to as "UV / vis".

[010] Some, but not limited to, reasons usually cited for the current increasing use of optics in the UV / vis region are: (1) the cost of light sources operating in the UV / vis range. (Both initial and maintenance costs) are reduced, and UV / vis light sources emit lower energy radiation and everything else than (2) light sources that penetrate deeper into the UV region and emit light. The fact is that if they are equal, they do not cause much damage to human tissue. For this reason, it does less harm during accidental exposure than those that operate deeper into the UV region. As additive manufacturing continues to grow in popularity in the consumer, "prosumer", and industrial market areas, additional modeling systems that utilize lower cost, less dangerous chemical sources to cure liquid photopolymers. The need will become more and more important.

[011] However, the benefits gained from the use of UV / vis light sources / optical systems are not without significant trade-offs. So far, the biggest drawback is the relatively great difficulty associated with developing photopolymers suitable for systems utilizing UV / vis optics. One of the main reasons for this is, in addition to the natural phenomenon that light with longer wavelengths has lower energy, the intensity of commercial light sources typically decreases with increasing wavelength of peak spectral output. .. Therefore, while traditional 355 nm laser-based optical systems can provide an irradiation dose of 1500 W / cm ² to the resin surface, commercial systems operating at about 400 nm are roughly only about 1/1000 of that value. It is known to give an amount to the resin surface. In fact, in existing 365 nm or 405 nm DLP-based commercial additive modeling systems, the dose to the resin surface provided by the UV / vis optics is 0.1 W / cm ² more for some more economical desktop units. May be as low as 0.0002 W / cm ² . Due to such relatively reduced radiation energy / intensity, it becomes more difficult to carry out a photopolymerization reaction of a radiation curable resin by a UV / vis optical element that takes an exposure time unless it is exorbitantly long. This in turn significantly increases component building time, and as a result, eliminates the theoretical speed advantage of photomask display systems. In addition, there are fewer photo-initiated systems, especially cationic light-initiated systems, for promoting photopolymerization at such longer UV / vis wavelengths on the market.

[012] Due to the issues listed above, various options are available for systems that operate deeper into the UV region, such as 355 nm laser-based systems, whereas they operate in the UV / vis region. The number of photopolymers available in modern optical systems is limited.

[013] It is known that there are radically polymerizable resins for systems that utilize UV / vis optical devices. Such resins generally consist of one or more (meth) acrylate compounds (or other free radical polymerizable organic compounds) with a free radical photoinitiator for radical generation. US Pat. No. 5,418,112 describes one such radical curable system. Radical-polymerizable resins will easily cure even under the relatively lower energies and lower intensities provided by UV / vis optics, but may not be suitable for all additive shaping applications. First, (meth) acrylate-based resins, which are considered suitable for addition molding processes, have traditionally produced cured parts with insufficient mechanical properties to be incorporated into many end applications. Therefore, parts are typically manufactured that do not have sufficient robustness for non-prototyping applications. In addition, such resins exhibit deformation problems, such as the production of warped or malformed parts, due to residual strain due to shrinkage differences during curing. This problem is exacerbated by add-on machines with larger platforms. In this case, as the hardened object becomes larger, the warp or poor shape of the part is amplified due to the influence of the cumulative shrinkage difference. These deformation problems can be partially remedied via software that compensates for known shrinkage by modifying the CAD file that produces the solid 3D component. However, software corrections are inadequate to completely compensate for deformation of parts that have intricate and complex shapes or require tight dimensional tolerances over long distances.

[014] Other well-known types of resins suitable for use in additive shaping systems are "hybrid" curable resins, i.e. (1) epoxys, oxetane, or other types of cationically polymerizable compounds, and (1) It contains one or more cationic photoinitiators, (3) acrylate resins or other types of free radical polymerizable compounds, and (4) one or more free radical photoinitiators. Examples of such hybrid curable systems are described, for example, in US Pat. No. 5,434,196. It has long been known that such resins have superior mechanical properties as compared to all-acrylate resins and result in cured parts manufactured by the addition molding process. In addition, hybrid curable systems are superior to all-acrylate systems in that they are less susceptible to the shrinkage difference problem that has long been a problem with all-acrylate systems.

[015] However, since the ring-opening process of cationic polymerization is generally slower and requires more activation energy than free radical polymerization, proper curing or three-dimensional objects of such formulations for addition shaping applications. Guaranteeing a satisfactory "construction" of is inherently more difficult. Also, even if the hybrid curable resin is at least partially cured after being exposed to chemical lines, the green model produced from it will be used in many additive manufacturing applications, for example when measured by modulus of elasticity or fracture strength. Has insufficient mechanical strength (or "green strength") to use. This problem is exacerbated by UV / vis optics that emit lower energy and intensity radiation than in conventional systems.

[016] Due to the limitations of cationic polymerization, this is a known hybrid liquid radiation curable resin for addition molding that is commercially suitable for use in more modern addition molding systems utilizing UV / vis optics. Does not exist. Further, it is suitable for an additive modeling system utilizing a UV / vis optical element, and has (1) sufficient high-speed curing property and (2) sufficient mechanical strength and shrinkage resistance to a three-dimensional component to be cured. There is no liquid thermosetting resin for addition molding (hybrid curable, etc.) that has both the applicability and the applicability at the same time.

[017] From the above, we utilize UV / vis optics capable of producing three-dimensional components with mechanical properties at least comparable to existing hybrid curable materials designed for traditional laser-based 355 nm systems. It is clear that there is a previously unsatisfied need to provide a hybrid curable liquid radiation resin composition suitable for use in an additive shaping system.

[Simple overview]
[018] A first aspect of the present invention comprises a cationically curable component further containing a cyclic aliphatic epoxy component for cationic polymerization, and at least one free radical curable component for free radical polymerization. UV / vis optics containing a cationic light initiator and a free radical light initiator and emitting radiation having a peak spectral output at 400 nm and a liquid UV / vis ray curable of at least 2 mW / cm ² in at least 10 seconds. After exposing the liquid UV / vis radical curable composition with an irradiation amount on the surface of the composition, the cyclic aliphatic epoxy component achieves a _T95 value of about 70 seconds or less and a plateau conversion rate of at least about 20%. , A liquid UV / vis radical curable composition for addition molding.

[019] The first aspect of the present invention is a cationically curable component for performing cationic polymerization, which further comprises a cyclic aliphatic epoxy component and an oxetane component, and performs free radical polymerization. UV / vis optics comprising a free radical curable component and a photoinitiator package further comprising a cationic photoinitiator, a vinyl ether diluent monomer and a free radical photoinitiator to emit radiation with a peak spectral output at 400 nm. When the liquid UV / vis radical curable composition was exposed to the device and the surface of the liquid UV / vis radical curable composition at 2 mW / cm ² for 10 seconds, the cyclic aliphatic epoxy component was as follows. Properties, ie, (i) a _T95 value of about 70 seconds or less, more preferably about 55 seconds or less, more preferably about 53 seconds or less, more preferably about 50 seconds or less, and (ii) at least about 20%, more. A plateau conversion of preferably at least about 30%, more preferably at least about 36%, more preferably at least about 43%, and the oxetane component has the following properties: (i) about 50 seconds or less. , More preferably less than about 42 seconds, more preferably less than about 34 seconds, more preferably less than about 23 seconds, and (ii) at least about 29 _% , more preferably at least about 34%, more preferably at least. A liquid UV / vis radical curable composition for addition shaping that achieves a plateau conversion of about 50%, more preferably at least about 59%.

[020] A second aspect of the present invention is (a) a cationically polymerizable component, (b) an iodonium salt cationic photoinitiator, and (c) a photosensitizer for photosensitizing the component (b). , (D) A reducing agent for reducing the component (b), (e) a free radical polymerizable component, and optionally (f) a free radical photoinitiator, at 20 mJ / cm ² . UV / vis optics that give a dose and emit radiation with a peak spectral intensity of about 375 nm to about 500 nm, more preferably about 380 nm to about 450 nm, more preferably about 390 nm to about 425 nm, more preferably about 395 nm to about 410 nm. It is a liquid radiation curable composition for addition molding that can be cured by

[021] A second aspect of the present invention is a cationically polymerizable component, an iodonium salt cation photoinitiator, a photosensitizer for photosensitizing the iodonium salt cation photoinitiator, and an iodonium salt cation light initiator. An iodonium salt cation light initiator having a first reducing agent for reducing the agent, a free radical polymerizable component, optionally a free radical photoinitiator, and an electron donating substituent bonded to a vinyl group. It contains a second reducing agent for reducing the agent, gives a dose of 20 mJ / cm ² , and has a peak spectral intensity of about 375 nm to about 500 nm, more preferably about 380 nm to about 450 nm, more preferably about 390 nm to. It is a liquid radiation curable composition for addition molding that can be cured by a UV / vis optical element that emits radiation of about 425 nm, more preferably about 395 nm to about 410 nm.

（式中、ＲはＣ_１～Ｃ_２０脂肪族鎖を含有する）
で示される約０．５ｗｔ．％～約３ｗｔ．％の化合物と、フリーラジカル重合性成分と、ジフェニル（２，４，６－トリメチルベンゾイル）ホスフィンオキシドフリーラジカル光開始剤と、を含み、２０ｍＪ／ｃｍ^２の線量を与えるかつピークスペクトル強度で約３７５ｎｍ～約５００ｎｍ、より好ましくは約３８０ｎｍ～約４５０ｎｍ、より好ましくは約３９０ｎｍ～約４２５ｎｍの放射線を放出するＵＶ／ｖｉｓ光学素子により硬化可能である、付加造形用液状放射線硬化性組成物である。 [022] A third aspect of the present invention further comprises about 30 wt. Cyclic aliphatic epoxide and oxetane. % ~ About 80 wt. % At least one cationically polymerizable component and about 1 wt. With an absorbance of less than 0.01 at 400 nm. % ~ About 8 wt. % Sulfonium salt cation photoinitiator and the following formula (V):

(In the formula, R contains C ₁ to C ₂₀ aliphatic chains)
Approximately 0.5 wt. Indicated by. % ~ About 3 wt. % Of compound, free radical polymerizable component, diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide free radical photoinitiator, giving a dose of 20 mJ / cm ² and peak spectral intensity of about 375 nm. It is a liquid radiation curable composition for addition molding that can be cured by a UV / vis optical element that emits radiation of about 500 nm, more preferably about 380 nm to about 450 nm, and more preferably about 390 nm to about 425 nm.

[023] A fourth aspect of the present invention is a method of forming a three-dimensional article by an additive modeling system utilizing a UV / vis optical element, wherein (1) the first, second, or third aspect of the present invention. The step of providing the liquid radiation curable composition for addition molding according to any one of the embodiments, (2) the step of providing the first liquid layer of the liquid radiation curable resin, and (3) the UV / vis optical configuration are used. The step of forming the first cured layer by exposing the first liquid layer in an image-like manner with chemical rays to form an image-forming cross section, and (4) the liquid in contact with the first cured layer. A step of forming a new layer of radiation-curable resin, (5) a step of exposing the new layer to an image like an image with a chemical line to form an additional image-forming cross section, and (6) constructing a three-dimensional article. For this purpose, the steps (4) and (5) are repeated a sufficient number of times, and the UV / vis optical element has a peak spectral intensity of about 375 nm to about 500 nm, more preferably about 380 nm to about 450 nm, and more preferably about. A method of emitting radiation from 395 nm to about 410 nm.

[024] The fifth aspect of the present invention is the process according to the fourth aspect of the present invention using the liquid radiation curable composition according to any one of the first, second, or third aspects of the present invention. It is a three-dimensional component that is formed.

FIG. 1 shows RT-FTIR (365 nm) of a cyclic aliphatic epoxide of Plastic ABS3650, a commercially available liquid hybrid radiocurable composition for addition molding designed to be suitable for addition molding machines operating at a peak spectral intensity of 365 nm. It is a plot showing the conversion rate (under curing conditions). FIG. 2 is a plot showing the RT-FTIR (365 nm curing condition) conversion rate of oxetane of Plastcure ABS3650. FIG. 3 shows RT-FTIR (400 nm cure) of a cyclic aliphatic epoxide of a liquid hybrid radiocurable composition for addition shaping utilizing a photoinitiator package using a photoinitiator that is believed to be useful for wavelengths of 400 nm. (Conditions) It is a plot showing the conversion rate. FIG. 4 shows the RT-FTIR (400 nm curing conditions) conversion of oxetane in a liquid hybrid radiation curable composition for addition shaping using a photoinitiator package using a photoinitiator that has been shown to be useful for wavelengths of 400 nm. It is a plot showing the rate. FIG. 5 shows the RT-of a cyclic aliphatic epoxide of a liquid hybrid radiocurable composition for addition modeling utilizing a light initiation package designed to be suitable for addition molding machines operating at a peak spectral intensity of 365 nm. It is a plot which shows the FTIR (365 nm curing condition) conversion rate. FIG. 6 shows RT-FTIR (365 nm curing) of oxetane in a liquid hybrid radiation curable composition for augmentation utilizing a light initiation package designed to be suitable for augmentation machines operating at peak spectral intensities of 365 nm. (Conditions) It is a plot showing the conversion rate. FIG. 7 is a plot showing the RT-FTIR (400 nm curing condition) conversion rate of the cyclic aliphatic epoxide of the liquid hybrid radiation curable composition for addition molding according to the present invention. FIG. 8 is a plot showing the RT-FTIR (400 nm curing condition) conversion rate of oxetane in the liquid hybrid radiation curable composition for addition molding according to the present invention. FIG. 9 is a plot showing the RT-FTIR (400 nm curing condition) conversion rate of the cyclic aliphatic epoxide of the liquid hybrid radiation curable composition for addition molding according to the present invention. FIG. 10 is a plot showing the RT-FTIR (400 nm curing condition) conversion rate of oxetane in the liquid hybrid radiation curable composition for addition molding according to the present invention. FIG. 11 is a plot showing the RT-FTIR (400 nm curing condition) conversion rate of the cyclic aliphatic epoxide of the liquid hybrid radiation curable composition for addition molding according to the present invention. FIG. 12 is a plot showing the RT-FTIR (400 nm curing condition) conversion rate of oxetane in the liquid hybrid radiation curable composition for addition molding according to the present invention. FIG. 13 is a plot showing the RT-FTIR (400 nm curing condition) conversion rate of the cyclic aliphatic epoxide of the liquid hybrid radiation curable composition for addition molding according to the present invention. FIG. 14 is a plot showing the RT-FTIR (400 nm curing condition) conversion rate of oxetane in the liquid hybrid radiation curable composition for addition molding according to the present invention.

