Methods and Compositions for Photopolymer Additive Manufacturing

Abstract

To disclose a method comprising a photopolymerizable composition for use in additive manufacturing, particularly for digital light processing, photo-modeling method or continuous liquid interface manufacturing, and a composition.SOLUTION: There is provided a method for photo-polymerizing and printing an article, which comprises steps of: a) temporarily exposing a photopolymerizable composition to light, in which the photopolymerizable composition contains (i) at least one kind of a photopolymerizable macromer component, (ii) at least one kind of a light-reflecting material component suspended in the photopolymerizable composition, and (iii) at least one kind of a photoinitiator component, and adjusting an irradiation amount requirement of the photopolymerizable composition when the light-reflecting material component is compared to an irradiation amount requirement of a composition that does not include the light-reflecting material; and b) forming a printed matter containing at least a polymerized macromer.SELECTED DRAWING: None

Description

Technical Field

[0001] [Cross - Reference to Related Applications] This application claims the benefit of U.S. Provisional Patent Application No. 62 / 653,584, filed on April 6, 2018, under 35 U.S.C. § 119(e), and the entire disclosure thereof is incorporated herein by reference for all purposes. The present disclosure relates to methods and compositions for photopolymerizable additive manufacturing, particularly manufacturing using UV and visible light photopolymerizable components.

Background Art

[0002] One widely used method of photopolymerizable additive manufacturing is three - dimensional (3D) printing by stereolithography (SLA). In the stereolithography (SLA) method, light such as ultraviolet (UV) or visible light is used to photopolymerize a liquid material into a designed structure such as a 3D article with high accuracy and precision. Thin, continuous layers are photocrosslinked by UV or visible light, for example, according to the instructions of a sliced CAD (computer - aided design) model. Other types of photopolymerizable 3D printing have also been developed and will continue to be developed for use in additive manufacturing. SLA generally uses a liquid photocrosslinkable polymer composition, which is also referred to as a resin or ink formulation and generally contains a photopolymerizable polymer or oligomer component and a photoinitiator. Other components such as diluents, crosslinkers, and dyes are optionally added to the composition. The macroscopic properties and degradation characteristics of the articles produced by photopolymerization can be modified by changing the polymer chemistry and processing techniques. For example, by using biodegradable polymer materials, articles with time - limited functions that cease to exist after a certain period can be produced. Such biodegradable articles are suitable, for example, for medical devices for tissue repair, and after a certain period, the presence of the article ceases, enabling tissue repair. SLA can also include non - biodegradable polymer materials used in methods for providing long - term articles. Concerns about photopolymerizable articles that come into contact with living organisms, i.e., subjects, include those related to the safety and effectiveness of the produced articles, particularly biocompatibility and cytotoxicity. There is a need for improved compositions for use in methods and 3D printing methods, as well as compositions that result in articles with high biocompatibility and / or low cytotoxicity.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Summary of the Invention

Means for Solving the Problems

[0004] This specification discloses methods and compositions for photopolymerization processes such as additive manufacturing, often referred to as 3D printing, for creating and using such photopolymerizable articles. This specification discloses a photopolymerizable composition comprising: a) at least one photopolymerizable macromer component; at least one light-reflecting material component comprising a light-reflecting material suspended in the photopolymerizable composition; and at least one photoinitiator component; a step of temporarily exposing the photopolymerizable composition to light such that the light-reflecting material component adjusts the irradiation amount of the photopolymerizable composition compared to the irradiation amount of the photopolymerizable composition without the light-reflecting material; and a step of forming a printed matter comprising at least a polymerized macromer. This specification discloses polymers polymerized by one or more of the methods disclosed herein. This specification discloses articles produced by one or more of the methods disclosed herein. This specification discloses a non-toxic polymer article comprising a photopolymerizable biodegradable polymer and a non-toxic amount of a photoinitiator. The polymer article may be wholly or partially biodegradable under physiological conditions. The polymer article may not be biodegradable under physiological conditions. This specification discloses a photopolymerizable composition comprising at least one photopolymerizable macromer component; at least one light-reflecting material component comprising a light-reflecting material suspended in the photopolymerizable composition; and at least one photoinitiator component. The composition disclosed herein may have a light-reflecting material component that adjusts the irradiation dose of the photopolymerizable composition as compared to the irradiation dose of a photopolymerizable composition that does not contain a light-reflecting material. This specification discloses a stereolithography photopolymerizable composition comprising at least one photopolymerizable macromer component; at least one light-reflecting material component comprising a light-reflecting material suspended in the photopolymerizable composition; and at least one photoinitiator component, wherein the light-reflecting material component adjusts the irradiation dose of the photopolymerizable composition as compared to the irradiation dose of a photopolymerizable composition that does not contain a light-reflecting material. This specification discloses a photopolymerizable composition for continuous liquid interface production comprising at least one photopolymerizable macromer component; at least one light-reflecting material component comprising a light-reflecting material suspended in the photopolymerizable composition; and at least one photoinitiator component, wherein the light-reflecting material component adjusts the irradiation dose of the photopolymerizable composition as compared to the irradiation dose of a photopolymerizable composition that does not contain a light-reflecting material. This specification discloses a photopolymerizable ink composition comprising at least one photopolymerizable macromer component; at least one light-reflecting material component comprising a light-reflecting material suspended in the photopolymerizable composition; at least one photoinitiator component, wherein the light-reflecting material component adjusts the irradiation dose of the photopolymerizable composition as compared to the irradiation dose of a photopolymerizable composition that does not contain a light-reflecting material; a reactive diluent; and a stabilizer. The composition disclosed herein may contain a dye. This specification discloses a light-reflecting material comprising at least one of an inorganic solid; an organic compound, a crystalline organic compound, a crystalline amino acid and / or its derivative, a crystalline fatty acid and / or its derivative, a crystalline peptide, or a combination thereof. This disclosure includes a method of making the disclosed composition.

Embodiments for Carrying Out the Invention

[0005] This specification discloses a method and composition comprising at least one reflective material for adjusting the effective exposure dose of a photopolymerizable composition. This specification discloses that a photopolymerizable composition comprises at least one photopolymerizable macromer component; at least one light-reflecting material component suspended in the photopolymerizable composition; and at least one photoinitiator component, and the light-reflecting material component temporarily exposes the photopolymerizable composition to light to adjust the exposure dose of the photopolymerizable composition as compared to a photopolymerizable composition without the light-reflecting material, and discloses a method for photopolymerizing (printing) an article comprising forming a printed matter containing a polymerized macromer. In one aspect, the light-reflecting material component enhances the exposure dose to the formulation containing the light-reflecting material component. By enhancing the exposure dose to the formulation, the polymerizable components can be polymerized at the same polymerization rate, or at a substantially similar polymerization rate, or in some cases at a faster polymerization rate, while using a smaller amount of photoinitiator in the formulation. In one aspect, the total concentration of the photoinitiator component can be less than 1.0% by mass. In one aspect, the composition disclosed herein comprises a light-reflecting material component that increases the polymerization rate at the surface of the photopolymerizable composition where light contacts the photopolymerizable composition as compared to the same photopolymerizable composition without the light-reflecting material component. In one aspect, by incorporating the light-reflecting material component into the photopolymerizable composition, the macromer is surface-cured at a lower photoinitiator concentration than that used in a photopolymerizable composition without the light-reflecting material component. In one aspect, the light-reflecting material component reflects light at one or more wavelengths that activate the photoinitiator.

[0006] Light is electromagnetic radiation of wavelengths, and these wavelengths (λ equal to about 400 to 770 nm) that can be perceived by the human eye are often called visible light. However, the word "light" is also sometimes used to refer to other adjacent regions of the spectrum, namely ultraviolet light (shorter wavelengths than visible light) and infrared light (longer wavelengths). "Light" as used herein refers to electromagnetic radiation of wavelengths including ultraviolet light, infrared light, and visible wavelengths. The wavelengths of UV (ultraviolet) radiation are about 10 to 400 nm, of which UV-A is 315 to 400 nm, UV-B is 280 to 315 nm, UV-C is 100 to 280 nm, and the description of visible light (VIS) visible to the human eye is 400 to 770 nm. The wavelengths of infrared light are about 770 to 1×106 It is so. Light in the spectrum of 10 to 770 nm may be referred to as "UV-VIS" light or "light" in this specification. Although radiation consists of various wavelength components, the term "monochromatic" is often used when the spectral region is narrow. Even a single photon cannot be assigned an exact wavelength. Also, since radiation moves in various directions, its direction is always distributed. "Parallel radiation" means that the angular distribution is very narrow. "Scattered or <diffused> radiation" means that the angular distribution is wide. To fully describe radiation, both the distribution of its wavelength components (spectral distribution) and their directions in addition to the "quantity" need to be considered. In the SLA method, the direction (radiation) of light is generally constant and is perpendicular to the photopolymerizable material, generally at 90 degrees. Other photopolymerization steps such as post-curing may use light sources at various angles.

[0007] Two variables of the photopolymerization method and composition are energy density and output density. Energy density is energy / surface area and is often expressed in joules or millijoules per square centimeter (J / cm 2 or mJ / cm 2 ). The energy density value generally means the total amount of energy required to activate all photoinitiators in the UV / Vis curable resin and fully polymerize the resin. The total energy required to fully cure a UV curable resin is a function of several components of the photopolymerization method and composition and changes in these components. Such components include cure thickness, photoinitiator concentration, photoinitiator structure, amount of reactive material, specific chemical functionality, etc. The photopolymerization method or composition may have a defined or determined (e.g., measured) energy density required to fully polymerize the photopolymerizable composition when the components of the method / composition (cure thickness or depth, photoinitiator concentration, amount of reactive material, specific macromer, etc.) are kept constant. In a process specification or technical data sheet, the UV light source emission can be specified together with the energy density requirement, such as setting the energy density requirement to 500 mJ / cm 2 using a 365 nm UV-LED light source. The output density, which is the second variable, is used when determining the rate at which radiation (UV / Vis light) is supplied to the photocurable resin (e.g., the photopolymerizable composition). The rate at which radiation is supplied to the UV / Vis curable resin correlates with the rate at which the photoinitiator absorbs the UV / Vis radiation and initiates monomer or macromer polymerization. In use, the peak irradiance can often be replaced with the output density in units of both output / surface area, typically watts or milliwatts per square centimeter (W / cm 2 or mW / cm 2 ). By definition, the peak irradiance is the highest output density applied to the UV / Vis curable resin, while the output density is generally considered the average irradiance applied to the UV / Vis curable resin.

[0008] The relationship between energy density and output density relates to the total exposure time at a specific irradiance combined to give the total amount of energy supplied to the UV curable resin (peak irradiance × exposure = energy density). This suggests that output density and exposure time are not independent. A watt is a unit of joules per second (J / s), and multiplying watts by seconds gives joules, and mW / cm 2 × seconds = mJ / cm 2 is represented. Once the energy density requirement of the composition is determined, photopolymerization can be controlled by changing the time and / or output density. For example, if a UV / Vis curable resin has an energy density requirement of 500 mJ / cm 2 using a 365 nm UV-LED light source, the energy requirement can be met under various exposure times, i.e., exposure for 50 seconds at an output density of 10 mW / cm 2 , exposure for 5 seconds at an output density of 100 mW / cm 2 , exposure for 0.1 seconds at an output density of 5000 mW / cm 2 , or other combinations of time and output where the product is 500 mJ / cm 2 .

[0009] The energy density requirement of the composition used in this specification corresponds to the exposure dose and refers to the measured amount of light, i.e., the energy required to activate the photoinitiator in the curable resin to sufficiently polymerize the resin in a specific time, and is measured in J / cm 2 or mJ / cm 2 , which is the energy per unit surface area. The energy density or exposure dose requirement of the composition depends on the components of the composition (photoinitiator concentration, amount of material, photopolymerizable macromer) and the conditions of the photopolymerization method, such as cure depth or cure thickness, distance from the light source, light source emission (mW / cm 2 ), and the time required for sufficient polymerization to occur. The exposure dose used in this specification can be expressed in mJ / cm 2 (mJ / cm 2 = 1,000 μW / cm per second 2 ), taking into account the polymerization time of the exposed photopolymerizable composition. For example, in a stereolithography apparatus, the distance between the radiation source and the photopolymerizable composition in the apparatus is constant, and a 365 nm light source can emit 3 mW / cm 2 to the photopolymerizable composition (irradiance). For the material to be sufficiently photopolymerized in an SLA apparatus, the photopolymerizable composition will be photopolymerized in 10 seconds, resulting in an exposure dose of 0.3 mJ / cm 2 (exposure time to sufficiently polymerize the material). Other photopolymerization apparatuses have similar conditions regarding the exposure depth in the photopolymerizable formulation. Different photopolymerizable materials require different exposure amounts for photopolymerization. For example, an irradiance of 3 mW / cm 2 for 5 seconds (an exposure dose of 0.8 mJ / cm 2 ) is sufficient to fully photopolymerize Material A during a 5 - second exposure to a 3 mW / cm 2 radiation source. To fully photopolymerize Material B, a radiation of 3 mW / cm 2 for 10 seconds (an exposure dose corresponding to 0.3 mJ / cm 2 ) may be required. The exposure dose (exposure time for polymerization) requirement for Material B is greater than the effective exposure dose (exposure time for polymerization) requirement for Material A.

