Fluorosilicone acrylate composition and use thereof

Abstract

The application discloses a fluorosilicone acrylate composition and application thereof, and relates to the technical field of polymers. The fluorosilicone acrylate composition provided by the application has the advantages of low bulk absorption and clear threshold response at 405 nm, high Dk, 1.0-1.6 GPa modulus, low shrinkage, high light transmittance and the like required by an OK mirror.

Description

Technical Field

[0001] This invention relates to the field of polymer technology, and in particular to a fluorosilicone acrylate composition and its application. Background Technology

[0002] 3D printing, also known as additive manufacturing, is a method of printing three-dimensional objects. These objects can be obtained from photosensitive powders, liquids, or molten starting materials. In particular, they can be obtained from resins such as monomers (which can be photopolymerized at room temperature).

[0003] The PCT application WO 2018 / 208378, published on November 15, 2018, the article "Volumetric 3D printing of elastomers by tomographic back-projection" by D. Loterie (2018), and the article "Volumetric additive manufacturing via tomographic reconstruction" by BE Kelly et al. in *Science* (2019) describe a method called "Computed Axial Lithography (CAL)," which is based on continuous volumetric printing. In the CAL method, a standard resin is contained in a rotatable, optically transparent container. It may include a radical-polymerizable liquid resin and radical stabilizers, including oxygen, which act as inhibitors of photopolymerization. Any and all stabilizers are already present in the resin and are not continuously supplied. Light is projected from one side of the container simultaneously at multiple angles. The superposition of exposures from different angles generates a 3D energy dose, which is sufficient to enable the resin to photopolymerize in the desired geometry.

[0004] Continuous 3D printing methods are advantageous over layer-by-layer methods, particularly due to their article formation speed and the quality of printed parts. Many of these methods rely on the use of inhibitors for photopolymerization, especially inhibitors for radical-polymerizable liquid resins, such as oxygen or air. In fact, regardless of the type of polymerizable liquid resin used, for example in the CLIP method, including polyurethane, epoxy, cyanate, and silicone resins, it relies on oxygen-inhibited acrylic curing. No alternative resin systems have yet been proven. However, the use of such liquid resins is associated with several drawbacks. First, the sensitivity of these liquid resins to radical photopolymerization during continuous printing needs to be fine-tuned, which in turn creates issues with product storage stability and often necessitates packaging and selling them as two-part formulations, mixing them before use. Second, these liquid resins require further fine-tuning to balance inhibition by controlling the diffusion of supplied oxygen. Third, oxygen diffusion varies with resin viscosity and therefore needs to be adjusted according to resin type and its shelf life. Fourth, expensive specialized films with high air / oxygen permeability and transparency are required to form optically transparent parts.

[0005] Different liquid resins are conventionally used in 3D printing methods. For example, theoretically, liquid resins can include polymerizable monomers selected from the group consisting of acrylic acid, methacrylic acid, acrylamide, styrene, olefins, halogenated olefins, cyclic olefins, maleic anhydride, chain olefins, alkynes, carbon monoxide, functionalized oligomers, monomers with multifunctional curing sites, functionalized PEGs, and combinations thereof. See, for example, WO 2015 / 164234 A1, WO 2015 / 164234 A1, and D. Loterie's article (2018). However, in practice, the vast majority of photopolymerizable 3D articles are obtained from radical-polymerizable monomers, particularly from (meth)acrylates and their derivatives that are typically suppressed by oxygen or air, as disclosed in the article "Role of Oxygen in polymerization reactions" by VABhanu et al., published in Chemical Reviews (vol. 91, No. 2, 1991). Oxygen or air-controlled suppression can be advantageously used, for example, in conventional CLIP methods to create polymerization dead zones during 3D printing. However, oxygen suppression is also disadvantageous because the surface of the article provided by printing with (meth)acrylate resin comes into contact with ambient air (oxygen) and thus remains partially uncured and tacky. To obtain a non-tacky surface, the 3D-printed article should therefore undergo post-processing (see, for example, WO 2019 / 043529 A1). Post-processing to complete the curing of the 3D-printed article may require additional hardware and is currently a time-consuming process that may also involve heating.