[Detailed explanation]
[033] Throughout this document, "UV / vis" is defined as the electromagnetic spectrum region of 375 nanometers (nm) to 500 nanometers (nm).

[034] Thus, throughout this document, the "UV / vis optics" is any electrical, mechanical, or electrical system that produces and directs / displays chemical lines operating at peak spectral intensities of 375 nm to 500 nm. Defined as a mechanical system. Specific examples of UV / vis optics include, but are not limited to, a laser, an LED, one or more LEDs coupled to a DLP display system, one or more LEDs coupled to an LCD display system, and a DLP display. Examples include lasers coupled to the system and lasers coupled to the LCD display system.

[035] The first embodiment of the present invention is:
A cationically curable component for performing cationic polymerization, which further contains a cyclic aliphatic epoxy component and an oxetane component, and a cationically curable component.
Free radical curable components that perform free radical polymerization and
The following, that is,
Cationic photoinitiator and
Vinyl ether diluent monomer and
Free radical photoinitiator and
Including a light start package and
Including
A UV / vis optical element that emits radiation with a peak spectral output at 400 nm and a 2 mW / cm ² liquid UV / vis ray-curable composition over 10 seconds. When exposed to
The cyclic aliphatic epoxy component has the following properties, that is,
i. With a _T95 value of about 70 seconds or less, more preferably about 55 seconds or less, more preferably about 53 seconds or less, more preferably about 50 seconds or less.
ii. With a plateau conversion rate of at least about 20%, more preferably at least about 30%, more preferably at least about 36%, more preferably at least about 43%.
And the oxetane component has the following properties, that is,
i. With a _T95 value of about 50 seconds or less, more preferably less than about 42 seconds, more preferably less than about 34 seconds, more preferably less than about 23 seconds.
ii. With a plateau conversion rate of at least about 29%, more preferably at least about 34%, more preferably at least about 50%, more preferably at least about 59%.
To achieve,
It is a liquid UV / vis line curable composition for addition molding.

[Cation curable component]
[036] According to one embodiment, the liquid radiation curable resin for addition molding of the present invention is at least one cationically polymerizable component which is a component that carries out polymerization initiated by a cation or in the presence of an acid generator. including. The cationically polymerizable component can be a monomer, an oligomer, and / or a polymer, as well as an aliphatic moiety, an aromatic moiety, a cyclic aliphatic moiety, an aryl aliphatic moiety, a heterocyclic moiety, and any combination thereof. May contain. Preferably, the cationically polymerizable component comprises at least one cyclic aliphatic compound. Suitable cyclic ether compounds may include cyclic ether groups as side groups or as groups forming part of an alicyclic or heterocyclic ring system.

[037] The cationically polymerizable component is selected from the group consisting of a cyclic ether compound, a cyclic acetal compound, a cyclic thioether compound, a spiro-ortho ester compound, a cyclic lactone compound, and any combination thereof.

Suitable cationically polymerizable components include cyclic ether compounds such as epoxy compounds and oxetane, cyclic lactone compounds, cyclic acetal compounds, cyclic thioether compounds, and spiro-ortho ester compounds. Specific examples of the cationically polymerizable component include bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, brominated bisphenol A diglycidyl ether, brominated bisphenol F diglycidyl ether, and brominated bisphenol S diglycidyl. Ether, epoxide novolak resin, hydride bisphenol A diglycidyl ether, hydride bisphenol F diglycidyl ether, hydride bisphenol S diglycidyl ether, 3,4-epoxycyclohexylmethyl-3', 4'epoxide cyclohexanecarboxylate, 2- (3,4-epoxide cyclohexyl-5,5-spiro-3,4-epoxy) -cyclohexane-1,4-dioxane, bis (3,4-epoxidecyclohexylmethyl) adipate, vinylcyclohexene oxide, 4-vinyl epoxycyclohexane , Vinyl Cyclohexene Dioxide, Limonen Oxide, Limonen Dioxide, Bis (3,4-Epoxide-6-Methylcyclohexylmethyl) Adipate, 3,4-Epoxide-6-Methylcyclohexyl-3', 4'-Epoxide-6' -Methylcyclohexanecarboxylate, ε-caprolactone-modified 3,4-epoxidecyclohexylmethyl-3', 4'-epoxide cyclohexanecarboxylate, trimethylcaprolactone-modified 3,4-epoxidecyclohexylmethyl-3', 4'-epoxide cyclohexanecarboxylate , Β-Methyl-δ-Valerolactone modified 3,4-epoxycyclohexylmethyl-3', 4'-epoxycyclohexanecarboxylate, methylenebis (3,4-epoxycyclohexane), bicyclohexyl-3,3'-epoxide,- O-, -S-, -SO-, -SO _2- , -C (CH ₃ ) _2- , -CBr _2- , -C (CBr ₃ ) _2- , -C (CF ₃ ) _2- , -C (CCl ₃ ) ₂ -or-CH (C _{6H 5 )} -bonded bis (3,4-epoxycyclohexyl), dicyclopentadiene diepoxide, di (3,4-epoxycyclohexylmethyl) of ethylene glycol Ether, ethylene bis (3,4-epoxycyclohexanecarboxylate), epoxyhexahydrodioctylphthalate, epoxyhexahydro-di-2-ethylhexylphthalate, 1,4-butanediol Diglycidyl ether, 1,6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, glycerol triglycidyl ether, trimethylolpropane triglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, aliphatic long chain bibase Diglycidyl ester of acid, monoglycidyl ether of aliphatic higher alcohol, monoglycidyl ether of phenol, cresol, butylphenol, or polyether alcohol obtained by addition of alkylene oxide to compound, glycidyl ester of higher fatty acid, epoxidized soybean oil , Epoxybutyl stearate, epoxyoctyl stearate, epoxidized flaxseed oil, epoxidized polybutadiene, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, 3-ethyl-3-hydroxymethyloxetane, 3-Ethyl-3- (3-hydroxypropyl) oxymethyloxetane, 3-ethyl-3- (4-hydroxybutyl) oxymethyloxetane, 3-ethyl-3- (5-hydroxypentyl) oxymethyloxetane, 3- Ethyl-3-phenoxymethyloxetane, bis ((1-ethyl (3-oxetanyl)) methyl) ether, 3-ethyl-3-((2-ethylhexyloxy) methyl) oxetane, 3-ethyl-((triethoxysilyl)) Propoxymethyl) oxetane, 3- (meth) -allyloxymethyl-3-ethyloxetane, 3-hydroxymethyl-3-ethyloxetane, (3-ethyl-3-oxetanylmethoxy) methylbenzene, 4-fluoro- [1- (3-Ethyl-3-oxetanylmethoxy) methyl] benzene, 4-methoxy- [1- (3-ethyl-3-oxetanylmethoxy) methyl] -benzene, [1- (3-ethyl-3-oxetanylmethoxy) ethyl ] Phenyl ether, isobutoxymethyl (3-ethyl-3-oxetanylmethyl) ether, 2-ethylhexyl (3-ethyl-3-oxetanylmethyl) ether, ethyldiethylene glycol (3-ethyl-3-oxetanylmethyl) ether, dicyclo Pentaziene (3-ethyl-3-oxetanylmethyl) ether, dicyclopentenyloxyethyl (3-ethyl-3-oxetanylmethyl) ether, dicyclopentenyl (3-ethyl-3-oxetani) Lumethyl) ether, tetrahydroflufil (3-ethyl-3-oxetanylmethyl) ether, 2-hydroxyethyl (3-ethyl-3-oxetanylmethyl) ether, 2-hydroxypropyl (3-ethyl-3-oxetanylmethyl) ether , And any combination thereof.

[039] The cationically polymerizable component is optionally a dendritic such as a dendrimer having an epoxy functional group or an oxetane functional group, a linear dendritic polymer, a dendrigraft polymer, a hyperbranched polymer, a starbranched polymer, and a hypergrafted polymer. It may also contain polyfunctional materials such as polymers. The dendritic polymer may contain one type of polymerizable functional group or a different type of polymerizable functional group, such as an epoxy functional group and an oxetane functional group.

[040] In embodiments, the compositions of the invention also include one or more monos or polyglycidyl ethers of fatty alcohols, aliphatic polyols, polyester polyols, or polyether polyols. Examples of preferred ingredients are 1,4-butanediol diglycidyl ether, polyoxyethylene and polyoxypropylene glycols having a molecular weight of about 200 to about 10,000 and triol glycidyl ethers, polytetramethylene glycol or poly (oxy). Ethylene-oxybutylene) random copolymers or block copolymers of glycidyl ethers can be mentioned. In a specific embodiment, the cationically polymerizable component comprises a polyfunctional glycidyl ether without a cyclohexane ring in the molecule. In another specific embodiment, the cationically polymerizable component comprises neopentyl glycol diglycidyl ether. In another specific embodiment, the cationically polymerizable component comprises 1,4-cyclohexanedimethanol diglycidyl ether.

[041] An example of a preferred polyfunctional glycidyl ether on the market is Erisys ™ GE22 (Elysis ™ product is available from Emerald Performance Materials ™). , Heroxy ™ 48, Heloxy ™ 67, Heloxy ™ 68, Heloxy ™ 107 (Heroxy ™ modifiers are available from Momentive Specialty Chemicals). There is), and Grironit® F713. Examples of preferred monofunctional glycidyl ethers on the market are Heroxy ™ 71, Heroxy ™ 505, Heroxy ™ 7, Heroxy ™ 8, and Heroxy ™ 61.

[042] In embodiments, the epoxide is 3,4-epoxide cyclohexylmethyl-3', 4-epoxycyclohexanecarboxylate (from Daicel Chemical to CELLOXIDE ™ 202IP or Dow Chemical. It is available from Chemical as CYRACURE ™ UVR-6105), hydrided bisphenol A epichlorohydrin-based epoxy resin (Momentive as EPON ™ 1510). ), 1,4-Cyclohexanedimethanol diglycidyl ether (available from Momentiv as heroxi ™ 107), hydrided bisphenol A diglycidyl ether (available from Momentiv as Epon ™ 825) dicyclohexyldi. A mixture of epoxides and nanosilica (available as NANOPOX ™), and any combination thereof.

（式中、Ｒは、炭素原子、エステル含有Ｃ_１～Ｃ_１０脂肪族鎖、またはＣ_１～Ｃ_１０アルキル鎖である）
で示される２個または２個超のエポキシ基を有する環式脂肪族エポキシを含む。 [043] In a specific embodiment, the cationically polymerizable component is a cyclic aliphatic epoxy, eg, Formula I:

(In the formula, R is a carbon atom, an ester-containing C ₁ to C ₁₀ aliphatic chain, or a C ₁ to C ₁₀ alkyl chain).
Includes cyclic aliphatic epoxies having 2 or more epoxy groups, as indicated by.

[044] In another specific embodiment, the cationically polymerizable component has an aromatic or aliphatic glycidyl ether group having two (bifunctional) or more than two (polyfunctional) epoxy groups. Contains epoxy.

[045] The cationically polymerizable compounds described above can be used alone or in combination of two or more thereof. In embodiments of the invention, the cationically polymerizable component further comprises at least two different epoxy components.

を有する。 [046] In another embodiment of the invention, the cationically polymerizable component also comprises an oxetane component. In a specific embodiment, the cationically polymerizable component comprises an oxetane, eg, an oxetane containing one, two, or more than two oxetane groups. In other embodiments, the oxetane utilized is monofunctional and has an additional hydroxyl group. According to embodiments, oxetane has the following structure:

Have.

[047] When used in the composition, the oxetane component is present in a suitable amount of about 5 to about 50 wt% of the resin composition. In other embodiments, the oxetane component is present in an amount of about 10 to about 25 wt% of the resin composition, and in yet another embodiment, the oxetane component is present in an amount of 20 to about 30 wt% of the resin composition.

[048] Therefore, the liquid radiation curable resin for addition molding is in a suitable amount, for example, about 10 to about 80% by weight of the resin composition in a specific embodiment, and about 20 to about 20 to about 20 to about 20 to about 20% by weight of the resin composition in a further embodiment. 70 wt%, in a further embodiment about 25-about 65 wt% of the resin composition, in a more preferred embodiment about 30-about 80 wt%, more preferably about 50-about 85 wt% of the cationically polymerizable component. Can be included.

[Free radically polymerizable compound]
[049] According to an embodiment of the present invention, the liquid radiation curable resin for addition molding of the present invention contains at least one free radically polymerizable component, that is, a component that carries out polymerization initiated by a free radical. Free radical polymerizable components are monomers, oligomers, and / or polymers and are monofunctional or polyfunctional materials, i.e., 1, 2, 3, 4, 5, 6 which can be polymerized by free radical initiation. , 7, 8, 9, 10 ... 20 ... 30 ... 40 ... 50 ... 100 or more functional groups, aliphatic, aromatic, cyclic aliphatic, aryl aliphatic, heterocyclic part Or any combination thereof may be contained. Examples of polyfunctional materials include dendritic polymers such as dendrimers, linear dendritic polymers, dendrigraft polymers, hyperbranched polymers, starbranched polymers, hypergraft polymers. See, for example, US Patent Application Publication No. 2009/093564A1. The dendritic polymer may contain one type of polymerizable functional group or a different type of polymerizable functional group, such as an acrylate functional group and a methacrylate functional group.