[0010] The exposure dose (the exposure time to sufficiently photopolymerize the material), which may also be referred to as the exposure dose requirement (of the composition) in this specification, can, in one aspect, be adjusted, increased, or decreased by changing the components of the photopolymerizable composition, such that the photopolymerizable composition can be sufficiently photopolymerized at an exposure time different from that of the unaltered material. For example, for Material B, the effective exposure dose requirement for sufficiently photopolymerizing with an SLA apparatus having a specific light source is 0.3 mJ / cm 2 is defined. When the components of Material B are changed to form the altered Material B, the exposure dose requirement of the altered Material B can be determined by holding the radiation source at the same distance, holding the radiation or irradiance constant, e.g., 3 mW / cm 2 , and determining the time for sufficient polymerization by the altered Material B. For example, one or more changes are made to Material B to change the exposure dose requirement from 0.3 mJ / cm 2 of Material B to 0.8 mJ / cm 2 of the altered Material B, and all other components of the reaction (the photopolymerizable composition and the polymerization conditions) are held constant when measuring the exposure dose requirements of Material B and the altered Material B. The altered Material B has a higher exposure dose requirement than Material B. This specification discloses compositions and methods in which the exposure dose requirement of the photopolymerizable composition is adjusted while holding the other components of the reaction constant. In one aspect, the photopolymerizable compositions disclosed herein include a photo-reflective material component or a photo-reflective material that adjusts the exposure dose requirement of the photopolymerizable composition as compared to a composition that does not include the photo-reflective material component or the photo-reflective material.

[0011] The exposure dose requirement can be adjusted by several factors. One of the factors is the increase or decrease in the amount of photoinitiator. Increasing the amount of photoinitiator in the composition generally increases the polymerization rate of the macromer. For example, in SLA printing, increasing the amount of photoinitiator can shorten the exposure time to UV / VIS light and accelerate the photopolymerization of the macromer in the resin or ink photo-curable composition. Further, decreasing the amount of photoinitiator can extend the exposure time to UV / VIS light and delay the photopolymerization of the macromer in the resin or ink photo-curable composition. In addition to the photoinitiator, a dye can be added to the disclosed photopolymerizable printing formulation. The dye can be added for the purpose of adjusting the formulation to a desired color. However, dyes for non-toxic and biocompatible formulations are typically used at concentrations of less than 2% by weight (see, e.g., PCT / US Patent Application Publication No. 2016 / 059910, which is incorporated herein by reference for its teachings regarding the use of such polymerizable compositions and dyes). For absorbent medical devices, the FDA regulates most dyes to contain between 0.1 and 0.3% by weight, as shown for D&C Violet additives for the most absorbent suture products. Combining high concentrations of dyes with high concentrations of photoinitiators results in an obvious toxicity of currently used 3D photoprintable formulations containing them, particularly the resulting photoprints.

[0012] In one aspect, the present disclosure provides a photopolymerization method and a photopolymerizable composition in which a photoinitiator photopolymerizes at a faster rate than expected with a low concentration of the photoinitiator. For example, the irradiation amount requirement of a photopolymerizable composition having a low concentration of a photoinitiator is adjusted by adding at least one light-reflective component to the photopolymerizable composition. The photopolymerizable composition disclosed herein contains at least one light-reflective material component and a low concentration of a photoinitiator, and photopolymerizes at a faster rate than expected with a low concentration of the photoinitiator. For example, compared with a photopolymerizable composition having a low concentration of a photoinitiator, the photopolymerizable composition of the present disclosure having at least one light-reflective material component photopolymerizes at a faster rate than a composition not containing the light-reflective material component. Without wishing to be bound by a particular theory, it is believed that the light-reflective material component reflects the light wavelength and at least a part of the light wavelength is absorbed by at least one photoinitiator present in the photopolymerizable composition, so that more photoinitiator units are activated or the photoinitiator units are activated multiple times. In an SLA apparatus, like other photopolymerization apparatuses, the depth of the material to be photopolymerized is generally kept constant. For example, in an SLA apparatus in which a layer on top of a layer of material is photopolymerized, "sufficiently polymerized" refers to a particular layer of material being exposed to a light source and being photopolymerized to a desired degree. The terms "sufficiently polymerized" and "polymerized" may be used interchangeably and mean that the desired amount of polymerization has occurred, and does not necessarily mean that all of the polymerizable polymers are completely polymerized. "Sufficiently polymerized" is well understood by those skilled in the art. "Sufficiently polymerized" can include partially polymerized materials in addition to wholly or completely polymerized materials. Thus, in this case, "sufficiently polymerized" is similar to sufficient surface curing of the photopolymerizable composition when the bulk composition is exposed to a light source.

[0013] The shape of an object also affects the measurements taken on the incident light hitting the object. For light hitting a flat surface, irradiance, i.e., the radiant power incident per unit area of the surface, is used. For a shaped object, energy fluence rate, i.e., the radiant power incident per unit cross-sectional area of a sphere, captures the curved surface of the object. The term "energy fluence rate" can also be called fluence rate. Other terms having the same meaning as energy fluence rate are spatial irradiance, scalar irradiance, and photon flux. Photon flux is mainly used by atmospheric scientists. Both irradiance and energy fluence rate can be explained from the perspective of photons. When giving a value of irradiance, it is necessary to specify the direction of the plane on which the irradiance is considered. This is often a horizontal plane, but it varies depending on the object being examined. For collimated radiation (coming from a single direction), when the radiation beam is perpendicular to the plane on which the irradiance is measured, the irradiance and fluence rate have the same numerical value. When completely isotropic radiation is incident from above (equally from any direction above the horizontal), the fluence rate is twice the irradiance on the horizontal plane. When a segmented radiation beam hits a plane perpendicularly, irradiance E is obtained, but if the same beam is tilted at an angle to the perpendicular, it spreads more, and thus the irradiance becomes lower. For verification, refer to Beyond the Visible: A handbook of best practice in plant UV photobiology (edited by Pedro Aphalo, published by COST, European Cooperation in Science and Technology, 2012), which is available online. A detailed discussion of energy density and output density in UV-curable materials is described in the Polymer Innovation Blog by Jeffrey Gotro.

[0014] Composition In one aspect, the compositions of the present disclosure include a photopolymerizable formulation, for example, such a formulation may be effective in additive manufacturing methods (3D printing) including, but not limited to, stereolithography, digital light processing (DLP), jet printing, inkjet, or continuous photopolymerization methods and apparatuses. In one aspect, the compositions of the present disclosure are photopolymerizable compositions comprising at least one photopolymerizable macromer component; at least one light-reflecting material component suspended in the photopolymerizable composition; and at least one photoinitiator component, for example, the total concentration of the photoinitiator may be less than 1.0% by mass. In one aspect, the light-reflecting material adjusts the irradiation dose requirement for the photopolymerizable composition as compared to a photopolymerizable composition that does not include the light-reflecting material. In one aspect, the photopolymerizable compositions disclosed herein include a light-reflecting material component that increases the polymerization rate at the surface of the photopolymerizable composition in contact with light as compared to the same photopolymerizable composition that does not include the light-reflecting material component. In one aspect, by incorporating the light-reflecting material component into the photopolymerizable composition, the macromer is surface-cured at a lower photoinitiator concentration than when used in a photopolymerizable composition that does not include the light-reflecting material component. In one aspect, the photopolymerizable composition is a stereolithography composition. The light-reflecting material component as used herein may include a light-reflecting material in addition to other materials (e.g., diluents or common viscosity modifiers), or may be a light-reflecting material.

[0015] Disclosed herein is a photopolymerizable composition comprising at least one photopolymerizable macromer component; at least one light reflecting material component comprising a light reflecting material suspended in the composition; and at least one photoinitiator component, where the light reflecting material component adjusts the dose requirement of the photopolymerizable composition compared to a photopolymerizable composition not comprising the light reflecting material. In one embodiment, the photopolymerizable composition further comprises a reactive diluent. In one embodiment, the photopolymerizable composition further comprises a non-reactive diluent. In one embodiment, the photopolymerizable composition further comprises a reactive or non-reactive viscosity modifier that enhances viscosity. In one embodiment, the photopolymerizable composition further comprises a stabilizer. In one embodiment, the stabilizer is a free radical stabilizer. In one embodiment, the light reflecting material component comprises a particulate light reflecting material. In one embodiment, the light reflecting material component comprises a light reflecting material that reflects UV light, visible light, or both. In one embodiment, the light reflecting material component comprises a light reflecting material that reflects UV light, visible light, or both at wavelengths absorbed by at least one photoinitiator in the photopolymerizable composition. The compositions disclosed herein may include an activator. In one aspect, the light reflecting material component includes an activator. In one aspect, the light reflecting material is an activator. For example, the light reflecting material component may include a light reflecting material and an activator, and optionally other materials such as a diluent, solvent, dispersant, etc. In one aspect, the photopolymerizable macromer component includes an activator. In one aspect, the photopolymerizable macromer includes an activator. In one aspect, the reactive diluent includes an activator. In one aspect, the non-reactive diluent includes an activator. In one aspect, the photopolymerizable composition includes a dye.

[0016] The compositions disclosed herein include a photopolymerizable macromer component that includes a macromer (polymer) capable of photopolymerization. In one aspect, the macromer component includes a monomer and is capable of photopolymerization. The compositions disclosed herein include a photopolymerizable macromer component that includes a macromer (polymer) capable of photopolymerization and that is biodegradable or absorbable under physiological conditions. The compositions disclosed herein include a photopolymerizable macromer component that includes a macromer (polymer) capable of photopolymerization and that is not biodegradable or absorbable under physiological conditions. In one aspect, the photopolymerizable macromer component includes an aliphatic or aromatic macromer, polymer, and / or oligomer having ethylenically unsaturated end groups. For example, the photopolymerizable macromer component includes a polymer having acrylate end groups. In one aspect, the acrylate end groups can be methacrylate end groups. In one aspect, the photopolymerizable macromer includes a photoreactive functional end group, such as acrylate or methacrylate. In one aspect, the photopolymerizable macromer includes a photoreactive functional end group, such as a thiol group. In one aspect, the photopolymerizable composition can include one or more macromers having photoreactive end groups, and the photoreactive functional end groups can be, for example, acrylate or methacrylate, thiol, or a combination of macromers having different end groups such as some having acrylate end groups and some having thiol end groups. In one aspect, the photopolymerizable macromer component can include one or more macromers disclosed in U.S. Provisional Patent Application No. 62 / 660,146, entitled "MACROMERS AND COMPOSITIONS FOR PHOTOCURING PROCESSES," filed Apr. 19, 2018, by applicant Poly-Med, Inc., with inventors M.A. Vaughn and P. Saini, and PCT / U.S. Patent Application Publication No. 2019 / 026,098, entitled "MACROMERS AND COMPOSITIONS FOR PHOTOCURING PROCESSES," filed Apr. 5, 2019, by applicant Poly-Med, Inc., with inventors M.A. Vaughn and P. Saini (both of which are incorporated herein by reference in their entirety).

[0017] In one aspect, the macromer may include a monofunctional, difunctional, trifunctional, tetrafunctional, or pentafunctional photocurable macromer, and in some cases, may include relatively low molecular weight species or relatively high molecular weight species. In one aspect, the macromer may include reactive groups such as, but not limited to, unsaturated functional acrylates (including methacrylates), allyls, and vinyl-based reactive groups, as well as thiol reactive groups. In the present disclosure, highly functional materials having 4, 5, 6, up to 18 reactive sites are considered. Generally, monomer materials have a molecular weight of less than 250 Daltons, while oligomer materials have molecular weights in the tens of thousands.