[0006] Furthermore, CAL requires "volume penetration + threshold curing". Existing resins have excessively high absorption at 405nm or no clear threshold, resulting in bulk fogging curing, ghosting, and yellowing; there is also a lack of material systems that meet the requirements of high Dk, stable modulus, and low shrinkage for orthokeratology lenses. Summary of the Invention

[0007] (a) Technical problems to be solved

[0008] Therefore, one of the main objectives of this invention is to provide a fluorosilicone acrylate composition and its application. Optical elements prepared from the fluorosilicone acrylate composition provided by this invention achieve low volume absorption and a clear threshold response at 405 nm, while also possessing the advantages required for orthokeratology (OK) lenses, such as high Dk, 1.0~1.6 GPa modulus, low shrinkage, and high light transmittance.

[0009] (II) Technical Solution

[0010] To achieve the above objectives, the present invention provides a fluorosilicone acrylate composition comprising, by weight of total composition, the following components: fluorosilicone acrylate oligomer: 35-55, TRIS (3-[tris(trimethylsiloxane)silyl]propyl methacrylate): 20-35, IBOMA (isobornyl methacrylate): 2-12, TCDMDA (tricyclodecanedimethylethanol diacrylate): 5-12, UDMA (polyurethane dimethacrylate): 2-10, TPO-L (ethyl(2,4,6-trimethylbenzoyl)phenylphosphonate): 0.04-0.12, TEMPO (2,2,6,6-tetramethylpiperidine-1-oxy radical): 0.005-0.03, MEHQ (hydroquinone monomethyl ether): 100-300 ppm.

[0011] Orthokeratology (Ortho-k) lens materials must meet the core physiological safety requirement of "high oxygen permeability (high Dk value)". The introduction of fluorine and siloxane segments is key to achieving a high Dk value.

[0012] TPO-L, with extremely low absorption at 405 nm, was selected as the main initiator, and initiators such as BAPO, which have higher absorption in this wavelength range, were explicitly prohibited or strictly limited. This ensures that light can "volume penetrate" the thick resin layer, which is a prerequisite for achieving precise CAL molding and avoiding surface over-curing and bulk fogging.

[0013] By introducing an extremely low amount of the inhibitor TEMPO, which works synergistically with dissolved oxygen in the system, an "inhibition period" is artificially created in the early stages of curing. Only when the accumulated exposure energy exceeds a critical value (D_c, the curing threshold dose) is the inhibitor consumed, and the polymerization reaction can occur rapidly. This macroscopically creates a "threshold curing" behavior with sharp boundaries and no ghosting, which is the key to the high precision of the CAL process.

[0014] In one embodiment, the energy level of the fluorinated silicone acrylate oligomer tube is 2 to 4.

[0015] In one embodiment, the energy level of the fluorinated silicone acrylate oligomer tube is 2.4.

[0016] In one embodiment, the molecular weight of the fluorinated silicone acrylate oligomer is 800-2000.

[0017] In one embodiment, the molecular weight of the fluorinated silicone acrylate oligomer is 1000-1200.

[0018] In one embodiment, the fluorinated silicone acrylate oligomer includes fluorinated polysiloxane diacrylate-terminated oligomer, fluorinated polysiloxane triacrylate-modified oligomer, fluorinated polyether-siloxane hybrid diacrylate; perfluoropolyether diacrylate (PFPE-DA), bis(methacryloyloxypropyl)-terminated poly(methyl / 3,3,3-trifluoropropyl)siloxane (difunctional, Mn: 1000~1200) and / or PFPE-DA (difunctional, Mn: 900~1100).

[0019] In one embodiment, the fluorinated silicone acrylate oligomer is a bis(methacryloyloxypropyl)-terminated poly(methyl / 3,3,3-trifluoropropyl)siloxane.

[0020] In one embodiment, the fluorosilicone acrylate composition comprises, by weight of total composition, the following components: bis(methacryloyloxypropyl)-terminated poly(methyl / 3,3,3-trifluoropropyl)siloxane: 35-55, TRIS: 20-35, IBOMA: 2-12, TCDMDA: 5-12, UDMA: 2-10, TPO-L: 0.04-0.12, TEMPO: 0.005-0.03, MEHQ: 100-300 ppm.