[050] Examples of free radically polymerizable components include isobornyl (meth) acrylate, bornyl (meth) acrylate, tricyclodecanyl (meth) acrylate, dicyclopentanyl (meth) acrylate, and dicyclopentenyl (meth) acrylate. , Cyclohexyl (meth) acrylate, benzyl (meth) acrylate, 4-butylcyclohexyl (meth) acrylate, acryloylmorpholin, (meth) acrylic acid, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2 -Hydroxybutyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, amyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, caprolactone acrylate, isoamyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (Meta) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, tridecyl (meth) acrylate, undecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, isostearyl ( Meta) acrylate, tetrahydrofurfuryl (meth) acrylate, butoxyethyl (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, polyethylene glycol mono (meth) acrylate and polypropylene glycol, Mono (meth) acrylate, methoxyethylene glycol (meth) acrylate, ethoxyethyl (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, diacetone (meth) acrylamide, beta-carboxyethyl (meth) Acrylate, phthalic acid (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, butylcarbamylethyl (meth) acrylate, n-isop Includes acrylates and methacrylates such as lopyr (meth) acrylamide fluorinated (meth) acrylates, 7-amino-3,7-dimethyloctyl (meth) acrylates.

[051] Examples of the polyfunctional free radically polymerizable component include those having a (meth) acryloyl group, for example, trimethylolpropanetri (meth) acrylate, pentaerythritol (meth) acrylate, ethylene glycol di (meth) acrylate. , Bisphenol A diglycidyl ether di (meth) acrylate, dicyclopentadiene dimethanol di (meth) acrylate, [2- [1,1-dimethyl-2-[(1-oxoallyl) oxy] ethyl] -5-ethyl- 1,3-Dioxane-5-yl] Methyl acrylate, 3,9-bis (1,1-dimethyl-2-hydroxyethyl) -2,4,8,10-Tetraoxaspiro [5.5] Undecandi (meth) ) Acrylate, dipentaerythritol monohydroxypenta (meth) acrylate, propoxylated trimethylol propantri (meth) acrylate, propoxylated neopentyl glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (Meta) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, polybutanediol di (meth) acrylate, tripropylene glycol Di (meth) acrylate, glycerol tri (meth) acrylate, monophosphate and di (meth) acrylate, C ₇ to C ₂₀ alkyl di (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, tris. (2-Hydroxyethyl) isocyanurate di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) crylate, tricyclodecandyldimethyldi (meth) acrylate, And any of the above monomers alkylated (eg, ethoxylated and / or propoxylated), as well as di (meth) acrylates of diols, which are additions of ethylene oxide or propylene oxide to bisphenol A, hydride bisphenol A. Di (meth) acrylate of diol, which is an adduct of ethylene oxide or propylene oxide, and (meth) acrylate adduct to bisphenol A diglycidyl ether. Examples include certain epoxy (meth) acrylates, diacrylates of polyoxyalkylated bisphenol A, and triethylene glycol divinyl ethers, as well as adducts of hydroxyethyl acrylates.

[052] According to the embodiment, the radically polymerizable component is a polyfunctional (meth) acrylate. The polyfunctional (meth) acrylate may include all methacryloyl groups, all acryloyl groups, or any combination of methacryloyl groups and acryloyl groups. In embodiments, the free radically polymerizable component is bisphenol A diglycidyl ether di (meth) acrylate, ethoxylated or propoxylated bisphenol A or bisphenol F di (meth) acrylate, dicyclopentadiene dimethanol di (meth) acrylate, [2- [1,1-dimethyl-2-[(1-oxoallyl) oxy] ethyl] -5-ethyl-1,3-dioxane-5-yl] methyl acrylate, dipentaerythritol monohydroxypenta (meth) acrylate , Dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) crylate, propoxylated trimethylolpropane tri (meth) acrylate, and propoxylated neopentyl glycol di (meth) acrylate, and any combination thereof. It is selected from the group consisting of.

[053] In embodiments, the polyfunctional (meth) acrylate has more than two functional groups. According to other embodiments, the polyfunctional (meth) acrylate has more than 3 functional groups. In yet another embodiment, the polyfunctional (meth) acrylate has more than 4 functional groups. In another preferred embodiment, the radically polymerizable component consists exclusively of a single polyfunctional (meth) acrylate component. In a further embodiment, the exclusive radically polymerizable component is tetrafunctional, in a further embodiment the exclusive radically polymerizable component is pentafunctional, and in a further embodiment, the exclusive radically polymerizable component is hexafunctional. It is sex.

[054] In another embodiment, the free radically polymerizable component contains an aromatic (meth) acrylate. Aromatic acrylates are derived from, but not limited to, bisphenol A, bisphenol S, or bisphenol F, for example. In certain embodiments, bisphenol A diglycidyl ether diacrylate, dicyclopentadiene dimethanol diacrylate, [2- [1,1-dimethyl-2-[(1-oxoallyl) oxy] ethyl] -5-ethyl- 1,3-Dioxane-5-yl] Methyl acrylate, dipentaerythritol monohydroxypentaacrylate, propoxylated trimethylolpropane triacrylate, and propoxylated neopentyl glycol diacrylate, and any combination thereof. The aromatic substance of choice. In embodiments, the aromatic (meth) acrylate is bifunctional.

[055] In a specific embodiment, the liquid radiation curable resin for addition molding of the present invention is bisphenol A diglycidyl ether di (meth) acrylate, dicyclopentadiene dimethanol di (meth) acrylate, dipentaerythritol monohydroxy. One or more of penta (meth) acrylates, propoxylated trimethylol propantri (meth) acrylates, and / or propoxylated neopentyl glycol di (meth) acrylates, more specifically bisphenol A diglycidyl ether diacrylates, Includes one or more of dicyclopentadiene dimethanol diacrylates, dipentaerythritol pentaacrylates, propoxylated trimethylol propanetriacrylates, and / or propoxylated neopentyl glycol diacrylates.

[056] The radically polymerizable compounds described above can be used alone or in combination of two or more thereof. The liquid radiation curable resin for addition molding is in an arbitrary suitable amount, for example, up to about 50 wt% of the resin composition in a specific embodiment, about 2 to about 40 wt% of the resin composition in a specific embodiment, and the like. About 5 to about 30 wt% in the embodiment, about 10 to about 20 wt% of the resin composition in a further embodiment, about 8 to about 50 wt% in another further preferred embodiment, and more preferably about 15 to about 15 to the resin composition. It may contain an amount of about 25 wt% free radically polymerizable component.

[Cation light initiator]
[057] According to one embodiment, the liquid thermosetting resin composition comprises a cationic photoinitiator. The cationic light initiator initiates cationic ring-opening polymerization upon light irradiation.

[058] In the embodiment, any suitable iodonium-based cation photoinitiator has a cation selected from the group consisting of, for example, diaryliodonium salt, triaryliodonium salt, aromatic iodonium salt, and any combination thereof. Things can be used.

[059] In other embodiments, the cations of the cation photoinitiator are aromatic diazonium salts, aromatic sulfonium salts, aromatic iodonium salts, metallocene compounds, aromatic phosphonium salts, acyl sulfonium salts, and any of them. Selected from a group of combinations. In other embodiments, the cation is a polymer sulfonium salt, eg, one described in US Pat. No. 5,380,923 or US Pat. No. 5,047,568, or other aromatic heteroatom-containing cations and naphthyl-sulfonium salts. For example, U.S. Patent No. 7611817, U.S. Patent No. 7230122, U.S. Patent Application Publication No. 2011/0039205, U.S. Patent Application Publication No. 2009/01822172, U.S. Patent No. 76785528, It is described in European Patent No. 23088865, International Publication No. 20140240, or European Patent No. 2218715. In another embodiment, the cationic photoinitiator is selected from the group consisting of triarylsulfonium salts, diaryliodonium salts, and metallocene compounds, and any combination thereof. Onium salts, such as iodonium and sulfonium salts as well as ferrosenium salts, generally have the advantage of being more thermally stable.

[060] In certain embodiments, the cationic photoinitiators are BF _4- ^, AsF _6- ^, SbF _6- ^, PF _6- ^, [B (CF ₃ ) ₄ ] ^- , B (C ₆ F ₅ ⁾ _4- , B [C ₆ H _3-3 , 5 (CF ₃ ) ₂ ] _4- ^, B (C ₆ H ₄ CF ₃ ) _4- ^, B (C ₆ H ₃ F ₂ ) _4- ^, B [C ₆ F ₄ -4 (CF ₃ )] _4- ^, Ga (C ₆ F ₅ ) _4- ^, [(C ₆ F ₅ ) ₃ B-C ₃ H ₃ N ₂ -B (C ₆ F ₅ ) ₃ ] ^- , [( C ₆ F ₅ ) ₃ B-NH ₂ -B (C ₆ F ₅ ) ₃ ] ^- , Tetrakiss (3,5-difluoro-4-alkyloxyphenyl) borate, Tetrakiss (2,3,5,6-tetrafluoro) -4-alkyloxyphenyl) borate, perfluoroalkyl sulfonate, tris [(perfluoroalkyl) sulfonyl] methide, bis [(perfluoroalkyl) sulfonyl] imide, perfluoroalkyl phosphate, tris (perfluoroalkyl) trifluorophosphate, bis (perfluoroalkyl) ) Tetrafluorophosphate, Tris (pentafluoroethyl) trifluorophosphate, and (CH ₆ B ₁₁ Br ₆ ) ^- , (CH ₆ B ₁₁ Cl ₆ ) ^- , and other halogenated carborane anions. Has an anion.

[061] An overview of other onium salt initiators and / or metallocene salts can be found in "UV Curing, Science and Technology", edited by SP Pappas, Technology Marketing Corporation, United States Connection Cut. Stamford, Stamford, Westover Road 642 (642 Westover Road, Stamford, Conn., USA) "Chemistry & Technology of UV & EB Formulation for Coatings, Inc., Volume 3 Inks & Pa. T. Oldring), or J. P. Fouassier, J. Mol. It can be found in Wiley 2012 ISBN978-3-527-33210-6, "Photoinitiators for polymer synthesis" by Lovelee.

[062] In embodiments, the cationic photoinitiators are SbF ₆ ⁻ , PF ₆ ⁻ , B (C ₆ F ₅ ) ₄ ⁻ , [B (CF ₃ ) ₄ ] ⁻ , Tetrakiss (3,5-difluoro-4). Aromatic with at least anions selected from the group consisting of-methoxyphenyl) borate, perfluoroalkyl sulfonates, perfluoroalkyl phosphates, tris [(perfluoroalkyl) sulfonyl] methides, and [(C ₂ F ₅ ) ₃ PF ₃ ] ^- . It has a cation selected from the group consisting of sulfonium salts, aromatic iodonium salts, and metallocene compounds.

[063] Examples of suitable cationic photoinitiators for other embodiments are 4- [4- (3-chlorobenzoyl) phenylthio] phenylbis (4-fluorophenyl) sulfonium hexafluoroantimonate, 4- [4. -(3-Chlorobenzoyl) phenylthio] phenylbis (4-fluorophenyl) sulfonium tetrakis (pentafluorophenyl) borate, 4- [4- (3-chlorobenzoyl) phenylthio] phenylbis (4-fluorophenyl) sulfonium tetrakis ( 3,5-Difluoro-4-methyloxyphenyl) borate, 4- [4- (3-chlorobenzoyl) phenylthio] phenylbis (4-fluorophenyl) sulfonium tetrakis (2,3,5,6-tetrafluoro-4) -Methyloxyphenyl) borate, tris (4- (4-acetylphenyl) thiophenyl) sulfonium tetrakis (pentafluorophenyl) borate (BASF Irgacure® PAG290), tris (4- (4-acetyl) Phenyl) thiophenyl) sulfonium tris [(trifluoromethyl) sulfonyl] methide (BASF irgacure® GSID26-1), tris (4- (4-acetylphenyl) thiophenyl) sulfonium hexafluorophosphate (BASF irgacure) (Registered Trademark) 270) and HS-1 available from San-Apro Ltd..

[064] In a preferred embodiment, the cationic photoinitiator component is either bis [4-diphenylsulfoniumphenyl] sulfide bishexafluoroantimonate, thiophenoxyphenylsulfonium hexafluoroantimonate (Chitec), either alone or in admixture. ), Chivacure 1176), Tris (4- (4-Acetylphenyl) Thiophenyl) Sulfonium Tetrakiss (Pentafluorophenyl) Borate (BASF Irgacure® PAG290), Tris (4-) (4-Acetylphenyl) Thiophenyl) Sulfonium Tris [(Trifluoromethyl) Sulfide] Metide (BASF Irgacure® GSID26-1), and Tris (4- (4-Acetylphenyl) Thiophenyl) Sulfonium Hexafluorophosphate (Irgacure® 270 manufactured by BASF), [4- (1-methylethyl) phenyl] (4-methylphenyl) iodonium tetrakis (pentafluorophenyl) borate (from Rhodia to Rhodolsil 2074) Available), 4- [4- (2-chlorobenzoyl) phenylthio] phenylbis (4-fluorophenyl) sulfonium hexafluoroantimonate (as SP-172 from Adeka), SP-300 from Adeca , And (PF _6-m (C _n F _{2n + 1} ) _m ) ^- (in the formula, m is an integer of 1 to 5 and n is an integer of 1 to 4) an aromatic sulfonium salt (in the formula). Includes TK-1 available from Sun Appro Co., Ltd. as CPI-200K or CPI-200S of monovalent sulfonium salt, TK-1 available from Sun Appro Co., Ltd., or HS-1) available from Sun Appro Co., Ltd.

[065] In embodiments of the present invention, the liquid radiation curable resin for addition shaping comprises an aromatic triarylsulfonium salt cationic photoinitiator. The use of aromatic triarylsulfonium salts in additive modeling applications is known. Aromatic triarylsulfonium salts with tetraarylborate anions, including tetrakis (pentafluorophenyl) borate, and the use of these compounds in stereolithographic applications are discussed in DSM IP Assets, B. et al. V. Please refer to US Patent Application Publication No. 20120251841 granted to Asahi Denki Kogyo and US Patent No. 6,368,769 granted to Asahi Denki Kogyo. Triaryl sulfonium salts are disclosed, for example, in J Photopolymer Science & Tech (2000), 13 (1), 117-118, and J Poly Science, Part A (2008), 46 (11), 3820-29. .. Triaryl sulfonium has a complex metal halide anion such as BF _4- ^, AsF _6- ^, PF _6- ^, SbF _6- ^and the Ar ₃ S + MXn ^- salt is J Polymr Sci, Part A (1996), 34 (16). , 3231-3253.