[0018] In one aspect, the photocurable macromer component is a multi-arm compound including a multi-axial central core (CC) and 2 to 4 arms of formula (A)-(B) or formula (B)-(A) extending from the central core, with at least one arm including a photoreactive functional group (Q). In the multi-arm compound, (A) is a polymer of a monomer selected from trimethylene carbonate (also referred to herein as T or TMC) and ε-caprolactone (also referred to herein as caprolactone or C or CAP), and (B) is a polymer of a monomer selected from glycolide, lactide, and p-dioxanone. The photoreactive functional group Q group is photocurable. In one embodiment, an exemplary Q group may have a thiol group that is photocurable. In one embodiment, an exemplary Q group may have a carbon-carbon double bond that is photocurable, for example, the Q group may include a vinyl group such as those present in acrylate groups or methacrylate groups each having a photocurable carbon-carbon double bond. Such multi-arm compounds can be prepared from the corresponding multi-arm compounds having a hydroxyl group instead of the Q group, and then the Q group is introduced through a reaction of the hydroxyl group. For example, to convert a hydroxyl group to a Q group having a photopolymerizable carbon-carbon double bond, a multi-arm compound having one or more terminal hydroxyl groups can be reacted with a reactive acrylate or methacrylate compound such as methacrylic anhydride, acrylic anhydride, methacryloyl chloride, or acryloyl chloride. As another example, to convert a hydroxyl group to a Q group having a photopolymerizable thiol group, a multi-arm compound having one or more terminal hydroxyl groups can be subjected to an esterification reaction. One method of esterification is to add a stoichiometric amount of a hydroxyl-terminated macromer and a mercaptocarboxylic acid compound in the presence of a carbodiimide (e.g., N,N'-dicyclohexylcarbodiimide) and a catalyst (e.g., dimethylaminopyridine). Exemplary mercaptocarboxylic acids include, but are not limited to, the following compounds: 3-mercaptopropionic acid, thiolactic acid, thioglycolic acid, mercaptobutanoic acid, mercaptohexanoic acid, mercaptobenzoic acid, mercaptoundecanoic acid, mercaptooctanoic acid, and N-acetylcysteine. For example, the multi-arm compounds having terminal hydroxyl groups disclosed herein can be reacted with thiolactic acid, in which case the resulting Q group has the formula -C(=O)-CH2-SH bonded to the terminal oxygen of the multi-arm compound.

[0019] In one embodiment, the multi-arm compound has the formula CC-[arm-Q] n wherein CC represents a central core and n is selected from numbers in the range of 2 to 18, or 2 to 14, or 2 to 8, or 2 to 6, or 2 to 4. Each arm is formed by the polymerization of monomers selected from two groups, represented as group A and group B. Thus, more specifically, in the multi-arm compound, CC-[arm] n is CC-[(A)p-(B)q-Q] n or CC-[(B)q-(A)p-Q] nIt can be represented as, where (A)p-(B)q and (B)q-(A)p each represent an arm. Optionally, the terminal functional group of the arm can be indicated, where Q generally represents a photopolymerizable functional group, and optionally, a terminal photopolymerizable functional group. In the formula, A represents a polymer of trimethylene carbonate (T) and caprolactone (C), and optionally, one or more monomers selected only from these, and p represents the number of monomers polymerized to form polymer A, where p is selected from 1 to 40, or 1 to 30, or 1 to 20, or 1 to 10. In the formula, B represents a polymer of glycolide (G), lactide (L), and p-dioxanone (D), and optionally, one or more monomers selected only from these, and q represents the number of monomers polymerized to form polymer B, where q is selected from 1 to 40, or 1 to 30, or 1 to 20, or 1 to 10.

[0020] In some embodiments, the present disclosure provides multi-arm photopolymerizable macromer compounds and compositions containing such compounds, which compounds are described by any one of the following: The compound has the structure CC-[A-B-Q]n, or includes this structure and n is 2; The compound has the structure CC-[A-B-Q]n, or includes this structure and n is 3; The compound has the structure CC-[A-B-Q]n, or includes this structure and n is 4; The compound has the structure CC-[B-A-Q]n, or includes this structure and n is 2; The compound has the structure CC-[B-A-Q]n, or includes this structure and n is 3; The compound has the structure CC-[B-A-Q]n, or includes this structure and n is 4. Optionally, the compound has four arms, has a molecular mass of less than 40,000 g / mol, or less than 20,000 g / mol, and is a solid at room temperature. Optionally, the compound has three arms, has a molecular mass of less than 15,000 g / mol, and is a liquid at room temperature. Optionally, the compound has two arms, has a molecular mass of less than 5,000 g / mol, and is a liquid at room temperature. Optionally, the photopolymerizable multi-arm compound has relatively short arms, for example, 1 to 10 monomer residues / arm. Optionally, the photopolymerizable multi-arm compound can be described by one or more of the following features characterizing the A region (also called a block) of the compound: having block A containing residues formed from trimethylene carbonate (TMC or T); having block A containing residues formed from caprolactone (CAP or C); having block A containing residues formed from both TMC and CAP; at least 90% of the residues of block A are residues formed from TMC or CAP; the compound contains 1 to 45 or 2 to 45 residues formed from TMC; the compound contains 1 to 15 or 2 to 15 residues formed from TMC; the compound contains 1 to 10 or 2 to 10 residues formed from TMC; the molecular weight of region A is 102 to 2500 g / mol; the molecular weight of region A is 102 to 1000 g / mol; the molecular weight of region A is 102 to 900 g / mol; each A region contains 2 to 45 monomer residues; each A region contains 2 to 15 monomer residues; each A region contains 2 to 10 monomer residues.Optionally, the photopolymerizable multi-arm compound can be described by one or more of the following features characterizing the B-block (also referred to as the region) of the compound: each B-block contains from 1 to 45 or from 2 to 45 monomer residues; each B-block contains from 1 to 15 or from 2 to 15 monomer residues; each B-block contains from 1 to 10 or from 2 to 10 monomer residues. Combining the features describing the A-block and the features describing the B-block can describe the multi-arm photopolymerizable macromer compound of the present disclosure. The compound can similarly or alternatively be described by one or more of the following: the molecular mass of the compound is less than 40,000 g / mol; the molecular mass of the compound is less than 25,000 g / mol; the molecular mass of the compound is less than 10,000 g / mol.

[0021] In any of the multi-arm photopolymerizable compounds and compositions described herein, Q can be a carbon-carbon double bond, such as a vinyl group. Exemplary vinyl groups are acrylate and methacrylate groups. In an additional aspect, a photopolymerizable compound having one or more Q groups photopolymerizes when exposed to light having a wavelength of, for example, 300 - 450 nm, or 300 - 425 nm, or 350 - 450 nm, or 350 - 425 nm, or 365 - 405 nm. In one embodiment, the compounds and compositions photopolymerize when exposed to UV radiation. In any of the multi-arm photopolymerizable compounds and compositions described herein, Q can be a thiol group. In an additional aspect, a photopolymerizable compound having one or more Q groups photopolymerizes when exposed to light having a wavelength of, for example, 300 - 450 nm, or 300 - 425 nm, or 350 - 450 nm, or 350 - 425 nm, or 365 - 405 nm. In one embodiment, the compounds and compositions photopolymerize when exposed to UV radiation.

[0022] Generally, for the free radical polymerization of thiols using a photoinitiator, a much higher concentration of photoinitiator is required than when the Q group has a photopolymerizable carbon-carbon double bond. When having a thiol group, the photoinitiator can initiate the thiol group, but two thiol groups can polymerize only when two thioyl radicals meet. Furthermore, since the bond of two thioyl radicals is the termination of the radical group, a high concentration of photopolymerization initiator is required. When the photopolymerizable group is a carbon-carbon double bond, such as a vinyl group, or contains it, one free radical can initiate and propagate a number of vinyl groups before termination. Therefore, when photopolymerization proceeds via a thiol group, it is advantageous to have a relatively high density of thiol groups. The lower the concentration of the thiol end group, the lower the probability of both the generation of thioyl radicals and the bond of two thioyl radicals causing polymerization. From this perspective, a multi-arm thiol compound of low molecular weight (i.e., preferably less than 5000 daltons, more preferably less than 3000 daltons, and even more preferably less than 2000 daltons) is preferred for the photopolymerization process of the present disclosure.

[0023] In one aspect, the present disclosure provides a photocurable composition comprising one or more photopolymerizable macromer compounds, the composition further comprising a photoinitiator and a light-reflecting material component comprising a light-reflecting material suspended in the composition; the photopolymerizable macromer compound is a multi-arm compound comprising a central core (CC) and two to four arms extending from the central core, at least one arm comprising a block copolymer comprising a photoreactive functional group (Q) and blocks A and B; wherein block A comprises a residue formed from at least one of trimethylene carbonate (TMC) and ε-caprolactone (CAP), i.e., a polymer thereof; and block B comprises a residue formed from at least one of glycolide, lactide, and p-dioxanone, i.e., a polymer thereof. Optionally, the multi-arm photopolymerizable compound has the structure CC-[A-B-Q]2. Optionally, the multi-arm photopolymerizable compound has the structure CC-[A-B-Q]3. Optionally, the multi-arm photopolymerizable compound has the structure CC-[A-B-Q]4. Optionally, the multi-arm photopolymerizable compound has the structure CC-[B-A-Q]2. Optionally, the multi-arm photopolymerizable compound has the structure CC-[B-A-Q]3. Optionally, the multi-arm photopolymerizable compound has the structure CC-[B-A-Q]4.

[0024] Disclosed herein is a photopolymerizable composition comprising a photopolymerizable macromer component comprising a macromer (having reactive end groups) comprising monomer units of at least one lactone monomer including, but not limited to, glycolide, lactide, ε-caprolactone, trimethylene carbonate, p-dioxanone, 1,5-dioxepan-2-one, or morpholine-2,5-dione. The photopolymerizable macromer can be, for example, a polyester. In one aspect, the polyester comprises a segmented / block or random copolymer having sequences derived from at least one monomer of glycolide, lactide, trimethylene carbonate, p-dioxanone, or caprolactone. The photopolymerizable macromer can include a polysaccharide or macromer comprising one or more of the following monosaccharide units: arabinose, fructose, galactose, galactopyranosyl, galacturonic acid, guluronic acid, glucuronic acid, glucose, glucoside, N-acetylglucosamine, mannuronic acid, mannose, pyranosyl sulfate, rhamnose, or xylose. Polysaccharides containing the aforementioned units include cyclodextrin, starch, hyaluronic acid, deacetylated hyaluronic acid, chitosan, trehalose, cellobiose, maltotriose, maltohexaose, chitohexaose, agarose, chitin50, amylose, glucan, heparin, xylan, pectin, galactan, glycosaminoglycan, dextran, aminated dextran, cellulose, hydroxyalkyl cellulose, carboxyalkyl cellulose, fucoidan, chondroitin sulfate, sulfated polysaccharide, mucopolysaccharide, gelatin, zein, collagen, alginic acid, agar, carrageenan, guar gum, gum arabic, ghatti gum, karaya gum, konnyaku gum, tamarind gum, tara gum, tragacanth gum, locust bean gum, pectin, and xanthan gum, etc. Polysaccharides that are either anionic or cationic include natural polysaccharides such as alginic acid, carrageenan, chitosan (partially deacetylated chitin), gum arabic, ghatti gum, karaya gum, tragacanth gum, pectin, and xanthan gum, etc. Synthetic polymers containing multiple pendant photopolymerizable groups are also suitable.Suitable synthetic polymers include poly(vinyl alcohol), poly(ethylene glycol), poly(propylene oxide), and PEG-block-PPO, PEG-block-PPO-block-PEG, and PPO-block-PEG-block-PPO, each containing acrylate or methacrylate end groups.