[0021] In one embodiment, the fluorosilicone acrylate composition comprises, by weight of total composition, the following components: bis(methacryloyloxypropyl)-terminated poly(methyl / 3,3,3-trifluoropropyl)siloxane: 40-50, TRIS: 25-33, IBOMA: 6-10, TCDMDA: 8-10, UDMA: 4-8, TPO-L: 0.01-0.02, TEMPO: 0.01-0.02, MEHQ: 100-300 ppm.

[0022] In one embodiment, the fluorosilicone acrylate composition comprises, by weight of total composition, the following components: bis(methacryloyloxypropyl)-terminated poly(methyl / 3,3,3-trifluoropropyl)siloxane: 45, TRIS: 32.88, IBOMA: 6, TCDMDA: 8, UDMA: 8, TPO-L: 0.08, TEMPO: 0.02, MEHQ: 0.02.

[0023] In one embodiment, the fluorosilicone acrylate composition further includes PFPE-DA (perfluoropolyether diacrylate).

[0024] In one embodiment, the PFPE-DA accounts for 0 to 15 wt% of the total mass of the composition.

[0025] In one embodiment, the PFPE-DA accounts for 5 to 12 wt% of the total mass of the composition.

[0026] In one embodiment, the PFPE-DA accounts for 10 wt% of the total mass of the composition.

[0027] In one embodiment, the fluorosilicone acrylate composition comprises, by weight of total composition, the following components: bis(methacryloyloxypropyl)-terminated poly(methyl / 3,3,3-trifluoropropyl)siloxane: 45, TRIS: 32.88, IBOMA: 6, TCDMDA: 8, UDMA: 8, TPO-L: 0.08, TEMPO: 0.02, MEHQ: 0.02, PFPE-DA: 10.

[0028] In another aspect, the present invention provides the use of the above-described fluorosilicone acrylate composition in the preparation of optical elements.

[0029] In another aspect, the present invention also provides an optical element prepared from the above-described fluorosilicone acrylate composition.

[0030] In one embodiment, the optical element includes a convex lens, a concave lens, a right-angle prism, a beam splitter, a bandpass filter, a neutral density filter, a diffraction grating, and / or a holographic recording medium.

[0031] (III) Beneficial Effects

[0032] This invention provides a fluorosilicone acrylate composition and its application. Compared with the prior art, it has the following advantages:

[0033] 1. Solidification at 405nm results in good body penetration, a clear threshold, and reduced ghosting and volumetric atomization during solidification.

[0034] 2. Low shrinkage combined with high Tg, resulting in curvature and geometric stability; high optical transmittance and low haze after post-curing;

[0035] 3. Low initiator / inhibitor dosage, combined with deep extraction, reduces the risk of extractables and biotoxicological factors. Attached Figure Description

[0036] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0037] Figure 1 It is a curing process curve.

[0038] Figure 2 This is a diagram showing the dynamic thermomechanical properties of the cured sample.

[0039] Figure 3 This is a graph showing the impact of deep extraction on the content of key residues. Detailed Implementation

[0040] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0041] Terms and Definitions

[0042] As used herein, the term "polymer" means a material formed by polymerizing / crosslinking one or more monomers or macromonomers or prepolymers or combinations thereof.

[0043] As used herein, the term “molecular weight” is exponential average molecular weight unless otherwise specified or unless the test conditions indicate otherwise.

[0044] As used in this article, the term "photoinitiator" refers to a chemical that initiates a free radical crosslinking / polymerization reaction by utilizing light.

[0045] As used herein, the term "oxygen permeability" and "Dki" refer to the rate at which oxygen passes through a material. As used in this application, the term "oxygen permeability (Dk)" relating to hydrogels (siloxane or non-siloxane) or contact lenses means corrected oxygen permeability (Dkc), which is measured at approximately 34°C to 35°C and corrected for surface resistance to oxygen flux caused by boundary layer effects, according to the procedure described in Example 1 of U.S. Patent Application Publication No. 2012-0026457A1. Oxygen permeability is conventionally expressed in barrers, where "barrers" is defined as [(cm²)]. 3 Oxygen (mm) / (cm) 2 (s)(mmHg)]×10 -10 .