[066] An example of a triarylsulfonium tetrakis (pentafluorophenyl) borate cationic photoinitiator is tris (4- (4-acetylphenyl) thiophenyl) sulfonium tetrakis (pentafluorophenyl) borate. Tris (4- (4-acetylphenyl) thiophenyl) sulfonium tetrakis (pentafluorophenyl) borate is commercially known as Irgacure® PAG-290 and is available from Ciba / BASF. ..

[067] In other embodiments, the cationic photoinitiators are SbF ₆ ⁻ , PF ₆ ⁻ , BF ₄ ⁻ , (CF ₃ CF ₂ ) ₃ PF ₃ ⁻ , (C ₆ F ₅ ) ₄ B ⁻ , (((C 6 F 5) 4 B −). CF ₃ ) ₂ C ₆ H ₃ ) ₄ B- ^, (C ₆ F ₅ ) ₄ Ga- ^, ((CF ₃ ) ₂ C ₆ H ₃ ) ₄ Ga- ^, Trifluoromethanesulfonate, Nonafluorobutane sulfonate, Methanesulfonate, An aromatic triarylsulfonium salt having an anion represented by butane sulfonate, benzene sulfonate, or p-toluene sulfonate. Such photoinitiators are described, for example, in US Pat. No. 8,617,787.

[068] Another cationic photoinitiator is an aromatic triarylsulfonium cationic photoinitiator with an anion of fluoroalkyl-substituted fluorophosphate. Examples of commercially available aromatic triarylsulfonium cation photoinitiators with fluoroalkyl substituted fluorophosphate anions are the CPI200 series (eg CPI-200K® or CPI-210S® available from San Apro Co., Ltd. )) Or 300 series.

[069] There are also some commercially available cationic photoinitiators designed to be particularly suitable for absorbing light at UV / vis wavelengths to generate photoreactive species. Incorporation of one or more of these cationic photoinitiators into a liquid radiation curable composition for UV / vis curing will be achieved via "direct" excitation of the photoinitiators. Some examples of UV / vis direct excitation cationic photoinitiators include, but are not limited to, Irgacure 261, Irgacure PAG103, and Irgacure PAG121 (commercially available from BASF, respectively), R-Gen®. 262 (η5-2,4-cyclopentadiene-1-yl) [(1,2,3,4,5,6-η)-(1-methylethyl) benzene] -iron (I) -hexafluoroantimonate ) (Commercially available from Chitec Technology Co.) and CPI400 series photoinitiators (available from Sun Appro Co., Ltd.).

[070] However, surprisingly, the UV / vis direct excitation cationic photoinitiators listed above achieve sufficient hybrid curing of the compositions used in the addition shaping process utilizing UV / vis optics. The applicant has found that it is not suitable for. Although not desired to be constrained by any theory, the free radical portion of the polymer network cures fairly quickly, so the free radical cure portion of the resin enhances viscosity and polymer structure and cures more slowly. It is speculated that the molecular mobility of the cured species is significantly reduced, thereby significantly reducing the overall curing speed to an unacceptably low rate. This problem is unique to dual curable hybrid resins and is exacerbated by the longer wavelengths, lower energies, and lower intensities typical of modern UV / vis optics. Therefore, the formulation of hybrid curable radiation curable compositions for addition shaping suitable for UV / vis wavelengths can be achieved by simply changing the cationic photoinitiator of the hybrid resin suitable for UV curing with, for example, a 355 nm laser-based system. The applicant found that it would not be done. Therefore, the inventor finds that such a "direct excitation" mechanism for achieving suitable hybrid curing is inadequate to address the processing reality of modern additive modeling systems utilizing UV / vis optics. They found.

[071] More precisely, surprisingly, a combination of one or more alternative mechanisms is needed instead to achieve sufficient curing in an additive modeling system utilizing UV / vis optics. , The applicant found. The first is due to the "indirect excitation" mechanism. The second is due to the free radical-accelerated cationic polymerization mechanism. The third is due to the vinyl ether polymerization mechanism. As further discussed below, liquid radiation curable compositions for addition shaping made in accordance with the present invention are these to achieve suitable hybrid curing in addition molding processes incorporating UV / vis optics. Synergistically utilize one or more of the mechanisms.

[072] The liquid radiation curable resin composition is in any suitable amount, eg, up to about 15% by weight of the resin composition in certain embodiments, up to about 5% by weight of the resin composition in certain embodiments. In a further embodiment, the cationic photoinitiator may be contained in an amount of about 2% by weight to about 10% by weight of the resin composition, and in another embodiment, an amount of about 0.1% by weight to about 5% by weight of the resin composition. In a further embodiment, the amount of cationic photoinitiator is from about 0.2 wt% to about 4 wt% of the total resin composition and from about 0.5 wt% to about 3 wt% in other embodiments.

[Free radical photoinitiator]
[073] In the embodiment, the liquid radiation curable resin for addition molding of the present invention contains a free radical photoinitiator. According to the embodiment, the liquid radiation curable resin composition comprises a photoinitiator containing at least one photoinitiator having a cation-initiated functional group and at least one photoinitiator having a free radical-initiated functional group. include. In addition, the photoinitiator system may include a photoinitiator containing both a free radical-initiated functional group and a cation-initiated functional group on the same molecule. A photoinitiator is a compound that chemically changes by the action of light or by the action of light and the synergistic action of electron excitation of a sensitizing dye to produce at least one of a radical, an acid, and a base.

[074] Typically, free radical photoinitiators are those that generate radicals by cleavage known as "Norish type I" and those that generate radicals by hydrogen abstraction known as "Norish type II". are categorized. Norish type II photoinitiators require a hydrogen donor that functions as a free radical source. Since initiation is based on a bimolecular reaction, Norish type II photoinitiators are generally slower than Norish type I photoinitiators based on the formation of single molecules of radicals. On the other hand, the Norish type II photoinitiator has better light absorption in the near UV spectroscopic region. Photolysis of aromatic ketones such as benzophenone, thioxanthone, benzyl and quinone in the presence of hydrogen donors such as alcohols, amines and thiols leads to radicals (ketyl-type radicals) generated from carbonyl compounds and hydrogen donors. Radicals and are generated. Photopolymerization of vinyl monomers is usually initiated by radicals generated from hydrogen donors. Ketyl radicals are usually not reactive with vinyl monomers due to steric hindrance and unpaired electron delocalization.

[075] In order to successfully formulate the liquid radiation curable resin for addition shaping, the wavelength sensitivity of the photoinitiator present in the resin composition is scrutinized and activated by a radiation source selected to provide the cured light. It is necessary to decide whether or not it will be transformed.

[076] According to embodiments, the liquid radiation curable resin for addition shaping is at least one free radical photoinitiator, such as a benzoylphosphine oxide, an aryl ketone, a benzophenone, a hydroxylated ketone, a 1-hydroxyphenyl ketone. Includes those selected from the group consisting of ketals, metallocenes, and any combination thereof.

[077] In the embodiment, the liquid radiation curable resin for addition molding is 2,4,6-trimethylbenzoyldiphenylphosphenyl oxide and 2,4,6-trimethylbenzoylphenyl, ethoxyphosphinoxide, bis (2,4,6). -Phenylbenzoyl) -Phenylphosphinoxide, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanol-1,2-benzyl-2- (dimethylamino) -1- [4- (4) -Morphorinyl) Phenyl] -1-butanone, 2-dimethylamino-2- (4-methyl-benzyl) -1- (4-morpholin-4-yl-phenyl) -butane-1-one, 4-benzoyl-4 'Methyldiphenylsulfide, 4,4'-bis (diethylamino) benzophenone, and 4,4'-bis (N, N'-dimethylamino) benzophenone (Michlerketone), benzophenone, 4-methylbenzophenone, 2,4,6- Trimethylbenzophenone, dimethoxybenzophenone, 1-hydroxycyclohexylphenylketone, phenyl (1-hydroxyisopropyl) ketone, 2-hydroxy-1- [4- (2-hydroxyethoxy) phenyl] -2-methyl-1-propanol, 4- Phenylisopropyl (1-hydroxyisopropyl) ketone, oligo- [2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone], camphorquinone, 4,4'-bis (diethylamino) benzophenone, Consists of benzyldimethylketal, bis (η5-2-4-cyclopentadiene-1-yl) bis [2,6-difluoro-3- (1H-pyrrole-1-yl) phenyl] titanium, and any combination thereof. Contains at least one free radical photoinitiator selected from the group.

[078] For light sources that emit light in the 300-475 nm wavelength range, particularly light sources that emit light at 365 nm, 390 nm, or 395 nm, examples of suitable free radical photoinitiators to absorb in this region are benzoylphosphinoxides, such as benzoylphosphinoxide. , 2,4,6-trimethylbenzoyldiphenylphosphenyl oxide (BASF lucillin TPO) and 2,4,6-trimethylbenzoylphenyl, ethoxyphosphinoxide (BASF lucilin TPO-L), bis (2, 4,6-trimethylbenzoyl) -Phenylphosphenyl oxide (Irgacure 819 or BAPO made by Ciba), 2-Methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1 (Irgacure 907 made by Ciba) , 2-benzyl-2- (dimethylamino) -1- [4- (4-morpholinyl) phenyl] -1-butanone (Irgacure 369 made by Ciba), 2-dimethylamino2- (4-methyl-benzyl)- 1- (4-morpholin-4-ylphenyl) -butane-1-one (Irgacure 379 made by Ciba), 4-benzoyl-4'-methyldiphenyl sulfide (Cibacure BMS made by Chitec), 4,4'-bis Examples thereof include (diethylamino) benzophenone (Cibacure EMK manufactured by Chitec) and 4,4'-bis (N, N'-dimethylamino) benzophenone (Mihiler ketone). A mixture thereof is also suitable. These acylphosphine oxide photoinitiators are preferred because they have good delocalization of phosphinoyl radicals upon light irradiation.

[079] According to embodiments of the present invention, the free radical photoinitiator is an acylphosphine oxide photoinitiator. Acylphosphine oxide photoinitiators are, for example, US Pat. Nos. 4,324,744, 4,737,593, 5,942,290, 5,534, US Pat. It is disclosed in the specification 559, 6,020,528, 6,486,228, and 6,486,226.

[080] Acylphosphine oxide The photoinitiator is bisacylphosphine oxide (BAPO) or monoacylphosphine oxide (MAPO).

で示される。
[082]上記式中、Ｒ_５０は、Ｃ_１～Ｃ_１２アルキル、シクロヘキシル、あるいは置換されていないまたは１～４個のハロゲンもしくはＣ_１～Ｃ_８アルキルにより置換されたフェニルであり、Ｒ_５１およびＲ_５２は、それぞれ互いに独立して、Ｃ_１～Ｃ_８アルキルまたはＣ_１～Ｃ_８アルコキシであり、Ｒ_５３は、水素またはＣ_１～Ｃ_８アルキルであり、かつＲ_５４は、水素またはメチルである。 [081] The bisacylphosphine oxide photoinitiator is of formula II :.

Indicated by.
[082] _In the above formula, _R50 is _a phenyl that is C1 to C12 alkyl, cyclohexyl, or undamaged or substituted with ₁ to ₄ halogens or C1 to C8 alkyl, and is _R51 and. R ₅₂ are C ₁ to C ₈ alkyl or C ₁ to C ₈ alkoxy, respectively, independently of each other, R ₅₃ is hydrogen or C ₁ to C ₈ alkyl, and R ₅₄ is hydrogen or methyl. be.

[083] For example, _R50 is a _C2 to _C10 alkyl, cyclohexyl, or phenyl substituted with ₁ to ₄ C1 to C4 alkyls, Cl, or Br. _In other embodiments, R50 is C ₃ to C ₈ alkyl, cyclohexyl, or phenyl substituted with undamaged or 2, 3, 4, or 2, 5 positions with C ₁ to C ₄ alkyl. .. For example, R ₅₀ is C ₄ to C ₁₂ alkyl or cyclohexyl, R ₅₁ and R ₅₂ are independent of each other, C ₁ to C ₈ alkyl or C ₁ to C ₈ alkoxy, and R ₅₃ is hydrogen. Alternatively, it is C ₁ to C ₈ alkyl. For example, R ₅₁ and R ₅₂ are C ₁ to C ₄ alkyl or C ₁ to C ₄ alkoxy, and R ₅₃ is hydrogen or C ₁ to C ₄ alkyl. In other embodiments, R ₅₁ and R ₅₂ are methyl or methoxy, and R ₅₃ is hydrogen or methyl. For example, R ₅₁ , R ₅₂ , and R ₅₃ are methyl. In other embodiments, R ₅₁ , R ₅₂ , and R ₅₃ are methyl and R ₅₄ is hydrogen. _In other embodiments _{, R50} is a C3 to C8 alkyl. For example, R ₅₁ and R ₅₂ are methoxy, R ₅₃ and R ₅₄ are hydrogen, and R ₅₀ is isooctyl. For example, _R50 is isobutyl. For example, _R50 is phenyl. The bisacylphosphine oxide photoinitiator of the present invention is, for example, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (CAS # 1628821-26-7) or bis (2,4,6-trimethylbenzoyl). -(2,4-Bis-pentyloxyphenyl) phosphine oxide.