[0025] This specification discloses a photopolymerizable composition comprising a macromer having an ethylenically unsaturated group and, optionally, a photopolymerizable macromer component comprising a monomer unit (monomer) having an ethylenically unsaturated group. Generally, any monomer that does not conflict with the objectives of the present disclosure may be used. In one aspect, the macromer or monomer comprises one or more of one or more (meth)acrylates, such as monofunctional, difunctional, trifunctional, tetrafunctional (meth)acrylates, and / or pentafunctional (meth)acrylates. In one aspect, the macromer or monomer comprises methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, n-hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, n-decyl (meth)acrylate, n-dodecyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2- or 3-hydroxypropyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, 2- or 3-ethoxypropyl (meth)acrylate, tetrahydrofurfuryl methacrylate, isobornyl (meth)acrylate, 2-(2-ethoxyethoxy)ethyl acrylate, cyclohexyl methacrylate, 2-phenoxyethyl acrylate, glycidyl acrylate, isodecyl acrylate, 2-phenoxyethyl (meth)acrylate, lauryl methacrylate, or a combination thereof. In one aspect, the monomer comprises one or more of allyl acrylate, allyl methacrylate, triethylene glycol di(meth)acrylate, tricyclodecane dimethanol diacrylate, and cyclohexane dimethanol diacrylate.In one aspect, the macromer or monomer comprises a diacrylate and / or dimethacrylate ester of an aliphatic, cycloaliphatic, or aromatic diol including 1,3- or 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, tripropylene glycol, 1,4-dihydroxymethylcyclohexane, 2,2-bis(4-hydroxycyclohexyl)propane or bis(4-hydroxycyclohexyl)methane, hydroquinone, 4,4'-dihydroxybiphenyl, bisphenol A, bisphenol F, or bisphenol S. In one aspect, the macromer or monomer may comprise 1,1-trimethylolpropane tri(meth)acrylate, pentaerythritol monohydroxy tri(meth)acrylate, dipentaerythritol monohydroxy penta(meth)acrylate, and / or bis(trimethylolpropane) tetra(meth)acrylate. In one aspect, the monomer may comprise ethoxylated or propoxylated species such as ethoxylated or propoxylated neopentyl glycol, ethoxylated or propoxylated bisphenol A, ethoxylated or propoxylated bisphenol F, ethoxylated or propoxylated bisphenol S, ethoxylated or propoxylated 1,1,1-trimethylolpropane tri(meth)acrylate, or ethoxylated or propoxylated glycerol tri(meth)acrylate.

[0026] In one aspect, the macromer or monomer may include isobornyl acrylate (IBOA) commercially available from Sartomer (Sartomer Americas, 502 Thomas Jones Way, Exton, PA 19341) under the trade name SR506; isobornyl methacrylate commercially available from Sartomer under the trade name SR423A; triethylene glycol diacrylate commercially available from Sartomer under the trade name SR272; triethylene glycol dimethacrylate commercially available from Sartomer under the trade name SR205; tricyclodecane dimethanol diacrylate commercially available from Sartomer under the trade name SR833S; tris(2-hydroxyethyl) isocyanurate triacrylate commercially available from Sartomer under the trade name SR368; 2-phenoxyethyl acrylate commercially available from Sartomer under the trade name SR339; ethoxylated (3 mol) bisphenol A diacrylate commercially available from Sartomer under the trade name SR349; and dipentaerythritol pentaacrylate commercially available from Sartomer under the trade name SR399LV.

[0027] In one aspect, the macromer may include at least the following classes of homopolymers or copolymers: polyester (meth)acrylate oligomers, polycarbonate (meth)acrylate oligomers, urethane (meth)acrylate oligomers, thiol-functionalized oligomers, or epoxy (meth)acrylate oligomers, or combinations thereof. The classes of polymers or copolymers are well known in the art. In one aspect, the macromer may include an aliphatic polyester urethane acrylate oligomer and / or an acrylate amine oligomer resin, such as EBECRYL 7100 (Allnex, Frankfurt - Global HQ, The Squaire 13, Am Flughafen, 60549 Frankfurt am Main, Germany). In one aspect, the macromer may include polypropylene glycol mono(meth)acrylate or polyethylene glycol mono(meth)acrylate. In one aspect, the macromer may include a monofunctional aliphatic urethane (meth)acrylate. In one aspect, the macromer may include diacrylates and / or dimethacrylate esters of aliphatic, cycloaliphatic, or aromatic diols including polyethylene glycol, ethoxylated or propoxylated neopentyl glycol, ethoxylated or propoxylated bisphenol A, ethoxylated or propoxylated bisphenol F, ethoxylated or propoxylated bisphenol S, ethoxylated or propoxylated 1,1,1-trimethylolpropane tri(meth)acrylate, or ethoxylated or propoxylated glycerol tri(meth)acrylate. In one aspect, the macromer may include alkoxylated tetrahydrofurfuryl acrylate commercially available from Sartomer under the trade name SR611; monofunctional urethane acrylate commercially available from RAHN (USA Kinetik Technologies, 8 Crown Plaza, Suite 110, Hazlet, NJ 07730, USA) under the trade name GENOMER 1122; and aliphatic urethane diacrylate commercially available from ALLNEX under the trade name EBECRYL 8402. Other commercially available oligomeric curable materials may also be used.In one aspect, the macromer may include urethane (meth)acrylate. In one aspect, the macromer may include a polyester carbonate (meth)acrylate oligomer.

[0028] The photopolymerizable composition disclosed herein includes a photoreactive compound that polymerizes at a light wavelength of 10 to 770 nm (UV light 10 to 400) (visible light 390 to 770) (referred to as UV / Vis light herein), or a compound having a photoreactive group (e.g., a photoreactive end group).

[0029] Light-reflecting material The photopolymerizable composition disclosed herein includes a light-reflecting material component including at least one light-reflecting material. When a light-reflecting material is present in the photopolymerizable composition, the photopolymerizable composition photopolymerizes in a shorter time than a photopolymerizable composition not including a light-reflecting material under the same polymerization conditions. In one aspect, when a light-reflecting material is present in the photopolymerizable composition, it photopolymerizes at a faster rate than a photopolymerizable composition not including a light-reflecting material at the same exposure amount (mJ / cm 2 2) under the same polymerization conditions. In one aspect, the light-reflecting material reflects light at the same wavelength at which the photoinitiator absorbs light.

[0030] The light-reflecting material includes an organic compound, an inorganic compound, or a combination thereof. In one aspect, the light-reflecting material may include an inorganic solid including, but not limited to, titanium dioxide, zinc oxide, barium sulfate, tricalcium phosphate, dicalcium phosphate, monocalcium phosphate, dicalcium pyrophosphate, tricalcium phosphate, hydroxyapatite, apatite, and tetracalcium phosphate. In one aspect, the light-reflecting material may include an organic compound including aliphatic polymers and copolymers including, but not limited to, polyester, polyurethane, polyether, polyanhydride, polyamide, polysulfide, polycarbonate, polyketone, polyethylene, polypropylene, polyvinyl alcohol, polytetrafluoroethylene, polyvinyl chloride, polyimide, and polyhydroxyalkanoate, or a combination thereof. For example, polyglycolide-co-lactide, polycaprolactone urethane, polyethylene glycol, and polyglycolide can be used as the light-reflecting material. In one aspect, the light-reflecting material may include an organic compound including aromatic polymers and copolymers including, but not limited to, polyester, polyurethane, polyarylate, polysulfide, polyether, polyanhydride, polyketone, polyamide, polycarbonate, and polyimide, or a combination thereof. For example, polyetheretherketone (PEEK) and poly-4-hydroxybenzoic acid can be used as the light-reflecting material.In one aspect, the light-reflecting material may include an organic compound including natural-derived polymers and derivatives including, but not limited to, cyclodextrin, starch, hyaluronic acid, deacetylated hyaluronic acid, chitosan, trehalose, cellobiose, maltotriose, maltohexaose, chitohexaose, agarose, chitin50, amylose, glucan, heparin, xylan, pectin, galactan, glycosaminoglycan, dextran, aminated dextran, cellulose, hydroxyalkyl cellulose, carboxyalkyl cellulose, fucoidan, chondroitin sulfate, sulfated polysaccharides, mucopolysaccharides, gelatin, zein, collagen, alginic acid, agar, carrageenan, guar gum, gum arabic, ghatti gum, karaya gum, konnyaku gum, tamarind gum, tara gum, tragacanth gum, locust bean gum, pectin, and xanthan gum. In one aspect, the light-reflecting material may include a crystalline organic compound including crystalline aliphatic and aromatic polymers. In one aspect, the light-reflecting material may include a crystalline organic compound including crystalline natural-derived polymers and derivatives. In one aspect, the light-reflecting material may include crystalline amino acids and their derivatives. In one aspect, the light-reflecting material may include crystalline fatty acids and their derivatives including, but not limited to, palmitic acid, ascorbyl palmitate, lauric acid, glyceryl monolaurate, myristic acid, and capric acid. In one aspect, the light-reflecting material may include a crystalline peptide. As used herein, the term "crystalline" includes semi-crystalline materials. As will be understood by those skilled in the art, a crystalline material is a material in which its components (chains in the case of polymers) are highly ordered to form an organized structure or arrangement. In the case of semi-crystalline polymers, there are ordered regions and non-ordered regions. The light-reflecting material component of the photopolymerizable composition disclosed herein may constitute about 5 to about 90% by mass of the photopolymerizable composition, or about 5 to about 85% by mass of the photopolymerizable composition, or about 5 to about 80% by mass, or about 5 to about 75% by mass, or about 5 to about 70% by mass, or about 5 to about 65% by mass, or about 5 to about 60% by mass, or about 5 to about 55% by mass, or about 5 to about 50% by mass, or about 15 to about 45% by mass, or about 5 to about 45% by mass, or about 10 to about 35% by mass of the photopolymerizable composition, and any range therebetween.In one aspect, the light-reflecting material component includes particulate light-reflecting materials sized from less than 1 micron to up to 500 microns, and any size range therebetween. For example, the particulate light-reflecting material can be less than 30 microns in size, less than 5 microns in size, or 1 micron or less, and including sizes that include nanoparticles. In one aspect, the light-reflecting material component includes particulate light-reflecting materials shaped as spheres, cubes, cones, rectangular prisms, cylinders, pyramids, prisms, polyhedrons, or irregular shapes, or combinations thereof. In one aspect, the light-reflecting material component includes particulate light-reflecting materials having smooth surfaces. In one aspect, the light-reflecting material component includes particulate light-reflecting materials having rough or uneven surfaces. In one aspect, the light-reflecting material component includes light-reflecting materials that are liquids.

[0031] In one aspect, the light-reflecting material component includes light-reflecting materials that are absorbent or biodegradable under physiological conditions. In one aspect, the light-reflecting material component includes light-reflecting materials that are biocompatible with biological organisms. In one aspect, the light-reflecting material component includes light-reflecting materials that are not absorbent or biodegradable under physiological conditions. In one aspect, the light-reflecting material can polymerize with at least one of a photopolymerizable macromer, a diluent, a light-reflecting material, or combinations thereof. In one aspect, the light-reflecting material component consists essentially of a light-reflecting material.

[0032] Photoinitiator The photopolymerizable composition disclosed herein contains a photoinitiator component including at least one photoinitiator. In one aspect, the photoinitiator component constitutes from about 0.01% to about 5.0% by mass, from about 0.05% to about 4.5% by mass, from about 0.05% to about 4.0% by mass, from about 0.1% to about 5.0% by mass, from about 0.05% to about 3.0% by mass, from about 0.1% to about 3.0% by mass, from about 0.05% to about 2.0% by mass, from about 0.05% to about 1.0% by mass, from about 0.1% to about 1.0% by mass, from about 0.07% to about 1.0% by mass, from about 0.2% to about 1.0% by mass, from about 0.5% to about 1.0% by mass, from about 1.0% to about 2.0% by mass, from about 0.1% to about 2.0% by mass, from about 0.05% to about 5.0% by mass, from about 0.05% to about 0.1% by mass, from about 0.01% to about 0.099% by mass, from about 0.01% to about 0.09% by mass, from about 0.01% to about 0.085% by mass, from about 0.01% to about 0.080% by mass, from about 0.01% to about 0.070% by mass, from about 0.01% to about 0.060% by mass, from about 0.01% to about 0.050% by mass, from about 0.01% to about 0.040% by mass, from about 0.01% to about 0.030% by mass, from about 0.01% to about 0.020% by mass, from about 0.01% to about 0.015% by mass, and all concentration ranges therebetween. In one aspect, the photoinitiator component constitutes less than 1.0% by mass of the photopolymerizable composition. In one aspect, the photoinitiator component is less than 0.50% by mass of the photopolymerizable composition. In one aspect, the photoinitiator component is 0.25% by mass of the photopolymerizable composition. In one aspect, the photoinitiator component is less than 0.25% by mass of the photopolymerizable composition. In one aspect, the photoinitiator component is 0.10% by mass of the photopolymerizable composition. In one aspect, the photoinitiator component is less than 0.10% by mass of the photopolymerizable composition.