[0046] As used herein, the term "oxygen transmittance," "Dk / t," refers to the rate at which oxygen passes through a specific lens or material of average thickness t [in mm] over the measured area. Oxygen transmittance is conventionally expressed in barrers / mm, where "barrers / mm" is defined as [(cm 3 oxygen) / (cm 2 (s)(mmHg)]×10 -9 .

[0047] As used herein, the term "modulus" or "elastic modulus" refers to the tensile modulus or Young's modulus as a measure of stiffness of a contact lens or material. Those skilled in the art are well aware of how to determine the elastic modulus of a siloxane hydrogel material or contact lens.

[0048] As used in this article, the term "UVA" refers to radiation occurring at wavelengths between 315 and 380 nanometers.

[0049] As used in this article, “containing,” “having,” or “including” includes “containing,” “mainly composed of,” “substantially composed of,” and “composed of”; “mainly composed of,” “substantially composed of,” and “composed of” are subordinate concepts of “containing,” “having,” or “including.”

[0050] Unless otherwise specified, the experimental methods used in the following examples are conventional methods, and the reagents, methods and equipment used are conventional reagents, methods and equipment in this technical field.

[0051] Example 1: Curing of photofluorosilicone acrylate composition #1:

[0052] 1. Composition: Bis(methacryloyloxypropyl)-terminated poly(methyl / 3,3,3-trifluoropropyl)siloxane 45.00wt% (22.50g), TRIS 32.88wt% (16.44g), IBOMA 6.00wt% (3.00g), TCDMDA 8.00wt% (4.00g), UDMA 8.00wt% (4.00g), TPO-L 0.08wt% (0.040g), TEMPO 0.02wt% (0.010g), MEHQ 0.02wt% (0.010g).

[0053] 2. Composition curing:

[0054] 2.1. Preparation of the composition: Under light-protected conditions, using yellow light as a safety illumination, add each liquid monomer and oligomer component to a brown glass bottle equipped with a magnetic stirrer. Turn on the magnetic stirrer, and after a homogeneous and clear solution is formed, add the solid photoinitiator (TPO-L), inhibitor (TEMPO), and stabilizer (MEHQ). Continue stirring until all solid components are completely dissolved. Degas the prepared resin composition under vacuum at room temperature for 15-30 minutes to remove dissolved air and bubbles introduced during stirring, and set aside for later use.

[0055] 2.2. Curing process:

[0056] Equipment: A commercially available CAL (Constrained Area Lithography) or DLP (Digital Light Processing) 3D printer equipped with a 405nm LED light source. The printing chamber must have oxygen concentration control capabilities.

[0057] Environmental control: Before printing begins, nitrogen is introduced into the printing chamber until the oxygen concentration drops below 200 ppm to eliminate the effect of oxygen inhibition on threshold curing.

[0058] Printing parameters:

[0059] Layer thickness: set to 50μm.

[0060] Exposure energy: According to the curing curve of the resin of the present invention (e.g.) Figure 1 As shown in the figure, the single-layer exposure energy is set within the ideal working range of 1.6×D_c to 2.0×D_c. For example, if D_c is approximately 12.5 mJ / cm², the single-layer exposure energy can be set to 20-25 mJ / cm².

[0061] Printing execution: Pour the prepared resin composition into the resin tank of the printer and start the printing process according to the preset CAD model (e.g., OK lens or performance test standard strip).

[0062] 2.3. Post-processing:

[0063] IPA Cleaning: After printing, remove the molded part from the build platform and ultrasonically clean it with isopropyl alcohol (IPA) for 2-5 minutes to remove any remaining uncured resin. (The effects of secondary curing and deep extraction on residues are as follows...) Figure 3 (As shown)

[0064] Secondary curing: Place the cleaned parts in a UV curing chamber under a nitrogen atmosphere and use a 405nm light source for 10-20 minutes of supplementary exposure to ensure complete resin curing and improve the final conversion rate.

[0065] Deep extraction: For samples requiring biotoxicological assessment, Soxhlet extraction should be performed in hexane or physiological saline for 24 to 72 hours in accordance with ISO 10993 standards to reduce the extractable content to a safe level.