で示される。上記式中、Ｒ_１およびＲ_２は、互いに独立して、Ｃ_１～Ｃ_１２アルキル、ベンジル、置換されていないまたはハロゲン、Ｃ_１～Ｃ_８アルキル、および／もしくはＣ_１～Ｃ_８アルコキシにより１～４回置換されたフェニルであり、あるいはシクロヘキシルまたは－ＣＯＲ_３基であり、あるいはＲ_１は－ＯＲ_４であり、Ｒ_３は、置換されていないまたはＣ_１～Ｃ_８アルキル、Ｃ_１～Ｃ_８アルコキシ、Ｃ_１～Ｃ_８アルキルチオ、および／もしくはハロゲンにより１～４回置換されたフェニルであり、かつＲ_４は、Ｃ_１～Ｃ_８アルキル、フェニル、またはベンジルである。たとえば、Ｒ_１は－ＯＲ_４である。たとえば、Ｒ_２は、置換されていないまたはハロゲン、Ｃ_１～Ｃ_８アルキル、および／もしくはＣ_１～Ｃ_８アルコキシにより１～４回置換されたフェニルである。たとえば、Ｒ_３は、置換されていないまたはＣ_１～Ｃ_８アルキルにより１～４回置換されたフェニルである。たとえば、本発明のモノアシルホスフィンオキシドは、２，４，６－トリメチルベンゾイルエトキシフェニルホスフィンオキシドまたは２，４，６－トリメチルベンゾイルジフェニルホスフィンオキシドである。 [084] The monoacylphosphine oxide photoinitiator is of formula III :.

Indicated by. In the above formula, R ₁ and R ₂ are independent of each other by C ₁ to C ₁₂ alkyl, benzyl, unsubstituted or halogen, C ₁ to C ₈ alkyl, and / or C ₁ to C ₈ alkoxy. It is phenyl substituted up to 4 times, or cyclohexyl or -COR ₃ groups, or R ₁ is -OR ₄ and R ₃ is unsubstituted or C ₁ to C ₈ alkyl, C ₁ to C. It is a phenyl substituted with ₈ alkoxy, C1 to _C8 alkylthio, and / or halogen ₁ to ₄ times, and _R4 is C1 to _C8 alkyl, phenyl, or benzyl. For example, R ₁ is −OR ₄ . For example, R ₂ is a phenyl that has not been substituted or has been substituted with halogen, C ₁ to C ₈ alkyl, and / or C ₁ to C ₈ alkoxy 1 to 4 times. For example, R ₃ is phenyl that has not been substituted or has been substituted 1 to 4 times with C ₁ to C ₈ alkyl. For example, the monoacylphosphine oxide of the present invention is 2,4,6-trimethylbenzoylethoxyphenylphosphine oxide or 2,4,6-trimethylbenzoyldiphenylphosphine oxide.

[085] The liquid radiation curable resin for addition shaping is in any suitable amount, for example, up to about 10 wt% of the resin composition in certain embodiments, from about 0.1 of the resin composition in certain embodiments. A free radical photoinitiator in an amount of about 10 wt%, and in a further embodiment about 1 to about 6 wt% of the resin composition, may be included as component (d).

[Light start package]
[086] According to certain embodiments, one or more cations and / or free radical photoinitiators are included in the resin composition along with the diluent monomer. Cationic and free radical photoinitiators are those discussed herein and any suitable diluent can be used. Conventional liquid diluents for dispersing certain cationic photoinitiators include (poly) propylene glycol or (poly) propylene carbonate. Surprisingly, the use of vinyl ether as a diluent monomer or dispersant in combination with at least one cationic photoinitiator has improved photopolymerization efficacy when cured under UV / vi optical conditions according to the present invention. The inventors have found that sex is brought about.

[087] In embodiments, the cationic photoinitiator is present in an amount of about 8 wt% to about 50 wt%, more preferably about 30 wt% to about 45 wt%, relative to the total weight of the photoinitiator package, and is vinyl ether diluted. The agent monomer is present in an amount of about 25 wt% to about 90 wt%, more preferably about 40 wt% to about 60 wt%, and the free radical photoinitiator is from about 8 wt% to about 30 wt%, more preferably about 10 wt%. It is present in an amount of ~ about 25 wt%, where the cationic photoinitiator is at least partially dissolved in the solution with the vinyl ether diluent monomer in a ratio of 0.1: 1 to 1: 1.

[088] A second aspect of the claimed invention is:
(A) Cationic polymerizable component and
(B) Iodium salt cation photoinitiator and
(C) A photosensitizer for photosensitizing component (b) and
(D) A first reducing agent for reducing the component (b) and
(E) Free radically polymerizable component and
(F) Optional free radical photoinitiator,
(G) A second reducing agent for reducing the component (b), which has an electron-donating substituent bonded to a vinyl group, and
Including
It gives a dose of 20 mJ / cm ² and emits radiation with a peak spectral intensity of about 375 nm to about 500 nm, more preferably about 380 nm to about 450 nm, more preferably about 390 nm to about 425 nm, more preferably about 395 nm to about 410 nm. Can be cured by UV / vis optical elements,
It is a liquid radiation curable composition for addition molding.

[089] The cationically polymerizable component, the free radically polymerizable component, and the free radical photoinitiator according to the first aspect of the present invention are similarly suitable for use in the second aspect of the claimed invention. Is. Furthermore, the above description of the iodonium salt cation photoinitiator according to the first aspect of the claimed invention is also similarly suitable for use in the second aspect of the claimed invention. In a preferred embodiment, the iodonium salt cationic photoinitiator is a diphenyliodonium salt. Some suitable diphenyliodonium salt photoinitiators are, for example, (4-methylphenyl) [4- (2-methylpropyl) phenyl]-, hexafluorophosphate, [4- (1-methylethyl) phenyl] ( 4-Methylphenyl)-, tetrakis (pentafluorophenyl) borate (1-) (bis (4-dodecylphenyl) iodonium hexafluoroantimonate), and (bis (4-tert-butylphenyl) iodonium hexaflurol phosphate) Is.

[Photosensitizer]
[090] In some embodiments, it is desirable that the liquid radiation curable resin composition comprises a photosensitizer, depending on the wavelength of light used to cure the liquid radiation curable resin. The term "photosensitizer" is used to mean any substance that either increases the rate of photoinitiative polymerization or shifts the wavelength at which polymerization occurs. See the textbook (G. Odian, Principles of Polymerization, 3rd Edition, 1991, p. 222). A substance that works with the latter definition and is used in combination with a photoinitiator that does not otherwise absorb light of a particular wavelength is said to work with its associated photoinitiator by an "indirect excitation" mechanism. Applicants have utilized this mechanism to formulate compositions of the invention suitable for curing with UV / vis optics.

[091] Various compounds such as heterocyclic and fused ring aromatic hydrocarbons, organic dyes, and aromatic ketones can be used as photosensitizers. Examples of photosensitizers include those selected from the group consisting of methanone, xanthenone, pyrenemethanol, anthracene, pyrene, perylene, quinone, xanthone, thioxanthone, benzoyl ester, benzophenone, and any combination thereof. .. Specific examples of the photosensitizer include [4-[(4-methylphenyl) thio] phenyl] phenylmethanone, isopropyl-9H-thioxanthene-9-one, 1-pyrenemethanol, and 9- (hydroxymethyl). Anthracene, 9,10-diethoxyanthracene, 9,10-dimethoxyanthracene, 9,10-dipropoxyanthracene, 9,10-dibutyloxyanthracene, 9-anthracene methanol acetate, 2-ethyl-9,10-dimethoxyanthracene, 2-Methyl-9,10-dimethoxyanthracene, 2-t-butyl-9,10-dimethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, and 2-methyl-9,10-diethoxyanthracene, anthracene , Anthracene, 2-Methylanthracene, 2-Ethracenetraquinone, 2-tertbutylanthracene, 1-chloroanthracene, 2-amylanthracene, thioxanthone and xanthone, isopropylthioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthone, 1- Chloro-4-propoxythioxanthone, methylbenzoylformate (BASF's Darocur MBF), methyl-2-benzoylbenzoate (Chitech's Cibacure OMB), 4-benzoyl-4'-methyldiphenylsulfide (Chitech's) CibaCure BMS), 4,4'-bis (diethylamino) benzophenone (CibaCure EMK manufactured by Chitec), and any combination thereof selected from the group.

[092] The novel mixture may also contain various photoinitiators with different sensitivities to emission line radiation of different wavelengths in order to achieve better utilization of UV light sources. The use of known photoinitiators with different sensitivities to emission line radiation is well known in the art of additive modeling and can be selected according to, for example, 351 nm, 355 nm, 365 nm, 385 nm, and 405 nm radio sources. In this context, it is advantageous to select different photoinitiators to produce equal light absorption at the emission lines used and utilize them at such concentrations.

およびそれらの任意の組合せである。 [093] In embodiments, the photosensitizer is a fluorone, eg, 5,7-diiodo-3-butoxy-6-fluorone, 5,7-diiodo-3-hydroxy-6-fluoroone, 9-cyano-5. , 7-Diode-3-hydroxy-6-fluoroone, or the photosensitizer is

And any combination thereof.

[094] When a photosensitizer is used, other photoinitiators that absorb at shorter wavelengths can be used. Examples of such photoinitiators include benzophenones such as benzophenone, 4-methylbenzophenone, 2,4,6-trimethylbenzophenone and dimethoxybenzophenone, and 1-hydroxycyclohexylphenylketone, phenyl (1-hydroxyisopropyl) ketone, 2 -Hydroxy-1- [4- (2-hydroxyethoxy) phenyl] -2-methyl-1-propanol, and 1-hydroxyphenylketones such as 4-isopropylphenyl (1-hydroxyisopropyl) ketone, benzyldimethylketal, And oligo- [2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone] (Esacure KIP150 from Lamberti).

It is noteworthy that some cationic photoinitiators have low absorption at preferred chemical ray wavelengths. For example, in an embodiment, a UV / optical device having a peak intensity of about 400 nm is used in the subject additive modeling application. For example, Rhodolucyl 2074 available from Rhodia Silicones, Irgacure 250 iodonium, (4-methylphenyl) [4- (2-methylpropyl) phenyl] hexafluorophosphate (1-) available from Ciba. ), Iodonium salts such as UV9380c available from GE Silicones have inadequate direct absorption at preferred wavelengths and therefore require excessive concentrations or sensitizers. Therefore, triplet sensitizers such as thioxanthone and Michlerketone may be used to absorb chemical beam energy and efficiently transfer that energy to the iodonium initiator. However, some thioxanthones and Michler ketones tend to produce an orange or red color, are of concern for safety, and have significant chemical ray absorption up to 430 nm but photoreact at a cured light wavelength of about 400 nm. Not very effective at sensitizing.

[096] However, in embodiments, chloropropylthioxanthone (CPTX) is a suitable sensitizer, especially for iodonium initiators for use in stereolithography. This is because above 500 nm it does not have significant light absorption and forms articles with less coloration.

[097] High extinction coefficient at 400 nm to reduce the concentration of sensitizers used in the formulation and prevent adverse effects that may result from relatively high concentrations of sensitizers with respect to the final physical properties of the composition. It is preferable to use a sensitizer having the above. For example, benzophenone can act as a triplet sensitizer in some cases, but at the laser wavelength of a frequency triplet YAG laser (Coherent AVIA model # 355-1800) operating at about 355 nm, for example. The absorption coefficient is about 108 liters / mol · cm. On the other hand, CPTX when the same laser is used at the same laser wavelength of about 400 nm has an extinction coefficient of approximately X times that of benzophenone, that is, 2585 liters / mol · cm. This suggests that CPTX may require a concentration of 1 / X in the formulation to provide an equivalent light absorption effect. Therefore, the sensitizer preferably has an extinction coefficient of 300 liters / mol cm or more, for example, 1000 liters / mol cm or more, preferably 2000 liters / mol cm or more at a cured light wavelength of more than 380 nm. However, it is not necessary to do so.

[098] It is taught that CPTX can be used to improve the activity of the cationic photoinitiator, but the sensitizers used in combination with the cationic photoinitiator described above are not necessarily limited thereto. Not exclusively. Various compounds such as heterocyclic and fused ring aromatic hydrocarbons, organic dyes, and aromatic ketones can be used as photosensitizers. Examples of sensitizers include J. V. Crivello, Advances in Polymer Science, Vol. 62, No. 1 (1984), and J. Mol. V. Crivello and K. Dietliker, Photoinitiator's for Chemical Polymerization, Chemistry & technology of UV & EB formation for photoinitiator, inks & cations, (Photoinitiators for free radical and chemical polymerization), K. et al. By Dietliker, [P. K. T. Oldring], SITA Technology Ltd, London, 1991. Specific examples include polycyclic aromatic hydrocarbons and their derivatives such as anthracene, pyrene, perylene and their derivatives, substituted thioxanthone, α-hydroxyalkylphenone, 4-benzoyl-4'-methyldiphenylsulfide, acridine orange. , And benzoflavin.

[099] The liquid radiation curable resin for addition molding is in an arbitrary suitable amount, for example, 0.1 to 10 wt% of the resin composition in a specific embodiment, and about 1 to 1 to 10 wt% of the resin composition in a specific embodiment. It may contain about 8 wt%, and in a further embodiment, about 2 to about 6 wt% of other cationic photoinitiators or photosensitizers. In embodiments, the above ranges are particularly suitable for use with epoxy monomers. In other embodiments, the photosensitizer is available in an amount of about 0.05% to about 2% by weight of the total composition incorporated.

[Reducing agent]
[0100] As used herein, a reducing agent is a component that loses one or more electrons, that is, a cationic photoinitiator component that undergoes a redox chemical reaction during polymerization of the liquid radiation composition for addition molding according to the present invention. A component that "donates" one or more electrons. Such components may have the ability to easily donate electrons until they generate free radicals, i.e., decompose into free radicals after dissociation, or else they are exposed to chemical rays of UV / vis wavelength and are excited. If not, it is still considered a reducing agent for the purposes of the present invention. Therefore, in the present specification, it can be referred to as an "activation reducing agent" instead.

[0101] Photo-initiated cationic polymerization of monomers such as epoxides and vinyl ethers plays a required role in hybrid curable addition molding applications. Due to the use of additives in a variety of applications, wavelength flexibility at the start of light is a fundamental factor in determining the cure performance of a particular formulation when targeting a particular spectral sensitivity. Therefore, photoinitiation systems for cationic polymerization, which are sensitive to longer wavelengths, such as those emitted by modern UV / vis optics, are becoming more important. Many of the existing photoinitiation systems for cationic polymerization are based on the use of onium salts such as diphenyliodonium salt, triphenylsulfonium salt, alkoxypyridinium salt. However, these salts do not absorb significantly (if absorbed) in the UV / vis spectrum unless additional chromophores are incorporated into the salt structure. Therefore, it is readily available, especially in light of the fact that commercially available photoinitiators already designed for absorption in the UV / vis spectral range are not suitable for incorporation into hybrid curing systems for additional modeling for other reasons. It is important to find alternatives that synthetically extend the sensitive region of possible onium salts to UV / vis wavelengths.