[0033] The photopolymerizable composition disclosed herein contains at least one photoinitiator that absorbs light in the wavelength range of about 200 to about 770 nm and all wavelengths therebetween. In one aspect, the photoinitiator component contains a photoinitiator that absorbs light at a wavelength of 300 nm or more. In one aspect, the photoinitiator component contains a photoinitiator that absorbs light at a wavelength of 365 nm or more. In one aspect, the photoinitiator component contains a photoinitiator that absorbs light at a wavelength of 375 nm or more. In one aspect, the photoinitiator component contains a photoinitiator that absorbs light at a wavelength of 400 nm or more. The photopolymerizable composition disclosed in this specification contains at least one photoinitiator in the photoinitiator component. In one aspect, the photoinitiator component contains a type I photoinitiator, a type II photoinitiator, or a combination of type I and type II photoinitiators. In one aspect, the photoinitiator component contains a cationic photoinitiator. Free radical generating photoinitiators are used to cure double bonds, most commonly acrylate and methacrylate monomers or oligomers. There are two types of free radical generating photoinitiators, referred to as type I and type II photoinitiators.

[0034] Type I photoinitiators are unimolecular free radical generators; that is, when they absorb UV-visible light, specific bonds within the initiator's structure undergo homolytic cleavage to generate free radicals. In homolytic cleavage, the bonding electron pair is split evenly to generate free radicals. Examples of homolytic cleavage can be seen in several general classes of Type I photoinitiators, namely benzoin ethers, benzyl ketals, α-dialkoxy-acetophenones, α-hydroxy-alkyl-phenones, and acylphosphine oxides. Type II photoinitiators generally require, in addition to the photoinitiator, a co-initiator (usually an alcohol or an amine) functional group that can readily abstract hydrogen. When a Type II photoinitiator absorbs UV-visible light, an excited electronic state is generated in the photoinitiator, which causes hydrogen to be abstracted from the co-initiator, and in the process, the bonding electron pair is split. Benzophenone, thioxanthone, and benzophenone-based photoinitiators are common Type II photoinitiators. Other examples of common Type II photoinitiators include, but are not limited to, riboflavin, eosin Y, and camphorquinone. Once free radicals are generated, the polymerization mechanism is the same as any free radical polymerization process. Other commercially available Type I photoinitiators include, for example, Irgacure 369, Irgacure 379, Irgacure 907, Darocur 1173, Irgacure 184, Irgacure 2959, Darocur 4265, Irgacure 2022, Irgacure 500, Irgacure 819, Irgacure 819-DW, Irgacure 2100, Lucirin TPO, Lucirin TPO-L, Irgacure 651, Darocur BP, Irgacure 250, Irgacure 270, Irgacure 290, Irgacure 784, Darocur MBF, Irgacure 754, lithium phenyl-2,4,6-trimethylbenzoylphosphinate, magnesium phenyl-2,4,6-trimethylbenzoylphosphinate, and sodium phenyl-2,4,6-trimethylbenzoylphosphinate, which are available from, for example, BASF, BASF SE (Ludwigshafen, Germany).

[0035] In one aspect, the stereolithography ink composition disclosed herein includes at least one photopolymerizable macromer component; at least one light-reflecting material component including a light-reflecting material suspended in the photopolymerizable composition; at least one photoinitiator component having a total concentration of less than 0.1% by mass or less than 1.0% by mass; wherein the light-reflecting material component adjusts the irradiation amount of the composition as compared to the irradiation amount of the composition not containing the light-reflecting material; a reactive diluent; and a stabilizer. In one aspect, the light-reflecting material component increases the polymerization rate at the surface of the photopolymerizable composition in contact with light as compared to the same photopolymerizable composition not containing the light-reflecting material component. In one aspect, by incorporating the light-reflecting material component into the photopolymerizable composition, the photopolymerizable macromer is surface-cured at a lower photoinitiator concentration than when used in a photopolymerizable composition not containing the light-reflecting material component. The photopolymerizable composition disclosed herein is created by combining the disclosed components, such as photopolymerizable macromers, UV-reflecting materials, and photoinitiators, and optionally other components such as stabilizers or diluents. The disclosed components are mixed until a homogeneous composition is formed. Optionally, the disclosed components may include a dispersant useful for suspension. The disclosed components may be mixed using a homogenizer. Optionally, the disclosed components may be heated prior to mixing. Optionally, the disclosed components may be placed under vacuum to remove air bubbles. The composition disclosed herein includes a non-toxic biocompatible polymer composition including a photopolymerizable macromer and a non-toxic amount of at least one photoinitiator. In one aspect, the non-toxic biocompatible polymer composition may include a photopolymerizable diluent. In one aspect, the non-toxic biocompatible polymer composition may include a photopolymerizable light-reflecting material. In one aspect, the non-toxic biocompatible polymer composition may include a medical device component. In one aspect, the non-toxic biocompatible polymer composition may include a photopolymerizable macromer and a non-toxic amount of at least one photoinitiator as a coating on at least a portion of an article and optionally other components disclosed herein, such as a light-reflecting material.

[0036] The methods disclosed herein include methods of creating and using a photopolymerizable composition, such as for creating an additively manufactured article. For example, the compositions disclosed herein can be used as a photopolymerizable or photocurable ink or resin in an additive manufacturing or 3D printing process. In one aspect, the compositions disclosed herein can be used as a photopolymerizable or photocurable ink or resin in any known or later-developed 3D printing process. For example, the compositions disclosed herein can be used as a photopolymerizable or photocurable ink or resin in a 3D printing process or stereolithography (SLA). The disclosed method of photopolymerizable 3D printing (additive manufacturing) an article is a photopolymerizable composition comprising at least one photopolymerizable macromer component; at least one light-reflecting material component comprising a light-reflecting material suspended in the photopolymerizable composition; and at least one photoinitiator component; temporarily exposing the photopolymerizable composition to light such that the light-reflecting material component adjusts the irradiation amount of the photopolymerizable composition compared to the irradiation amount of a photopolymerizable composition that does not contain the light-reflecting material; and forming a print comprising at least the polymerized macromer. In one aspect, the light-reflecting material component increases the polymerization rate at the surface of the photopolymerizable composition in contact with light compared to the same photopolymerizable composition that does not contain the light-reflecting material component. In one aspect, by incorporating the light-reflecting material component into the photopolymerizable composition, the macromer is surface-cured at a lower photoinitiator concentration than when used in a photopolymerizable composition that does not contain the light-reflecting material component. Any of the compositions disclosed herein can be used in a method of photopolymerizable 3D printing an article. For example, the photopolymerizable composition can include a reactive diluent or a non-reactive diluent. A reactive diluent is a diluent that participates in the polymerization reaction, for example, a reactive diluent polymerizes with, for example, a macromer. The photopolymerizable composition can include a stabilizer, such as a free radical stabilizer. The compositions disclosed herein can include a particulate light-reflecting material. In one aspect, the light-reflecting material can reflect UV light, visible light, or both. In one aspect, the photopolymerizable composition can be heated or cooled, and the method of SLA printing an article can include one or more steps of heating or cooling the photopolymerizable composition. In one aspect, the photopolymerizable composition may include an activator. The activator may be one of any of the components of the photopolymerizable composition, or any of the components of the photopolymerizable composition may include an activator. For example, a light reflecting material, a macromer, a diluent, or a stabilizer may include an activator or may be an activator.

[0037] The method of printing an article by photopolymerizable 3D printing may further include a secondary curing step including a step of curing the printed article. The method may include pre-treatment and post-treatment of the printed article. For example, the printed article may be rinsed after printing, before the secondary curing step, after a secondary printing step, or before or after each step. Since the secondary curing step includes a step of exposing at least a part of the printed article, at least a part of the printed article undergoes a second polymerization reaction. For example, a part of the article may be exposed to radiation of the same or different wavelength as that used in the first polymerization step, and activate a photoinitiator, which may be the same or different photoinitiator as that reacted in the first polymerization step, to cause a polymerization reaction in a reactive group that has not been polymerized or has been partially polymerized previously, and may be polymerized. The secondary curing step may change the properties of the printed article. For example, after the first printing step, the printed article is generally flexible and easy to bend. When the outside of the printed article is exposed to the secondary curing step using, for example, radiation of a different wavelength, the outside of the printed article becomes hard and difficult to bend. The printed article is an article that results after the photopolymerizable 3D printing stage. The printed article may be a structure or a part of a structure. The printed article may be a coating printed on a surface. Printing is used to mean contacting a polymer composition with a surface and polymerizing the polymer composition. Printing may include a step of contacting a polymer composition with a surface and then exposing it to UV / Vis light to polymerize the polymer composition. The surface in contact with the polymer composition may be any surface including a polymerized layer of the polymer composition.

[0038] The printed matter may or may not contain the remaining amount of the components of the photopolymerizable composition. For example, the printed matter may contain a diluent or a photopolymerizable diluent, or a photoinitiator. In one aspect, the printed matter or the photopolymerizable composition may have an additive. The additive may include a thixotropic material, a colorant, a tracer material, or a conductive material. For example, the additive may be a dye. The printed matter may be colored due to the presence of the dye, or may have any desired attributes such as fluorescence, radioactivity, reflectivity, flexibility, or hardness, bendability, breakability, or a combination thereof (but not limited thereto), and may have at least a part of an article having these properties. The method of 3D printing an article to be photopolymerizable may include the step of photopolymerizing a photopolymerizable composition including a polymerizable monomer or macromer, such as a monomer or macromer having a functional group capable of undergoing a photopolymerization reaction to form an oligomer and / or a polymer. In one aspect, the aliphatic or aromatic macromer and monomer may include an ethylenically unsaturated reactive group or end group. The disclosed macromer and monomer are functional in the methods disclosed herein.

[0039] The method of 3D printing an article to be photopolymerizable, such as DLP, SLA, jet printing, inkjet, or CLIP, may include the step of photopolymerizing the photopolymerizable composition at a light wavelength of about 10 to 770 nm (UV light 10 to 400) (visible light 390 to 770). In one aspect, a photopolymerizable composition including a light-reflecting material component photopolymerizes in a shorter exposure time than a photopolymerizable composition not including the light-reflecting material component under the same polymerization conditions. A method of printing an article using a photopolymerization technique with a 3D photopolymerization printing apparatus includes the step of photopolymerizing a photopolymerizable composition containing a photoinitiator component. The photoinitiator component may include one or more photoinitiators and may also include other materials such as diluents, excipients, inhibitors, or other solutions. In one aspect, the photoinitiator component constitutes a concentration range of about 0.05 to about 5.0% by mass, about 0.05 to about 4.5% by mass, about 0.05 to about 4.0% by mass, about 0.1 to about 5.0% by mass, about 0.05 to about 3.0% by mass, about 0.1 to about 3.0% by mass, about 0.05 to about 2.0% by mass, about 0.05 to about 1.0% by mass, about 0.1 to about 1.0% by mass, about 0.07 to about 1.0% by mass, about 0.2 to about 1.0% by mass, about 0.5 to about 1.0% by mass, about 1.0 to about 2.0% by mass, about 0.1 to about 2.0% by mass, about 0.05 to about 5.0% by mass, about 0.05 to about 0.1% by mass, and any concentration ranges therebetween in a photopolymerizable composition. In one aspect, the photoinitiator component may be at a concentration of less than 0.50% by mass of the photopolymerizable composition. In one aspect, the photoinitiator component may be 0.25% by mass of the photopolymerizable composition. In one aspect, the photoinitiator component may be less than 0.25% by mass of the photopolymerizable composition. In one aspect, the photoinitiator component may be 0.10% by mass of the photopolymerizable composition. In one aspect, the photoinitiator component may be less than 0.10% by mass of the photopolymerizable composition. A method of printing an article using a stereolithography (SLA) technique with an SLA printing apparatus includes photopolymerizing a photopolymerizable composition including at least one photoinitiator component that is a type I, type II, cationic photoinitiator, or a combination thereof. A method of printing an article using a photopolymerization technique with a 3D photopolymerization printing apparatus includes the step of photopolymerizing a photopolymerizable composition including at least one photoinitiator that absorbs at a wavelength of light reflected by at least one light-reflective component of the photopolymerizable composition. A method of printing an article using a photopolymerization technique with a 3D photopolymerization printing apparatus includes the step of photopolymerizing a photopolymerizable composition containing at least one photoinitiator that absorbs at a wavelength of light in the range of about 10 to about 770 nm. In one aspect, the photoinitiator absorbs at a wavelength of light of 300 nm or greater. In one aspect, the photoinitiator absorbs at a wavelength of light of 365 nm or greater. In one aspect, the photoinitiator absorbs at a wavelength of light of 375 nm or greater. In one aspect, the photoinitiator absorbs at a wavelength of light of 400 nm or greater.