[0066] Example 2: Curing of photofluorosilicone acrylate composition #2:

[0067] 1. Composition: 45.00wt% (22.50g) of bis(methacryloyloxypropyl)-terminated poly(methyl / 3,3,3-trifluoropropyl)siloxane, 32.88wt% (16.44g) of TMPTA (trimethylolpropane triacrylate), 6.00wt% (3.00g) of IBOMA, 8.00wt% (4.00g) of TCDMDA, 8.00wt% (4.00g) of UDMA, 0.08wt% (0.040g) of TPO-L, 0.02wt% (0.010g) of TEMPO, and 0.02wt% (0.010g) of MEHQ.

[0068] 2. Composition curing: Same as in Example 1.

[0069] Example 3 Curing of photofluorosilicone acrylate composition #3:

[0070] 1. Composition: Bis(methacryloyloxypropyl)-terminated poly(methyl / 3,3,3-trifluoropropyl)siloxane 45.00wt% (22.50g), TRIS 32.88wt% (16.44g), IBOMA 6.00wt% (3.00g), HDDA (1,6-hexanediol diacrylate) 8.00wt% (4.00g), UDMA 8.00wt% (4.00g), TPO-L 0.08wt% (0.040g), TEMPO 0.02wt% (0.010g), MEHQ 0.02wt% (0.010g).

[0071] 2. Composition curing: Same as in Example 1.

[0072] The oxygen permeability (Dk), glass transition temperature (Tg), flexural modulus (GPa), curing shrinkage (%), and α405 (cm) of the cured optical elements in Examples 1-3 were measured respectively. -1 ).

[0073] The test results are shown in Table 1 and Figures 1-2 As shown:

[0074] Table 1

[0075]

[0076] It should be noted that, in this document, relational terms such as "first" and "second" are used only to distinguish one entity or operation from another, and do not necessarily require or imply any such actual relationship or order between these entities or operations. Furthermore, the terms "comprising," "including," or any other variations thereof are intended to cover non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements includes not only those elements but also other elements not expressly listed, or elements inherent to such a process, method, article, or apparatus. Without further limitations, an element defined by the phrase "comprising one..." does not exclude the presence of other identical elements in the process, method, article, or apparatus that includes said element.

[0077] The above embodiments are only used to illustrate the technical solutions of the present invention, and are not intended to limit it. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some of the technical features. Such modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims

1. A fluorosilicone acrylate composition, characterized in that, The composition comprises, by total mass, the following components: fluorosilicone acrylate oligomer: 35-55, TRIS: 20-35, IBOMA: 2-12, TCDMDA: 5-12, UDMA: 2-10, TPO-L: 0.04-0.12, TEMPO: 0.005-0.03, MEHQ: 100-300 ppm; wherein the fluorosilicone acrylate oligomer is a bis(methacryloyloxypropyl)-terminated poly(methyl-3,3,3-trifluoropropyl)siloxane.

2. The fluorosilicone acrylate composition according to claim 1, characterized in that, The functionality of the fluorinated silicone acrylate oligomer is 2 to 4.

3. The fluorosilicone acrylate composition according to claim 2, characterized in that, The functionality of the fluorinated silicone acrylate oligomer is 2.

4.

4. The fluorosilicone acrylate composition according to claim 1, characterized in that, The fluorinated silicone acrylate oligomer Mn is 800~2000.

5. The fluorosilicone acrylate composition according to claim 4, characterized in that, The fluorinated silicone acrylate oligomer Mn is 1000~1200.

6. The fluorosilicone acrylate composition according to any one of claims 1-5, characterized in that, The fluorosilicone acrylate composition also includes perfluoropolyether diacrylate.

7. The use of the fluorosilicone acrylate composition according to any one of claims 1-6 in the preparation of optical elements.

8. An optical element, characterized in that, It is prepared from the fluorosilicone acrylate composition according to any one of claims 1-6.

9. The optical element according to claim 8, characterized in that, The optical elements include convex lenses, concave lenses, right-angle prisms, beam splitters, bandpass filters, neutral density filters, diffraction gratings, and / or holographic recording media.

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