[0102] As discussed herein, Applicants have achieved at least in part by a mechanism called indirect excitation utilizing a combination of sensitizers. In addition, the onium salt acts as an electron acceptor in a redox reaction in combination with a free radical, an electron donor compound of a charge transfer complex, and a long-lived electron excited state of a sensitizer. Of these methods, so-called "free radical-promoted" cationic polymerization appears to be an additional effective and flexible method for generating cationic species capable of initiating cationic polymerization of monomers. The overall mechanism involves the oxidation of photochemically formed radicals with an onium salt (On +) having a suitable reduction potential.
R ・ ＋ ON ＋ → R ＋ (1)

[0103] Suitable reducing agents for promoting free radical-accelerated cationic polymerization are generally on amines, benzoins and derivatives thereof, o-fataldehide, polysilanes, and vinyl groups such as vinyl ethers and vinyl halides, to name a few. Includes some of the above mentioned free radical photoinitiators, such as acylphosphine oxides, as well as compounds with attached electron donating substituents.

[0104] Amines are considered to be effective hydrogen donors and will readily form free radicals by chain transfer mechanism that reduce the associated cationic photoinitiators. Therefore, in certain embodiments, it can act as a suitable reducing agent. However, it is known that the nitrogen atoms contained therein tend to inhibit the cationic polymerization reaction in addition to the above, so care must be taken when such compounds are contained in the hybrid radiocurable composition for addition shaping. ..

[0105] There are several systems that generate oxidative radicals in the presence of UV / vis light sources. For example, radicals formed by irradiating a system containing a xanthene dye and an aromatic amine can function as a reducing agent for a diphenyliodonium salt. Similarly, the dimanganese decacarbonyl-organic halide combination is an effective reducing agent for cationic polymerization at UV / vis wavelengths when used in combination with onium salts. In addition, a commercially available titanocene-type photoinitiator such as Irgacure 784 can be used as a reducing agent source generated by irradiation with visible light.

[0106] Acylphosphine oxides and acylphosphanates having various structures have been used as photoinitiators for free radical polymerization. Extensive studies on the photochemistry of acylphosphine oxides have shown that they undergo alpha cleavage with fairly high quantum yields.

[0107] In embodiments, acylphosphine oxide, when combined at least in combination with a second reducing agent having an electron donating substituent attached to a vinyl group, promotes cationic polymerization of suitable monomers at UV / vis wavelengths. It is a suitable reducing agent that contributes. Cationic polymerization of tetrahydrofuran and butyl vinyl ethers can be easily initiated by irradiation at UV / vis wavelengths in the presence of bisacylphosphine oxides and diphenyliodonium salts. Although not desired to be constrained by theory, photoinitiated bisacylphosphine oxides readily desorb hydrogen from a suitable donor (eg, solvent or monomer) and become a reducing agent when used in combination with a cationic photoinitiator. It is considered to be. The obtained carbon center radical is converted into a carbocation by a reaction with PhI + ion to initiate cationic polymerization. As disclosed herein, acylphosphine oxides, more preferably substituted acylphosphine oxides, promote free cationic polymerization at UV / vis cure wavelengths when combined with suitable onium salts such as iodonium and pyridinium salts. It has been found to be an efficient and effective reducing agent for this purpose. The proposed initiation mechanism appears to involve photogeneration of phosphinoyl and benzoyl radicals in the first step. The onium salt then oxidizes the phosphinoyl radical to produce phosphonium ions capable of initiating the polymerization of the monomer. The efficiency of the latter step should be controlled by the redox potential of the onium salt and the electron delocalization (p property) of the phosphinoyl radical. Therefore, one embodiment of the invention is a redox between the onium salt and the acylphosphine oxide free radical photoinitiator so that the effect of this mechanism is maximized with 400 nm wavelength light and the maximum cationic curing speed is achieved. At the same time as maximizing the potential, it is to search for an acylphosphine oxide having a maximum electron delocalization (p characteristic).

により表される。上記式中、Ａｒ_１は、置換または非置換の芳香族基であり、Ｒ_１は、Ａｒ_１、Ｃ_２～Ｃ_２０脂肪族鎖、またはＣ_２～Ｃ_２０アルキル鎖であり、かつＲ_２は、Ｒ_１であるかまたは１個以上の置換もしくは非置換のアシルフェニル基を含有する。 [0108] In the embodiment, the reducing agent for reducing the cationic photoinitiator is the following formula IV:

Represented by. In the above formula, Ar ₁ is a substituted or unsubstituted aromatic group, R ₁ is an Ar ₁ , C ₂ to C ₂₀ aliphatic chain, or C ₂ to C ₂₀ alkyl chain, and R ₂ is. , R ₁ or contains one or more substituted or unsubstituted acylphenyl groups.

[0109] The liquid radiation curable resin for addition molding is, for example, an arbitrary suitable amount in a specific embodiment, an amount of 0.01 to 30 wt% in a specific embodiment, and a resin composition in another preferred embodiment. Cationic photoinitiators in an amount of 0.01-10 wt%, in certain other embodiments from about 1 to about 8 wt% of the resin composition, and in further embodiments from about 2 to about 6 wt% of the resin composition. May include a reducing agent for reducing. In the embodiment, the above range is particularly suitable when the iodonium salt photoinitiator is used in combination. In embodiments, both free radical polymerization and cationic polymerization are promoted simultaneously, as the same reducing agent component can simultaneously function as a free radical photoinitiator and reducing agent. In other embodiments, the reducing agent is available in an amount of about 0.05% to about 4% by weight of the total composition incorporated.

[Reducing agent having an electron-donating substituent bonded to a vinyl group]
[0110] By additionally including a component having an electron donating substituent bonded to a vinyl group, the cationic curing of the liquid radiation curable composition for an addition molding system utilizing a UV / vis optical element is improved. Further mechanisms can be provided. Such compounds, such as vinyl ethers, are excessive in many modern commercial hybrid curable compositions used in additive shaping systems that utilize traditional UV-based radiation sources: (1) due to the exothermic reaction of rapid polymerization. It is avoided because it tends to generate heat and (2) it tends to result in copolymerization and incidental heterogeneous polymers to produce inconsistent and inferior physical properties. .. Nonetheless, surprisingly, when used in combination with other requirements of the invention, to compositions tailored to suit systems utilizing UV / vis optics with lower energy / intensity. We have found that integration is desirable. Specifically, by including an additional component with an electron donating substituent attached to a vinyl group, surprisingly, the other reaction mechanisms cited herein (ie, indirect excitation and free radicals). The inventor has further found that the polymerization is synergistically improved with the presence of a component that induces (accelerated cationic polymerization).

[0111] A preferred example of a component having an electron donating substituent attached to a vinyl group is vinyl ether. Vinyl ethers can be produced from a variety of starting materials, such as ethers, esters, or biscarbamates, or vinyl ether-terminated (poly) urethanes or carbonates. Some examples, but not limited to, of each include:

[0112] Vinyl Ether Monomer from Ether: Specific examples of polyfunctional vinyl ethers include divinyl ethers such as ethylene glycol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, polyethylene glycol divinyl ether, propylene glycol divinyl ether, and divinyl ether. Propropylene glycol divinyl ether, isobutyl vinyl ether, butylene glycol divinyl ether, butanediol divinyl ether, hexanediol divinyl ether, cyclohexanediol divinyl ether, bisphenol A alkylene oxide divinyl ether, and bisphenol F alkylene oxide divinyl ether, and polyfunctional vinyl ethers, for example. , Trimethylol ethanetrivinyl ether, trimethylolpropane trivinyl ether, ditrimethylolpropane tetravinyl ether, glycerol trivinyl ether, pentaerythritol tetravinyl ether, pentaerythritol divinyl ether, dipentaerythritol pentavinyl ether, dipentaerythritol hexavinyl ether, trimethylolpropanetrivinyl ether Ethylene oxide adduct, Trimethylol propanetrivinyl ether propylene oxide adduct, Ditrimethylol propanetetravinyl ether ethylene oxide adduct, Ditrimethylol propanetetravinyl ether propylene oxide adduct, pentaerythritol tetravinyl ether ethylene oxide adduct, pentaerythritol tetravinyl ether Examples thereof include propylene oxide adducts of dipentaerythritol hexavinyl ether, ethylene oxide adducts of dipentaerythritol hexavinyl ether, and propylene oxide adducts of dipentaerythritol hexavinyl ether.

[0113] Vinyl ether monomers from esters or biscarbamates: Specific examples of polyfunctional vinyl ethers such as divinyl adipate, divinyl terephthalate, divinyl cyclohexyl dicaroxylate. Bis [4- (vinyloxy) butyl] adipate (Vectomer (registered trademark) 4060), bis [4- (vinyloxy) butyl] succinate (Vectomer (registered trademark) 4030), bis [4- (vinyloxy) butyl] Isophthalt (Vectomer® 4010), Bis [4- (vinyloxymethyl) cyclohexylmethyl] glutarate (Vectomer® 4020), Tris [4- (vinyloxy) butyl] trimellitate (Vectomer® 5015) , Bis [4- (vinyloxymethyl) cyclohexylmethyl] isophthalate (Vectomer® 4040), bis [4- (vinyloxy) butyl] (4-methyl-1,3-phenylene) biscarbamate (Vectomer (registered) 4220), and bis [4- (vinyloxy) butyl] (methylenedi-4,1-phenylene) biscarbamate (Vectomer (registered trademark) 4210) and the like.

[0114] Vinyl ether-terminated urethane or carbonate: Specific examples of polyfunctional vinyl ethers such as polyurethane and polycarbonate endcapped with hydroxyvinyl ether having at least a hydroxyl group and at least a vinyl ether group in the molecule. For example, 2-hydroxyethyl vinyl ether, 3-hydroxypropyl vinyl ether, 2-hydroxypropyl vinyl ether, 2-hydroxyisopropyl vinyl ether, 4-hydroxybutyl vinyl ether, 3-hydroxybutyl vinyl ether, 2-hydroxybutyl vinyl ether, 3-hydroxyisobutyl vinyl ether. , 2-Hydroxyisobutyl vinyl ether, 1-methyl-3-hydroxypropyl vinyl ether, 1-methyl-2-hydroxypropyl vinyl ether, 1-hydroxymethylpropyl vinyl ether, 4-hydroxycyclohexylvinyl ether, 1,6-hexanediol monovinyl ether, 1 , 4-Cyclohexanedimethanol monovinyl ether, 1,3-Cyclohexanedimethanol monovinyl ether, 1,2-Cyclohexanedimethanol monovinyl ether, p-xylene glycol monovinyl ether, m-xylene glycol monovinyl ether, o-xylene glycol monovinyl ether, Diethylene-Glycol Monovinyl Ether, Triethylene Glycol Monovinyl Ether, Tetraethylene Glycol Monovinyl Ether, Pentaethylene Glycol Monovinyl Ether, Oligoethylene Glycol Monovinyl Ether, Polyethylene Glycol Monovinyl Ether, Dipropylene Glycol Monovinyl Ether, Tripropylene Glycol Monovinyl Ether, Tetrapropylene Glycol Monovinyl ethers, derivatives thereof, such as pentapropylene glycol monovinyl ethers, oligopropylene glycol monovinyl ethers, and polypropylene glycol monovinyl ethers.

[0115] In a preferred embodiment, the components having an electron donating substituent attached to a vinyl group are: vinyl ether, vinyl ester, vinyl thioether, n-vinylcarbazole, n-vinylpyrrolidone, n-. One or more of vinyl caprolactam, allyl ether, and vinyl carbonate.

[0116] In another preferred embodiment, the component having an electron donating substituent attached to a vinyl group is polyfunctional.

[0117] One or more of the above-mentioned components having an electron-donating substituent bonded to a vinyl group can be used in any suitable amount in the composition according to the present invention, alone or herein. You can choose from one or more combinations of the listed types. In a preferred embodiment, the component having an electron donating substituent attached to a vinyl group is about 1 wt. % ~ About 25 wt. %, More preferably about 5 wt. % ~ About 20 wt. %, More preferably about 5 wt. % ~ About 12 wt. It is present in the amount of%. In another embodiment, the component having an electron donating substituent bonded to a vinyl group is 1 wt. % ~ 15 wt. %, More preferably 1 wt. % To 10 wt%, more preferably 3 wt. % ~ About 8 wt. It is present in the amount of%.

[Other ingredients]
[0118] Stabilizers are often added to the resin composition to further prevent the increase in viscosity, eg, the increase in viscosity during use in the solid image forming process. Useful stabilizers include those described in US Pat. No. 5,665,792. The presence of stabilizers is optional. In a specific embodiment, the liquid radiation curable resin composition for addition molding contains 0.1 wt% to 3% stabilizer.

[0119] Other available additives include organic and inorganic fillers, dyes, pigments, antioxidants, wetting agents, bubble disintegrants, chain transfer agents, leveling agents, defoaming agents, surfactants, etc. Can be mentioned. Such additives are known and, as will be appreciated by those skilled in the art, are generally available upon the request of a particular application.

[0120] The liquid radiation curable resin composition for addition molding of the present invention comprises a bubble disintegrant, an antioxidant, a surfactant, an acid trapping agent, a pigment, a dye, a thickener, a flame retardant, a silane coupling agent, and the like. It may further comprise one or more additives selected from the group consisting of UV absorbers, resin particles, core-shell particle impact resistance improvers, soluble polymers, and block polymers.