[0040] This disclosure contemplates the use of the disclosed formulations in a photopolymerization printing apparatus or method and is not limited to a particular manufacturing or production method. The disclosed manufacturing or production methods include, but are not limited to, DLP (Digital Light Processing), SLA (Stereolithography), jet printing, inkjet, and CLIP (Continuous Liquid Interface Production). A method of printing an article using SLA in an SLA-based printing apparatus includes the step of photopolymerizing or curing a photopolymerizable composition at a depth of less than 150 microns. In one aspect, the methods disclosed herein include the step of photopolymerizing or curing a photopolymerizable composition at a depth of from about 1 to about 50 microns and at any depth therebetween. A method of printing an article from a photopolymerizable macromer, a UV reflective material, and a photoinitiator using continuous liquid interface printing (see, e.g., U.S. Patent No. 9,205,601), CLIP, is a 3D printing method that utilizes photopolymerization to create solids of various shapes using a photopolymerizable resin. The continuous process begins with a pool of liquid photopolymer resin. A portion of the bottom of the pool is transmissive to ultraviolet light ("window"). An ultraviolet light beam is inserted through the window and shines light on the exact cross-section of the object. The light solidifies the resin. The object slowly rises such that resin can flow in under the object and maintain contact with the bottom of the object. There is an oxygen permeable membrane under the resin, creating a "dead zone" (continuous liquid interface) that prevents the resin from sticking to the window (photopolymerization is inhibited between the window and the polymerization apparatus).

[0041] A method of printing an article using photopolymerization in a printing apparatus by photopolymerization-based 3D additive manufacturing includes the step of photopolymerizing a photopolymerizable composition including at least one light-reflecting material component including a light-reflecting material including, but not limited to, inorganic or organic compounds. In one aspect, the light-reflecting material may include inorganic solids including, but not limited to, titanium dioxide, zinc oxide, barium sulfate, tricalcium phosphate, dicalcium phosphate, monocalcium phosphate, dicalcium nilinate, tricalcium phosphate, hydroxyapatite, apatite, and tetracalcium phosphate. In one aspect, the light-reflecting material may include organic compounds including aliphatic polymers and copolymers including, but not limited to, polyester, polyurethane, polyether, polyanhydride, polyamide, polycarbonate, polyketone, polyethylene, polypropylene, polyvinyl alcohol, polytetrafluoroethylene, polyvinyl chloride, polyimide, and polyhydroxyalkanoate, or combinations thereof. In one aspect, the light-reflecting material may include organic compounds including aromatic polymers and copolymers including, but not limited to, polyester, polyurethane, polyether, polyanhydride, polyketone, polyamide, polycarbonate, and polyimide, or combinations thereof. In one aspect, the light-reflecting material may include organic compounds including naturally-derived polymers and derivatives including, but not limited to, cyclodextrin, starch, hyaluronic acid, deacetylated hyaluronic acid, chitosan, trehalose, cellobiose, maltotriose, maltohexaose, chitohexaose, agarose, chitin50, amylose, glucan, heparin, xylan, pectin, galactan, glycosaminoglycan, dextran, aminated dextran, cellulose, hydroxyalkyl cellulose, carboxyalkyl cellulose, fucoidan, chondroitin sulfate, sulfated polysaccharides, mucopolysaccharides, gelatin, zein, collagen, alginic acid, agar, carrageenan, guar gum, gum arabic, ghatti gum, karaya gum, konnyaku gum, tamarind gum, tara gum, tragacanth gum, locust bean gum, pectin, and xanthan gum. In one aspect, the light-reflecting material may include crystalline organic compounds including crystalline aliphatic and aromatic polymers.In one aspect, the light-reflective material may include a crystalline organic compound including a crystalline natural-derived polymer and derivatives. In one aspect, the light-reflective material may include crystalline amino acids and their derivatives. In one aspect, the light-reflective material may include crystalline fatty acids and their derivatives including, but not limited to, palmitic acid, ascorbyl palmitate, lauric acid, glycerol monolaurate, myristic acid, and capric acid. In one aspect, the light-reflective material may include a crystalline peptide.

[0042] In one aspect, the light-reflective material component constitutes about 5 to about 90% by mass, or about 5 to about 85% by mass, or about 5 to about 80% by mass, or about 5 to about 75% by mass, or about 5 to about 70% by mass, or about 5 to about 65% by mass, or about 5 to about 60% by mass, or about 5 to about 55% by mass, or about 5 to about 50% by mass, or about 15 to about 45% by mass, or about 5 to about 45% by mass, or about 10 to about 35% by mass of the photopolymerizable composition, and all ranges therebetween. In one aspect, the light-reflective material component constitutes about 5 to about 45% by mass of the photopolymerizable composition. In one aspect, the light-reflective material component constitutes about 10 to about 35% by mass of the photopolymerizable composition. In one aspect, the light-reflective material component includes a particulate light-reflective material having a size of less than 500 microns. In one aspect, the light-reflective material component includes a particulate light-reflective material having a size of less than 30 microns. In one aspect, the light-reflective material component includes a particulate light-reflective material having a size of less than 5 microns. In one aspect, the light-reflective material component includes a particulate light-reflective material having a size of less than 1 micron. In one aspect, the light-reflective material component includes a particulate light-reflective material formed into a sphere, cube, cone, rectangular prism, cylinder, pyramid, prism, polyhedron, or irregular shape, or a combination thereof. In one aspect, the light-reflective material component includes a particulate light-reflective material having a smooth surface. In one aspect, the light-reflective material component includes a particulate light-reflective material having a rough or uneven surface. In one aspect, the light-reflective material component includes a liquid.

[0043] A method of printing an article using photopolymerization in a printing apparatus by photopolymerizable 3D additive manufacturing such as DLP, SLA, jet printing, inkjet, or CLIP includes the step of photopolymerizing a photopolymerizable composition comprising a light-reflecting material component comprising a light-reflecting material that is absorbent under physiological conditions. In one aspect, the light-reflecting material component comprises a light-reflecting material that is biocompatible with a biological body. In one aspect, the light-reflecting material component comprises a light-reflecting material that polymerizes with at least one of a photopolymerizable macromer, a diluent, a light-reflecting material, or a combination thereof.

[0044] The present disclosure includes a polymer polymerized from a composition disclosed herein by the method disclosed herein. In one aspect, the polymer comprises macromers and / or monomers known to those skilled in the art, macromers and / or monomers disclosed herein, or both macromers and / or monomers disclosed herein and well-known in the art.

[0045] The present disclosure includes an article (also referred to herein as a print) made from a composition disclosed herein by the method disclosed herein. In one aspect, the article can be a medical device. In one aspect, the article can be part of a medical device. In one aspect, the article can be a coating, such as a light-printed coating, applied to all or part of a solid such as a medical device. In one aspect, the article can be porous. In one aspect, the article can be biodegradable under physiological conditions. In one aspect, the biodegradable article can have a degradation rate of from about 3 days to about 5 years. In one aspect, the article need not be biodegradable. In one aspect, a portion of the article can be biodegradable and a second portion can be non-biodegradable, or can have a degradation time different from that of the first or remaining portion of the article. The article can be drug-eluting, for example, all or part of the article can elute an active agent contained in the photopolymerizable composition.

[0046] The present disclosure includes a kit containing a photopolymerizable composition or a part of the photopolymerizable composition disclosed herein, such as a light-reflecting material component, contained in a container, and optionally further including its instruction manual. The kit may include a printed matter disclosed herein contained in a container, and may optionally further include its instruction manual. The kit may include one or more kinds of each of the photopolymerizable composition, the light-reflecting material, and the photoinitiator. In one aspect, the kit may include one or more kinds of a photopolymerizable composition containing a photoinitiator and a light-reflecting material. In one aspect, the kit may include one or more kinds of a photopolymerizable composition containing a photoinitiator, the photopolymerizable composition, and the light-reflecting material. The kit may include a printed sterilization part disclosed herein contained in a container, and may optionally further include its instruction manual.

[0047] Definition The naming of compounds such as organic compounds used herein can be carried out using common names, IUPAC, IUBMB, or CAS naming recommendations. When there are one or more stereochemical features, the Cahn-Ingold-Prelog sequence rules of stereochemistry can be used to specify stereochemical priorities, E / Z notation, etc. Those skilled in the art can easily confirm the structure of a compound by systematic simplification of the compound structure using the naming rules when a name is given, or by commercially available software such as ChemDraw (trademark) (Cambridgesoft Corporation, USA).

[0048] As used in this specification and the appended claims, the singular forms "a", "an", and "the" include plural referents unless the context clearly dictates otherwise. Thus, for example, references to "a functional group", "an alkyl", or "a residue" include mixtures of two or more such functional groups, alkyls, or residues. References in this specification and the claims of the conclusion to parts by mass of a particular element or component in a composition refer to the mass relationship between the element or component and any other element or component in the composition or article expressed in parts by mass. Thus, in a compound containing 2 parts by mass of component X and 5 parts by mass of component Y, X and Y are present in a mass ratio of 2:5 and are present in such a mass ratio regardless of whether the compound contains additional components. The mass percentage (mass %) of a component is based on the total mass of the formulation or composition in which the component is included, unless otherwise specified. When the terms monomer or compound are used herein to refer to a compound, it is understood that this is not to be construed as one molecule or one compound. For example, two monomers generally refer to two different monomers and not to two molecules. As used herein, "adjust" and "adjusting" mean a change in the property being measured. The change can be an increase or a decrease in the property. A change can occur by adjusting a factor or component. The effect after adding the adjustment factor is the change, compared to the original state that existed before adding the adjustment factor, or the same configuration or situation that would exist without the adjustment factor.

[0049] As used herein, the term "optional" or "optionally" means that the event or circumstance described thereafter may or may not occur, and this description includes both the case where the event or circumstance occurs and the case where it does not occur. As used herein, the terms "about", "approximately", and "at or about" mean that the quantity or value in question can be the specified exact value, or a value that results in the same result or effect as detailed in the claims or taught herein. That is, quantities, sizes, formulations, parameters, etc., such as amounts and properties, are not exact and need not be exact, and may, as appropriate, reflect tolerances, conversion factors, rounding, measurement errors, etc., and other factors known to those of ordinary skill in the art, so as to be approximate values and / or larger or smaller, and be understood to be so. Depending on the circumstances, a value that results in the same result or effect may not be reasonably determinable. In such cases, as used herein, "about" and "at or about" generally mean that the nominal value has shown a variation of ±10% unless otherwise indicated or inferred. Generally, amounts or properties such as quantities, sizes, formulations, parameters, etc., are "about", "approximately", or "at or about", whether or not explicitly stated as such. When "about", "approximately", or "at or about" is used before a quantitative value, the parameter is understood to include the particular quantitative value itself as well, unless otherwise specified.

[0050] As used herein, "curing" means a change in the physical, chemical, or physical and chemical properties of a material, and as generally understood for polymeric materials, "curing" means that the composition changes from a liquid to a solid or semi-solid. As used herein, the term "subject" can be a vertebrate such as a mammal, fish, bird, reptile, or amphibian. Thus, the subjects of the methods disclosed herein can be a human, non-human primate, horse, pig, rabbit, dog, sheep, goat, cow, cat, guinea pig, or rodent. The term does not mean a particular age or sex. Thus, it is intended to cover adult and neonatal subjects, as well as fetuses or embryos, regardless of sex. In one aspect, the mammalian subject is a human. A patient refers to a subject suffering from a disease or disorder. The term "patient" includes human and animal subjects. As used herein, "active agent" means a compound or molecule, or a protein-, carbohydrate-, or nucleic acid-based substance that can produce an effect. Active agents include, but are not limited to, chemical agents, therapeutic agents, pharmaceuticals, diagnostic agents, prophylactic agents, contrast agents, and other agents having specific physiological effects, such as growth factors, immunological agents, healing factors, etc. In some cases, the active agent may include an active force, such as radiation. As used herein, "reactive diluent" means a liquid formulation that can polymerize with one or more components or molecules in a mixture. As used herein, "macromer" is an aggregate of prepolymerized monomers, which may or may not be modified and acts as a photopolymerizable unit in a polymerization reaction. As used herein, the terms "administer" and "administration" refer to a method of providing the disclosed composition to a subject. As used herein, the terms "comprising," "comprised of," "including," "included," "containing," "characterized by," "having," "including," or other variations thereof are intended to cover non-exclusive inclusion. For example, a process, method, article, or apparatus that includes a list of elements is not necessarily limited to only those elements, and may include other elements not expressly listed or associated with such process, method, article, or apparatus.

[0051] The transitional phrase "consisting of" excludes any element, step, or ingredient not specified in the claim, and may close the claim against the inclusion of materials other than those recited, excluding usually accompanying impurities. When the phrase "consisting of" appears not immediately after the preamble but in the body clause of the claim, it limits the claim to only the elements specified in that clause, and other elements are not excluded from the claim as a whole. The transitional phrase "consisting essentially of" may limit the scope of the claim to those that do not materially affect the basic and novel characteristics of the claimed invention, namely specific materials or steps. "Consisting essentially of" claims lie between closed claims written in the "consisting of" format and fully open claims drafted in the "comprising" format. Optional additives, additives in concentrations suitable for such additives, and minor impurities are not excluded from the composition by the term "consisting essentially of".

[0052] When a composition, process, structure, or a part of a composition, process, or structure is described herein using open-ended terms such as "comprising", the description includes, unless otherwise stated, embodiments "consisting essentially of" or "consisting of" the elements of the composition, process, structure, or part of the composition, process, or structure. Many of the embodiments described herein are described using the open-ended language "comprising". Such embodiments include a plurality of closed-ended "consisting of" and / or "consisting essentially of" embodiments, which may alternatively be claimed or described using such language. As used herein, the term "polymer" refers to a chain of repeating structural units or "monomers". Examples of polymers include homopolymers (one type of monomer subunit), copolymers or heteropolymers (two or more types of monomer subunits). As used herein, the term "linear polymer" refers to a polymer in which the molecules form long chains without a branched or cross-linked structure. As used herein, the term "branched polymer" refers to a polymer having a polymer backbone with one or more additional monomers, or chains or monomers extending from the polymer backbone. The articles "a" and "an" may be used in connection with various elements or components of the compositions, processes, or structures described herein. This is for convenience only and to give a general sense of the composition, process, or structure. Such descriptions include "one or at least one" of the element or component. Further, as used herein, the singular articles include descriptions of multiple elements or components unless it is clear from the particular context that the plural is excluded.

[0053] The term "about" means that the amounts and characteristics such as quantity, size, formulation, parameters, etc. are not exact and need not be exact, and may, as appropriate, reflect tolerances, conversion factors, rounding, measurement errors, etc., and other factors known to those skilled in the art, and can be approximate values and / or larger or smaller. Generally, amounts or characteristics such as quantity, size, formulation, parameters, etc. are "about" or "approximately" whether or not explicitly stated as such. The term "or" as used herein is inclusive. That is, the phrase "A or B" means "A, B, or both A and B". More specifically, the condition "A or B" is satisfied by any of the following: A is true (or exists) and B is false (or does not exist); A is false (or does not exist) and B is true (or exists); or both A and B are true (or exist). Exclusive "or" is specified herein by terms such as "either A or B" and "one of A or B". Also, the ranges defined herein include their endpoints unless explicitly stated otherwise. Further, when amounts, concentrations, or other values or parameters are given as a range, one or more preferred ranges, or a list of preferred upper and lower values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range or preferred upper value and any lower range or preferred lower value, whether or not such pairs are individually disclosed. The scope of the present invention is not limited to the specific values recited when defining the ranges.

[0054] When a material, method, or machine is described herein in conjunction with the terms "known to those of ordinary skill in the art," "conventional," or synonymous phrases, this term is meant to represent that the materials, methods, and machines that are common at the time of filing of this application are encompassed by this description. Also encompassed are materials, methods, and machines that are not currently common but that become recognized as suitable for similar purposes in the art. Unless otherwise specified, all amounts such as percentages, parts, ratios, etc. are defined by mass. All patents, patent applications, and references included herein are hereby specifically incorporated by reference in their entirety. Of course, it is to be understood that the foregoing relates only to the preferred embodiments of the present disclosure and that numerous modifications or variations can be made therein without departing from the spirit and scope of the present disclosure as described herein.

[0055] Disclosed herein is a method of photopolymerizing an article, for example printing. The steps can include: a) a photopolymerizable composition comprising i) at least one photopolymerizable macromer component; ii) at least one light-reflecting material component comprising a light-reflecting material suspended in the photopolymerizable composition; and iii) at least one photoinitiator component; temporarily exposing the photopolymerizable composition, in which the light-reflecting material component adjusts the irradiation amount of the composition as compared to the irradiation amount of the photopolymerizable composition without the light-reflecting material, to light, and forming a printed article comprising at least a polymerized macromer. The light-reflecting material component can increase the polymerization rate at the surface of the photopolymerizable composition in contact with light as compared to the same photopolymerizable composition without the light-reflecting material component. By incorporating the light-reflecting material component into the photopolymerizable composition, the macromer is surface-cured at a lower photoinitiator concentration than when used in a photopolymerizable composition without the light-reflecting material component. The total concentration of the photoinitiator component can be less than 0.01% by mass. The photopolymerizable composition can further comprise a reactive diluent. The photopolymerizable composition can further comprise a non-reactive diluent. The photopolymerizable composition can further comprise a reactive or non-reactive viscosity modifier that increases the viscosity. The photopolymerizable composition can further comprise a stabilizer that can be a free radical stabilizer. The light-reflective material component may further include particulate light-reflective materials. The light-reflective material component may include light-reflective materials that reflect UV light, visible light, or both. The photopolymerizable composition may be heated before or during the manufacturing step. The photopolymerizable composition may be cooled before or during the manufacturing step. The photopolymerizable composition may further include an activator. The light-reflective material component may include an activator. The light-reflective material may be an activator. The photopolymerizable macromer component may include an activator. The photopolymerizable macromer may be an activator. The reactive diluent may include an activator. The reactive diluent may be an activator. The non-reactive diluent may include an activator. The non-reactive diluent may be an activator. The photopolymerizable composition may further include a dye.

[0056] A method of photopolymerizing an article, for example printing, may include steps including a secondary curing step including the step of curing a printed matter. The method may include the step of rinsing the printed matter. The method may include the step of rinsing the secondarily cured printed matter. The method may include the step of providing a printed matter including a residual diluent or a photopolymerization diluent. The method may include the step of providing a printed matter including a residual photoinitiator. The methods disclosed herein may include a step of including a photopolymerizable composition, and the photopolymerizable macromer component includes a monomer having an ethylenically unsaturated group or a macromer having a monomer unit (monomer) having an ethylenically unsaturated group. The methods disclosed herein may include a step of providing a printed matter including a photopolymerizable composition, and the photopolymerizable macromer component includes a monomer having a thiol group or a macromer having a monomer unit (monomer) having a thiol group. The methods disclosed herein may include a step of providing a printed matter including a photopolymerizable composition, and the photopolymerizable macromer component includes a monomer having a thiol group or a macromer having a monomer unit (monomer) having a thiol group, and a monomer having an ethylenically unsaturated group or a macromer having a monomer unit (monomer) having an ethylenically unsaturated group. The photopolymerizable composition and methods of making and using such photopolymerizable compositions may include a photopolymerizable macromer component including a macromer including at least one monomer unit of a lactone monomer, glycolide, lactide, ε-caprolactone, trimethylene carbonate, p-dioxanone, 1,5-dioxepan-2-one, or morpholine-2,5-dione, or a combination thereof.

[0057] The methods disclosed herein may include a step in which the light wavelength used for photopolymerization is 10 to 700 nm (UV light 10 to 400) (visible light 390 to 700). The methods disclosed herein may include a step in which the photopolymerizable composition photopolymerizes in a shorter time than a photopolymerizable composition not including a reflective material under the same polymerization conditions. The methods disclosed herein may include a step in which the photopolymerizable composition photopolymerizes in a shorter time than a photopolymerizable composition not including a reflective material under the same polymerization conditions. The methods disclosed herein may include a step in which the photopolymerizable composition photopolymerizes at a faster rate than a photopolymerizable composition not including a reflective material under the same exposure amount (mW / cm 2 ). The methods disclosed herein may include a step in which the photopolymerizable composition photopolymerizes at a faster rate than a photopolymerizable composition not including a reflective material under the same exposure amount (mW / cm 2 ).

[0058] The method disclosed herein may include a step of including a photopolymerizable composition in which the photoinitiator component is less than 5.00% by mass of the photopolymerizable composition, or the photoinitiator component is less than 0.50% by mass of the photopolymerizable composition, or the photoinitiator component is 0.25% by mass of the photopolymerizable composition, or the photoinitiator component is less than 0.25% by mass of the photopolymerizable composition, or the photoinitiator component is 0.10% by mass of the photopolymerizable composition, or the photoinitiator component is less than 0.10% by mass of the photopolymerizable composition, or the concentration of the photoinitiator component is in the range of about 0.05 to about 5.0% by mass. The method disclosed herein may include a step of including a photopolymerizable composition in which the photoinitiator component includes a photoinitiator that absorbs light having a wavelength of 300 nm or more, or the photoinitiator component includes a photoinitiator that absorbs light having a wavelength of 365 nm or more, or the photoinitiator component includes a photoinitiator that absorbs light having a wavelength of 375 nm or more, the photoinitiator component includes a photoinitiator that absorbs light having a wavelength of 400 nm or more, or the photoinitiator component includes at least one photoinitiator that absorbs light having a wavelength in the range of about 200 to about 770 nm. The method disclosed herein may include a step of including a photopolymerizable composition in which the photoinitiator component includes a type I photoinitiator, a type II photoinitiator, or a combination of type I and type II photoinitiators, or the photoinitiator component includes a cationic photoinitiator, or the photoinitiator absorbs at a wavelength reflected by a light reflecting material. The method disclosed herein may include a step in which the curing depth is less than 150 microns, or the curing depth is about 1 to about 50 microns.

[0059] The method disclosed herein may include a step of including a photopolymerizable composition in which the light-reflecting material component constitutes about 5 to about 90% by mass of the photopolymerizable composition, or the light-reflecting material component constitutes about 5 to about 45% by mass of the photopolymerizable composition, or the light-reflecting material component is about 10 to about 35% by mass of the photopolymerizable composition. The method disclosed herein may include a step of including a photopolymerizable composition in which the light-reflecting material component includes particulate light-reflecting material having a size of less than 500 microns, or the light-reflecting material component includes particulate light-reflecting material having a size of less than 30 microns, or the light-reflecting material component includes particulate light-reflecting material having a size of less than 5 microns, or the light-reflecting material component includes particulate light-reflecting material having a size of less than 1 micron. The method disclosed herein may include a step of including a photopolymerizable composition in which the light-reflecting material component includes particulate light-reflecting material formed into a sphere, cube, cone, rectangular parallelepiped, cylinder, pyramid, prism, polyhedron, or irregular shape, or a combination thereof, or the light-reflecting material component includes particulate light-reflecting material and has a smooth surface, or the light-reflecting material component includes particulate light-reflecting material and has a rough or uneven surface. The method disclosed herein may include a step of including a photopolymerizable composition in which the light-reflecting material component includes a light-reflecting material including an organic compound, an inorganic compound, or a combination thereof, or the light-reflecting material component includes a light-reflecting material that is a liquid, or the light-reflecting material component includes a light-reflecting material that is absorbent under physiological conditions, or the light-reflecting material component includes a light-reflecting material that is non-degradable or non-absorbent under physiological conditions, or the light-reflecting material component includes a light-reflecting material that is biocompatible with a biological living body. The method disclosed herein may include a step of including a photopolymerizable composition in which the light-reflecting material component includes a light-reflecting material that polymerizes with at least one of a photopolymerizable macromer, a diluent, a light-reflecting material, or a combination thereof, or the light-reflecting material component includes a photopolymerizable composition consisting essentially of a light-reflecting material.