[0121] In addition, many of the known liquid radiation curable resin compositions for addition molding use hydroxy functional compounds to improve the properties of parts made from the resin compositions. Any hydroxy group, if present, can be used for a particular purpose. If present, the hydroxyl-containing material preferably contains one or more primary or secondary aliphatic hydroxyl groups. Hydroxy groups can be intramolecular or terminal. Monomers, oligomers, or polymers can be used. The hydroxyl equivalent, i.e., the number average molecular weight divided by the number of hydroxyl groups, is preferably in the range of 31-5000. If present, the resin composition is preferably one or more non-free radical polymerizations of at most 10 wt%, more preferably at most 5 wt%, most preferably at most 2 wt% based on the total weight of the resin composition. Includes sex hydroxy functional compounds.

[ratio]
[0122] Surprisingly, the compositions according to the invention were particularly optimized for curing by certain additive shaping processes utilizing UV / vis optics, provided that the ratios of the various required components were controlled from each other. We have found that it can be in a state. In a preferred embodiment, the weight ratio of the iodonium salt cation photoinitiator, the photosensitizer, the first reducing agent and the second reducing agent having an electron donating substituent attached to a vinyl group is , About 2: 2: 1: 2 to about 20: 1: 5: 25, more preferably about 10: 1: 2: 12. If the amount of iodonium salt cation photoinitiator is too high, the radiation absorption will be too significant and the ability to cure to a sufficiently deep layer will be impaired. If it is too low compared to the other components, it will not reach the level required to produce a 3D component with adequate green strength even when cationic curing is initiated. The amount of photosensitizer should generally not exceed the amount of iodonium salt cationic photoinitiator, but should be present in sufficient quantity to allow indirect excitation of said cationic photoinitiator. The reducing agent should also generally not exceed the amount of cationic photoinitiator to be reduced, but should also be present in sufficient quantity to promote free radical-accelerated cationic polymerization. Finally, the component with the electron donating substituent attached to the vinyl group is in maximum amount on a weight basis compared to the other components listed above in order to fully enable additional cationic polymerization mechanisms. Although present, it should not be present in disproportionately large amounts as it can accelerate curing and lead to uncontrolled exothermic reactions and excessive heat generation.

[0123] In other embodiments, the ratio of iodonium salt cation photoinitiator to photosensitizer is from 1: 3 to 10: 1. In embodiments, the ratio of iodonium salt cation photoinitiator to reducing agent is 1: 5-10: 1.

（式中、ＲはＣ_１～Ｃ_２０脂肪族鎖を含有する）
で示される約０．５ｗｔ．％～約３ｗｔ．％の化合物と、
（ｄ）フリーラジカル重合性成分と、
（ｅ）ジフェニル（２，４，６－トリメチルベンゾイル）ホスフィンオキシドフリーラジカル光開始剤と、
を含み、
２０ｍＪ／ｃｍ^２の線量を与えるかつピークスペクトル強度で約３７５ｎｍ～約５００ｎｍ、より好ましくは約３８０ｎｍ～約４５０ｎｍ、より好ましくは約３９０ｎｍ～約４２５ｎｍの放射線を放出するＵＶ／ｖｉｓ光学素子により硬化可能である、
付加造形用液状放射線硬化性組成物である。 [0124] A third aspect of the claimed invention is:
(A) Approximately 30 wt. Further containing a cyclic aliphatic epoxide and oxetane. % ~ About 80 wt. % With at least one cationically polymerizable component,
(B) Approximately 1 wt. With an absorbance of less than 0.01 at 400 nm. % ~ About 8 wt. % Sulfonium salt cation photoinitiator,
(C) The following formula (V):

(In the formula, R contains C ₁ to C ₂₀ aliphatic chains)
Approximately 0.5 wt. Indicated by. % ~ About 3 wt. % Compound and
(D) Free radically polymerizable component and
(E) Diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide-free radical photoinitiator,
Including
It can be cured by a UV / vis optical device that gives a dose of 20 mJ / cm ² and emits radiation with a peak spectral intensity of about 375 nm to about 500 nm, more preferably about 380 nm to about 450 nm, more preferably about 390 nm to about 425 nm. be,
It is a liquid radiation curable composition for addition molding.

[0125] According to another aspect of the invention, the cationic photoinitiator used in the formulation of liquid radiation curable compositions for addition shaping that can be cured by UV / vis optics is a sulfonium salt. The above description of the sulfonium salt cation photoinitiator according to the first aspect of the claimed invention is similarly suitable for the use of this third aspect of the claimed invention. In a preferred embodiment of the third aspect of the invention, the cationic photoinitiator is a triarylsulfonium salt. In a preferred embodiment, the (triaryl) sulfonium salt cationic photoinitiator actually has a very low direct absorbance at the UV / vis wavelength. In embodiments, the (triaryl) sulfonium salt photoinitiator used has an absorbance of less than 0.05, more preferably less than 0.01, more preferably less than 0.005, most preferably less than 0.001 at 400 nm. Has. Surprisingly, as described, indirect excitation of the cationic photoinitiator has a significant absorbance at 400 nm in initiating cationic polymerization of the liquid radiation curable composition for addition shaping using UV / vis optics. Applicants have found that it is a preferred mechanism over direct excitation of cationic photoinitiators with.

で示されるカチオンを有するトリアリールスルホニウム塩である。 [0126] In the embodiment, the sulfonium salt cation photoinitiator has the following structure:

It is a triarylsulfonium salt having a cation represented by.

[0127] In embodiments, the triarylsulfonium salt further comprises a hexafluoroantimonate counterion or a hexafluorophosphate counterion.

[0128] In the embodiment, the sulfonium salt cation photoinitiator is in any suitable amount of 0.01 wt% to 15 wt%, 1 wt% to 8 wt% in other embodiments and 2 wt% to 5 wt% in other embodiments. Present in the composition.

[0129] Further, the cationically polymerizable component and the free radically polymerizable component according to the first and second aspects of the present invention are similarly suitable for use in the third aspect of the claimed invention.

[0130] The liquid radiation curable composition for addition molding according to the third aspect of the present invention also contains a free radical photoinitiator. The description of the free radical photoinitiator according to the first and second aspects of the invention is generally similarly suitable for use in the third aspect of the claimed invention. However, in a preferred embodiment, the free radical photoinitiator comprises diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide. Further, surprisingly, in embodiments, the free radical photoinitiator component is less than 50% containing two or more carboxyl groups relative to the total amount of free radical photoinitiator present in the composition. We have found that when a compound, preferably less than 33% of a compound containing two or more carboxyl radicals, can be used in combination with a sulfonium salt cation photoinitiator to produce improved curability. I found it.

（式中、ＲはＣ_１～Ｃ_２０脂肪族鎖を含有する）
で示される構造を有する。 [0131] The liquid radiation curable composition for addition molding according to the third aspect of the present invention also contains a photosensitizer. In embodiments, the photosensitizer is generally selectable according to the description of the photosensitizer according to the second aspect of the invention. In a preferred embodiment, the photosensitizer utilized is the following formula (V):

(In the formula, R contains C ₁ to C ₂₀ aliphatic chains)
It has the structure shown by.

[0132] In a preferred embodiment of the third aspect of the invention, the photosensitizer utilized is an anthracene-based photoinitiator. Commercially available products of such photosensitizers include Anthracure ™ UVS-1101 and UVS-1331 available from Kawasaki Chemical.

[0133] The photosensitizer is about 0.5 wt. % ~ About 10 wt. %, More preferably 0.5 wt. % To 3 wt. % Is present in any suitable amount.

[0134] A fourth aspect of the claimed invention is a method of forming a three-dimensional article by an additive modeling system utilizing a UV / vis optical element.
(1) A step of providing the liquid radiation curable composition for addition molding according to the first, second, or third aspect of the present invention.
(2) The step of providing the first liquid layer of the liquid radiation curable resin and
(3) A step of forming the first cured layer by exposing the first liquid layer like an image with a chemical line using a UV / vis optical configuration to form an image-forming cross section.
(4) A step of forming a new layer of liquid thermosetting resin in contact with the first cured layer, and
(5) A step of exposing the new layer like an image with a chemical line to form an additional image-forming cross-section.
(6) A step of repeating steps (4) and (5) a sufficient number of times to construct a three-dimensional article, and
Including
The UV / vis optics emit radiation with a peak spectral intensity of about 375 nm to about 500 nm, more preferably about 380 nm to about 450 nm, more preferably about 390 nm to about 425 nm, more preferably about 395 nm to about 410 nm.
The method.

[0135] The liquid radiation curable composition provided in the aspect of the present invention described above must be suitable for curing by an additive modeling system utilizing a UV / vis optical element. Such compositions are specifically described in the first, second, and third aspects of the invention. When providing the first liquid layer or forming a new layer of liquid thermosetting resin, the layer can take any suitable thickness and shape and depends on the additive shaping process utilized. For example, it can be selectively dispensed by jet processing, or a layer that has already been cured, as is often the case in most stereolithography processes, is immersed in a resin vat to produce a layer of substantially uniform thickness. Can be added by In other embodiments, but not limited to, cartridges or dispensers can be used to alternative transfer to a predetermined thickness via a foil, membrane, or carrier.

[0136] In the above, "exposure" means to irradiate chemical rays. As described above, the liquid radiation composition for addition molding of the present invention described herein is particularly suitable for applying hybrid curing via UV / vis optics. In embodiments, the UV / vis optics utilize one or more LEDs as a light source. In embodiments, the light source is a laser. In embodiments, the LED or laser light source is coupled to a DLP or LCD image projection system. In embodiments where the image projection system includes an LCD display, the light source may be configured to emit chemical rays greater than 400 nm exclusively to minimize the adverse effects of UV wavelengths on the LCD components.

[0137] The fifth aspect of the claimed invention is formed by the fourth aspect of the present invention using the liquid radiation curable composition of the first, second or third aspect of the present invention. It is a three-dimensional component.

[0138] The following examples further illustrate the invention, but of course should not be construed as limiting its scope in any way.

[Example]
[0139] These examples exemplify the embodiment of the liquid radiation curable resin for addition molding of the present invention. Table 1 shows various components of the liquid radiation curable resin for addition molding used in the examples of the present invention.

[Test method]
[0140] Real-time Fourier Transform Infrared (FTIR) spectroscopy was used to measure the polymerization rate (curing speed) of each example. A mercury cadmium telluride (MCT) detector was used to increase the data acquisition frequency and even the resolution. An attenuated total reflection (ATR) configuration was used instead of the transmission mode. All polymerization rate measurements were performed using the Thermo Scientific Nicorette 8700 model. The table below shows the experimental condition settings for the measurement. Under this condition, a total of 41 spectra were obtained in 200 seconds for each measurement.

[0141] A Digital Light Lab LED spot lamp (365 nm, 395 nm, and 400 nm) and a controller (AccuCure Photo Rheometer) were used for UV / Vis light control. The calibration continuous mode was selected. Light intensity and duration (exposure time) were selected prior to measurement.

[0142] For measurement, a few drops of the selected sample are placed in the center of the ATR crystal setup. Then, about 3 mil film (± 0.4 mil) was coated on the ATR crystal using a 3 mil (± 0.4 mil) drawdown bird bar. Immediately after applying the 3-mil coating, the LED lamp was held on top of the ATR setup and positioned in the hole at the center of holding. Then, real-time FTIR scanning was started. After acquiring one spectrum, the light source was turned on to initiate polymerization. Based on the above program input, each spectrum was acquired every 5 seconds for a total of 200 seconds. A total of 41 spectra were obtained in each experiment.

[0143] Polymerization conversion-to-time was calculated based on the specific IR peak changes representing each functional group. Examples of IR peak changes are shown in the above picture. To calculate the conversion of each related functional group, the peak height or peak area was calculated according to the table below as needed.

[0144] When using the raw data obtained, the first 1-because the experimental cure speed procedure has an unknown short time lag between the turn-on of the FTIR detector and the turn-on of the light source used to cure the sample. It was important to remove the two data points. Three curve fits were created for each dataset to compensate for any uncertainty associated with the amount of statistical noise generated by these preliminary data points. In each case, the model formula used to fit the dataset was Conv = a (1-e (-b * (time-c))). To this end, raw data was fitted using Microsoft Excel version 14.0.7116.5000 (32-bit) with a data analysis add-on.

[0145] In the first case, the entire data set (including the first two data points) was fitted. In the second case, the first data point was subtracted from the entire data set to fit. In the third case, the first and second data points were subtracted from the entire data set to fit. In ^each case, the curve fitting coefficient r2 was generated. A dataset was selected and used that had a first data point with a conversion rate of greater than 1% and the combined curve fitting yielded r2 greater ^than 0.90, and the results of the obtained curve fitting equation were plateau converted. Used for further calculation of cure speed at 95% of rate. If the curve fitting factor r ² was less than 0.90, the data was rerun.

[0146] As discussed above, the data fit into the formula Conv = a (1-e (-b * (time-c))). In the formula, "Conv" is the conversion rate% measured by the FTIR peak ratio, time is the exposure duration, "a" is the plateau conversion rate, and "b" is the curing speed. It is the obtained derived curing speed coefficient used for the above-mentioned, and "c" is the obtained derived curing induction time. After fitting the data, software created an experimental derivation formula containing the experimental data and the numerical parameters of "a", "b", and "c" determined from the fitting. For cationically curable materials (ie, epoxies and oxetane), the "c" has no meaning because there is no cure induction time. Therefore, in such a case, "c" was ignored. The variable "a" is used as the plateau conversion rate under the curing conditions used and represents the overall asymptotic range in which the components are converted. The variable "b" was used to calculate the time of the 95% plateau conversion rate (T ₉₅ ) of "a" by the equation T ₉₅ = ln (.05 / b). T- ₉₅ is set forth in Tables 2, 3 and 4 as needed (and if available).

[Examples 1 to 8]
[0147] First, a base for addition molding by combining an oxetane component, a cyclic aliphatic epoxide component, a polyol component, a glycidyl ether epoxide component, and an acrylate component according to a method well known in the art. A resin was prepared.

[0148] Irgacure PAG103 (used in Comparative Example 1) and Irgacure PAG121 (used in Comparative Example 2) are available from BASF and are not for cationic curable resins with significant absorbance in the UV / vis spectrum. It is clearly promoted as an ionic cationic photoacid photoinitiator. CPI400 (used in Comparative Example 3) is a cationic photoinitiator available from Sunapro, which has a significant absorbance at 400 nm. The three above mentioned cationic photoinitiators would be expected to be suitable candidates for potential incorporation into liquid hybrid radiation curable compositions for additive modeling systems utilizing UV / vis optics.

[0149] The _T95 and plateau conversion of the cyclic aliphatic epoxy component are calculated as described in the section of test methods above.

[0150] Comparative Example 4 utilizes a light initiation package that has been shown to be suitable for curing at wavelengths of 365 nm. Therefore, it is useful for benchmarking the embodiments of the present invention provided in Table 3 using the same base resin.

[Consideration of results]
[0151] Table 1 is the base resin used in most of the formulations of Tables 2, 3, and 4.

[0152] In Table 2, known commercial techniques used for 365 nm curing applications are used to determine acceptable levels of performance using the RT-FTIR method described herein. These test results will be used to benchmark the results in Tables 3 and 4 to establish acceptance criteria.

[0153] In Table 3, it is known to absorb in the UV / vis spectral region, and is suitable for incorporation into a liquid hybrid radiation curable composition for an addition modeling system by a direct excitation mechanism utilizing a UV / vis optical element. A cationic photoinitiator, which is expected to be present, is used. However, as you can see, none of these alternative methods reach the curing performance of the benchmarks in Table 2 created at 365 nm. Three different photoinitiators have been identified by the supplier as useful for curing at wavelengths of about 405 nm. When all three were tested, only CPI-400 showed some measurable curing activity. The data generated from this experiment was entered into the curve fitting software described in the above test method section, but the r2 value never reached acceptable levels because the data ^were statistically very insignificant in the test. rice field. Therefore, although not statistically significant to demonstrate actual T- ₉₅ and plateau conversion, the data in Table 3 and FIGS. 3 and 4 nevertheless show the performance of such photoinitiators utilizing the direct excitation mechanism. Is useful to show how inadequate.

[0154] Table 4 shows tests based on the concepts of the invention considered herein as curing at 400 nm (at the listed strength and duration). As can be seen, all the examples achieve results that are comparable to and even better than the 365 nm tolerance criteria established in Table 2. The time to reach ₉₅ % of the plateau T95 should be short, while the plateau conversion rate should be high.

[0155] Unless otherwise stated, wt. The term% means the mass-based amount of a particular component incorporated as compared to the entire liquid radiation curable composition for addition shaping.

[0156] The use of the terms "a" and "an" and "the" and similar reference terms in connection with the description of the present invention (particularly in connection with the following claims) is not specified herein. It should be construed to include both the singular and the plural, unless there is a limit or obvious contradiction in the context. The terms "comprising", "having", "inclating", and "contining" are open-ended unless otherwise noted. It should be construed as a term (ie, "meaning, but not limited to, including, but not limited to). Recitation of the range of values herein is in particular herein. Unless otherwise specified in, each individual value contained within this range acts as a shorthand notation for individually referencing, and is simply intended and each, as if each individual value were individually resited herein. As incorporated herein, all of the methods described herein can be performed in any suitable order, unless otherwise specified in the specification or there is no apparent contradiction in the context. The use of any example or exemplary expression provided herein (eg, "such as") is solely intended to provide a better understanding of the invention, in particular. Unless there is a patent request, the scope of the present invention is not limited. The wording herein should not be construed as representing any non-patentable element essential to the practice of the invention.

[0157] Preferred embodiments of the invention are described herein, including the best known embodiments of the present inventor for carrying out the invention. Modifications of such preferred embodiments will be apparent to those skilled in the art upon reading the above description. The present inventor expects that those skilled in the art will utilize such modifications as necessary, and that the present invention will be carried out in a form other than that specifically described in the present specification. The present inventor intends. Accordingly, the invention includes all modifications and equivalents of the subject matter resited within the scope of the claims attached herein to the extent permitted by applicable law. Moreover, any of the combinations of elements described above in all possible variants are included in the invention unless otherwise specified herein or in context.

[0158] Although the invention has been described in detail with reference to its particular embodiments, those skilled in the art will be able to make various changes and modifications without departing from the spirit and scope of the claimed invention. Will be obvious.

Claims (23)

A cationically curable component for performing cationic polymerization, which further contains a cyclic aliphatic epoxy component and an oxetane component, and a cationically curable component.
Free radical curable components that perform free radical polymerization and
The following, that is,
Cationic photoinitiator and
Vinyl ether diluent monomer and
Free radical photoinitiator and
Including a light start package and
Including
A UV / vis optical element that emits radiation with a peak spectral output at 400 nm and a 2 mW / cm ² liquid UV / vis ray-curable composition over 10 seconds. When exposed to
The cyclic aliphatic epoxy component has the following properties, that is,
i. With a _T95 value of about 70 seconds or less, more preferably about 55 seconds or less, more preferably about 53 seconds or less, more preferably about 50 seconds or less.
ii. With a plateau conversion rate of at least about 20%, more preferably at least about 30%, more preferably at least about 36%, more preferably at least about 43%.
Achieved,
The oxetane component has the following properties, that is,
i. With a _T95 value of about 50 seconds or less, more preferably less than about 42 seconds, more preferably less than about 34 seconds, more preferably less than about 23 seconds.
ii. With a plateau conversion rate of at least about 29%, more preferably at least about 34%, more preferably at least about 50%, more preferably at least about 59%.
A liquid UV / vis ray-curable composition for additional modeling that achieves the above. The liquid UV / vis ray-curable composition for addition molding according to claim 1, wherein the photo-initiated package further contains a photosensitizer. With reference to the entire composition
The cationically curable component is present in an amount of about 30 wt% to about 80 wt%, more preferably about 50 wt% to about 75 wt%.
The free radical curable component is present in an amount of about 8 wt% to about 50 wt%, more preferably about 15 wt% to about 25 wt%.
The photosensitizer is present in an amount of about 0.05 wt% to about 5 wt%, more preferably about 0.1 wt% to about 1 wt%, and the light initiation package is from about 3 wt% to about 20 wt%. The liquid UV / vis linear curable composition for addition molding according to claim 1 or 2, more preferably present in an amount of about 5 wt% to about 10 wt%. Based on the entire optical start package,
The cationic photoinitiator is present in an amount of about 8 wt% to about 50 wt%, more preferably about 30 wt% to about 45 wt%.
The vinyl ether diluent monomer is present in an amount of about 25 wt% to about 90 wt%, more preferably about 40 wt% to about 60 wt%, and the free radical photoinitiator is more preferably from about 8 wt% to about 30 wt%. Is present in an amount of about 10 wt% to about 25 wt%,
The addition molding according to any one of claims 1 to 3, wherein the cationic photoinitiator is at least partially dissolved in the solution together with the vinyl ether diluent monomer at a ratio of 0.1: 1 to 1: 1. Liquid UV / vis ray curable composition for use. (A) Cationic polymerizable component and
(B) Iodium salt cation photoinitiator and
(C) A photosensitizer for photosensitizing component (b) and
(D) A first reducing agent for reducing the component (b) and
(E) Free radically polymerizable component and
(F) Optional free radical photoinitiator,
(G) A second reducing agent for reducing the component (b), which has an electron-donating substituent bonded to a vinyl group, and
Including
It gives a dose of 20 mJ / cm ² and emits radiation with a peak spectral intensity of about 375 nm to about 500 nm, more preferably about 380 nm to about 450 nm, more preferably about 390 nm to about 425 nm, more preferably about 395 nm to about 410 nm. A liquid radiation curable composition for addition molding that can be cured by a UV / vis optical element. The first reducing agent (d) is a free radical photoinitiator configured to reduce the component (b) when it receives a chemical ray having a UV / vis wavelength and generates a free radical after dissociation. 5. The liquid radiation curable composition for addition molding according to 5. (B) The iodonium salt cation photoinitiator, (c) the photosensitizer for photosensitizing the component (b), and (d) the first reduction for reducing the component (b). The ratio of the agent to (g) the second reducing agent for reducing component (b), which has an electron-donating substituent attached to a vinyl group, is about 2: 2: 1: 2 to. The liquid radiation curable composition for addition molding according to claim 5 or 6, which is about 20: 1: 5: 25, most preferably about 10: 1: 2: 12. The cationically curable component (a) further contains a cyclic aliphatic epoxide and an oxetane, and the liquid radiation curable composition emits radiation having a peak intensity at about 400 nm at 20 mJ / by a UV / vis optical element. When receiving an energy dose of cm ²
The cyclic aliphatic epoxide has the following properties, that is,
i. With a _T95 value of less than about 55 seconds, more preferably less than 50 seconds,
ii. With a plateau conversion rate of at least about 30%, more preferably at least about 40%,
And the oxetane has the following properties:
i. With a _T95 value of less than about 45 seconds, more preferably less than about 25 seconds,
ii. With a plateau conversion rate of at least about 33%, more preferably at least about 55%,
The liquid radiation curable composition for addition molding according to any one of claims 5 to 7, wherein the liquid radiation curable composition for addition molding is achieved. One of claims 5 to 8, wherein the component (a) additionally contains a glycidyl ether epoxy selected from the group consisting of bisphenol A-based glycidyl ether, bisphenol S-based glycidyl ether, and bisphenol F-based glycidyl ether. The liquid radiation curable composition for addition molding according to. The diphenyliodonium salt is (4-methylphenyl) [4- (2-methylpropyl) phenyl]-, hexafluorophosphate, [4- (1-methylethyl) phenyl] (4-methylphenyl)-, tetrakis ( Selected from the group consisting of (pentafluorophenyl) borate (1-), (bis (4-dodecylphenyl) iodonium hexaflurol antimonate), and (bis (4-tert-butylphenyl) iodonium hexafluorophosphate). The liquid radiation curable composition for addition molding according to any one of claims 5 to 9. The liquid radiation-curable composition for addition molding according to any one of claims 5 to 10, wherein the photosensitizer is thioxanthone. The liquid radiation-curable composition for addition molding according to claim 11, wherein the thioxanthone is further selected from the group consisting of chloropropoxythioxanthone and isopropylthioxanthone. The first reducing agent (d) for reducing the component (b) is the following formula (IV) :.

(In the formula, Ar ₁ is a substituted or unsubstituted aromatic group, R ₁ is an Ar ₁ or C ₂ to C ₂₀ aliphatic chain, and R ₂ is R ₁ or one. (Contains the above substituted or unsubstituted acylphenyl group)
The liquid radiation curable composition for addition molding according to any one of claims 5 to 12, represented by. The liquid radiation curable composition for addition molding according to any one of claims 5 to 13, wherein the free radical photoinitiator is hydroxycyclohexylphenylketone rather than optional. The second reducing agent (g) having an electron-donating substituent bonded to a vinyl group is vinyl ether, vinyl ester, vinyl thioether, n-vinylcarbazole, n-vinylpyrrolidone, n-vinylcaprolactam, allyl ether, and the like. The liquid radiation curable composition for addition molding according to any one of claims 5 to 14, selected from the group consisting of vinyl carbonate and vinyl carbonate. The liquid radiation curable composition for addition molding according to any one of claims 5 to 15, wherein the second reducing agent (g) having an electron-donating substituent bonded to a vinyl group is vinyl ether. The liquid radiation curable composition for addition molding according to claim 15 or 16, wherein the second reducing agent (g) having an electron-donating substituent bonded to a vinyl group is polyfunctional. (A) Approximately 30 wt. Further containing a cyclic aliphatic epoxide and oxetane. % ~ About 80 wt. % With at least one cationically polymerizable component,
(B) Approximately 1 wt. With an absorbance of less than 0.01 at 400 nm. % ~ About 8 wt. % Sulfonium salt cation photoinitiator,
(C) The following formula (V):

(In the formula, R contains C ₁ to C ₂₀ aliphatic chains)
Approximately 0.5 wt. Indicated by. % ~ About 3 wt. % Compound and
(D) Free radically polymerizable component and
(E) Diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide-free radical photoinitiator,
Including
It can be cured by a UV / vis optical element that gives a dose of 20 mJ / cm ² and emits radiation with a peak spectral intensity of about 375 nm to about 500 nm, more preferably about 380 nm to about 450 nm, more preferably about 390 nm to about 425 nm. A liquid radiation curable composition for addition molding. When an energy dose of 20 mJ / cm ² is received by a UV / vis optical element that emits radiation with a peak intensity of about 400 nm, the cyclic aliphatic epoxide has a _T95 value of less than about 55 seconds and at least about 30%. The liquid radiation curable composition for addition molding according to claim 18, wherein the plateau conversion rate is achieved, and the oxetane achieves a _T95 value of less than about 45 seconds and a plateau conversion rate of at least about 33%. The free radical photoinitiator component is less than 50% compound containing two or more carboxyl groups, preferably two or more carboxyls, based on the total amount of free radical photoinitiators present in the composition. The liquid radiocurable composition for addition molding according to claim 18 or 19, which has a compound containing less than 33% of radicals. It is a method for forming a three-dimensional article by an additional modeling system using a UV / vis optical element.
1. 1. The step of providing the liquid radiation curable composition for additional modeling according to any one of claims 1 to 20, and the step of providing the liquid radiation curable composition.
2. 2. The step of providing the first liquid layer of the liquid radiation curable resin and
3. 3. A step of forming a first cured layer by exposing the first liquid layer to an image like an image using a UV / vis optical configuration to form an image-forming cross section.
4. A step of forming a new layer of liquid thermosetting resin in contact with the first cured layer, and
5. A step of exposing the new layer to an image with chemical rays to form an additional image-forming cross-section.
6. A process of repeating steps (4) and (5) a sufficient number of times to construct a three-dimensional article, and
Including
A method in which the UV / vis optical element emits radiation with a peak spectral intensity of about 375 nm to about 500 nm, more preferably about 380 nm to about 450 nm, more preferably about 395 nm to about 410 nm. The additive modeling system utilizing the UV / vis optical element according to claim 21, wherein the UV / vis optical configuration is selected from the group consisting of LED / DLP, laser / DLP, LED / LCD, and laser / LCD. How to form an original article. A three-dimensional component formed by the process according to claim 21 or 22, using the liquid radiation curable composition according to any one of claims 1 to 20.

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