[0060] This specification discloses polymers polymerized by the methods disclosed herein and in the photopolymerizable compositions disclosed herein. This specification discloses articles made by the methods disclosed herein or by the photopolymerizable compositions disclosed herein. This specification discloses articles made by the methods disclosed herein or by the photopolymerizable compositions disclosed herein that may be or be at least a part of a medical device. In one aspect, the photopolymerizable composition is used as a medical device photopolymerized in situ. Some examples of medical devices can include, but are not limited to, device coatings, tissue adhesives, bone cements, void fillers, and drug eluting depots. This specification discloses articles made by the methods disclosed herein and the photopolymerizable compositions disclosed herein, wherein all or part of the article is porous, or at least part or all of the article is biodegradable or non-biodegradable under physiological conditions, or at least part or all of the article has a degradation rate from about 3 days to about 5 years, or at least part or all of the article is non-biodegradable, or at least part or all of the article is drug eluting. This specification discloses articles made by the methods disclosed herein or by the photopolymerizable compositions disclosed herein that include a photopolymerizable biodegradable polymer and a non-toxic amount of a photoinitiator. This specification discloses articles made by the methods disclosed herein or by the photopolymerizable compositions disclosed herein that include a non-toxic polymer composition that includes a photopolymerizable macromer and a non-toxic amount of a photoinitiator. Such articles further include a photopolymerizable diluent. Such articles further include a photopolymerizable light-reflecting material. Such articles may have the features disclosed herein, and the articles may be or be at least a part or all of a medical device, or may be a coating on all or part or the surface of a medical device.

[0061] This specification discloses a photopolymerizable composition. For example, the photopolymerizable composition is a photopolymerizable composition comprising at least one photopolymerizable macromer component; at least one light-reflecting material component comprising a light-reflecting material suspended in the composition; and at least one photoinitiator component, wherein the light-reflecting material component may include a photopolymerizable composition that adjusts the irradiation amount of the composition as compared to the irradiation amount of a composition not containing the light-reflecting material. In the photopolymerizable composition, the light-reflecting material component increases the polymerization rate at the surface of the photopolymerizable composition in contact with light as compared to the same photopolymerizable composition not containing the light-reflecting material component. In the photopolymerizable composition, by incorporating the light-reflecting material component into the photopolymerizable composition, the macromer is surface-cured at a lower photoinitiator concentration than when used in a photopolymerizable composition not containing the light-reflecting material component. In the photopolymerizable composition, the total photoinitiator concentration may be less than 1.0% by mass. The photopolymerizable composition of the present disclosure may include a reactive diluent, or a non-reactive diluent, or both. The photopolymerizable composition of the present disclosure may include a stabilizer that may be a free radical stabilizer. The photopolymerizable composition of the present disclosure may include a particulate light-reflecting material that may include a light-reflecting material that reflects UV light, visible light, or both. The photopolymerizable composition of the present disclosure may be heated or cooled. The photopolymerizable composition may include a reactive or non-reactive viscosity modifier that increases the viscosity. The photopolymerizable composition of the present disclosure may contain an activator. The photopolymerizable composition of the present disclosure may contain a light-reflecting material that is an activator, or a light-reflecting material containing an activator. The photopolymerizable composition of the present disclosure may contain a photopolymerizable macromer component containing an activator, or a photopolymerizable macromer containing an activator. The photopolymerizable composition of the present disclosure may contain a reactive diluent containing an activator, or a non-reactive diluent containing an activator. The photopolymerizable composition of the present disclosure may contain a dye. The photopolymerizable composition of the present disclosure contains a monomer having an ethylenically unsaturated group, or a macromer having a monomer unit (monomer) having an ethylenically unsaturated group, or a monomer having a thiol group, or a monomer unit (monomer) having a thiol group. It may contain a photopolymerizable macromer component containing a macromer having a thiol group, or both. The photopolymerizable composition of the present disclosure contains a lactone monomer, glycolide, lactide, ε-caprolactone, trimethylene carbonate, p-dioxanone, 1,5-dioxepan-2-one, or morpholine-2,5-dione, or It may contain a photopolymerizable macromer component containing a macromer containing at least one monomer unit of a combination thereof.

[0062] The photopolymerizable composition of the present disclosure may include a photopolymerizable composition that polymerizes when exposed to a light wavelength of 10 to 700 nm (UV light 10 to 400) (visible light 390 to 700). The photopolymerizable composition of the present disclosure may include a photopolymerizable composition that photopolymerizes in a shorter time than a photopolymerizable composition that does not contain a reflective material under the same polymerization conditions. The photopolymerizable composition of the present disclosure may include a photopolymerizable composition that photopolymerizes in a shorter time than a photopolymerizable composition that does not contain a reflective material under the same polymerization conditions. The photopolymerizable composition of the present disclosure is faster than a photopolymerizable composition that does not contain a reflective material under the same polymerization conditions and at the same exposure amount (mW / cm 2 ) It may include a photopolymerizable composition that photopolymerizes at a speed. The photopolymerizable composition of the present disclosure is faster than a photopolymerizable composition that does not contain a reflective material under the same polymerization conditions and at the same exposure amount (mW / cm 2) may contain a photopolymerizable composition that undergoes photopolymerization at a high speed. The photopolymerizable composition of the present disclosure may contain a photoinitiator component that is less than 1.00% by mass of the photopolymerizable composition. The photopolymerizable composition of the present disclosure may contain a photoinitiator that absorbs at a wavelength reflected by a light-reflecting material. The photopolymerizable composition of the present disclosure may contain a light-reflecting material component that contains a light-reflecting material that polymerizes with at least one of a photopolymerizable macromer, a diluent, a light-reflecting material, or a combination thereof. The photopolymerizable composition of the present disclosure may contain a light-reflecting material component that consists of or consists essentially of a light-reflecting material. The photopolymerizable composition of the present disclosure may include a photopolymerizable composition for stereolithography. The photopolymerizable composition of the present disclosure may include a photopolymerizable composition for continuous liquid interface production. The photopolymerizable composition of the present disclosure may include a photopolymerizable ink composition. The photopolymerizable ink composition may include at least one photopolymerizable macromer component; at least one light-reflecting material component that contains a light-reflecting material suspended in the composition; at least one photoinitiator component; wherein the light-reflecting material component adjusts the irradiation amount of the composition as compared to the irradiation amount of the photopolymerizable composition that does not contain a light-reflecting material; a diluent; and a stabilizer.

[0063] The light-reflecting materials disclosed in this specification, when added to a photopolymerizable ink formulation, can include at least one of inorganic solids; organic compounds, crystalline organic compounds, crystalline amino acids and / or their derivatives, crystalline fatty acids and / or their derivatives, crystalline peptides, or combinations thereof, so as to adjust the irradiation amount requirement of the ink formulation as compared to the irradiation amount requirement of an ink formulation without the light-reflecting material. The light-reflecting materials of inorganic compounds can include titanium dioxide, zinc oxide, barium sulfate, tricalcium phosphate, dicalcium phosphate, monocalcium phosphate, dicalcium nilinate, tricalcium phosphate, hydroxyapatite, apatite, and tetracalcium phosphate, or combinations thereof. The light-reflecting materials of organic compounds can include aliphatic polymers and copolymers of polyester, polyurethane, polyether, polyanhydride, polyamide, polycarbonate, polyketone, polyethylene, polypropylene, polyvinyl alcohol, polytetrafluoroethylene, polyvinyl chloride, polyimide, and polyhydroxyalkanoate, or combinations thereof. The light-reflecting materials of organic compounds can include aromatic polymers and copolymers of polyester, polyurethane, polyether, polyanhydride, polyketone, polyamide, polycarbonate, and polyimide, or combinations thereof. The light-reflecting materials of organic compounds can include natural-derived polymers and derivatives of cyclodextrin, starch, hyaluronic acid, deacetylated hyaluronic acid, chitosan, trehalose, cellobiose, maltotriose, maltohexaose, chitohexaose, agarose, chitin50, amylose, glucan, heparin, xylan, pectin, galactan, glycosaminoglycan, dextran, aminated dextran, cellulose, hydroxyalkyl cellulose, carboxyalkyl cellulose, fucoidan, chondroitin sulfate, sulfated polysaccharides, mucopolysaccharides, gelatin, zein, collagen, alginic acid, agar, carrageenan, guar gum, gum arabic, ghatti gum, karaya gum, konnyaku gum, tamarind gum, tara gum, tragacanth gum, locust bean gum, pectin, xanthan gum, or combinations thereof. The light-reflecting materials of crystalline organic compounds can include crystalline aliphatic and aromatic polymers, and combinations thereof.The light-reflecting material of the crystalline organic compound may include crystalline natural-derived polymers and derivatives, as well as combinations thereof. The light-reflecting material of the crystalline organic compound may include crystalline amino acids and their derivatives, as well as combinations thereof. The light-reflecting material of the crystalline organic compound may include crystalline fatty acids including, but not limited to, palmitic acid, ascorbyl palmitate, lauric acid, glycerol monolaurate, myristic acid, capric acid, and combinations thereof. In one aspect, the light-reflecting material is insoluble in the macromer formulation. In one aspect, the light-reflecting material does not swell in the macromer formulation. The present disclosure will be further illustrated by the examples described herein, which should in no way be construed as limiting these scopes. On the contrary, after reading the description of this specification, it should be clearly understood that those skilled in the art can rely on various other embodiments, modifications, and equivalents thereof that may be suggested by themselves without departing from the spirit of the present disclosure and / or the appended claims.

Examples

[0064] Preparation of Photopolymerizable Formulation The photopolymerizable formulation was synthesized by mixing the macromer, photoinitiator, light-reflecting material, dye, and reactive diluent described in Table 1. Examples of the macromer used in the following examples are polyester dimethacrylate (PEDMA; M n = 2,500 daltons; 6,750 cP) and polyethylene glycol diacrylate (PEGDA; M nIt was =575;57 cP). The photoinitiators used were 2,4,6-trimethylbenzoyl phenylphosphinate (Irgacure® TPO-L) and 2-hydroxy-1-[4-(2-hydroxyethoxy)phenyl]-2-methyl-1-propanone (Irgacure® 2959). The UV-reflective material microparticles described below for these formulations were barium sulfate microparticles (BaSO4; 1 - 3 μm), polyglycolide microparticles (PGA; <10 μm), absorbent phosphate ceramic microparticles (PHC), amorphous polylactide copolymer microparticles (ACPLA; <75 μm), and semi-crystalline polylactide microparticles (PLA; <75 μm). The dye used in the formulations of these examples was D&C Green 6. The reactive diluent described in Table 1 was polyethylene glycol diacrylate (57 cP). Most of these components were commercially available and could be obtained, for example, from Millipore-Sigma (28820 Single Oak Drive, Temecula, California 92590, USA). For formulation number 20, 1 g of PEDMA, 1 g of PEGDA, 0.4 g of barium sulfate, and 0.086 g of Irgacure® TPO-L were weighed into an opaque container. The formulation was stirred until all components were completely mixed and homogeneous.

Table 1

Examples

[0065] Surface curing of the photopolymerizable formulation The formulations of the examples in Table 1 were photopolymerized using Dymax BlueWave® 200 at a certain distance from the light source. Before photopolymerization, the light intensity was measured using a UVA detector and was 3 mW / cm 2It was set to. Each formulation was photopolymerized for a set time, and the total irradiation dose or exposure dose was calculated by multiplying the light intensity by the irradiation time. After irradiation, the samples were inspected and evaluated. The samples could be described as 0 (remaining in a fluid state), 1 (increased viscosity; signs of a partially cured film), and 2 (surface film layer). A part of the photopolymerized film increased in layer thickness over time after the initial surface curing. However, the scores of such samples were all 2. The scores of the surface curing tests are shown in Table 2. From Table 2, only formulation No. 5 containing a macromer and a photoinitiator achieved surface curing with an irradiation dose of 30 mJ / cm 2 and a photoinitiator concentration of 7.4 mass%. The addition of 0.1% D&C Green 6 did not change the concentration of the photoinitiator required to achieve surface curing of the polymer. However, when barium sulfate was added as a light-reflecting material, the composition of formulation No. 11 achieved surface curing at a photoinitiator concentration of 0.6%. In formulation No. 16 using a macromer and a reactive diluent in a 50:50 ratio, the formulation achieved surface curing at a concentration of 0.2% and an irradiation dose half that of the previous formulation (15 mJ / cm 2 ). As observed here, the addition of a light-reflecting material enables a significant reduction in the amount of photoinitiator. A significant reduction in the amount of photoinitiator and a halving of the irradiation were reproduced with other materials such as polyglycolide microparticles and absorbent phosphate ceramic microparticles.

Table 2

Examples

[0066] Surface Curing of SLA Formulations with Respect to Changes in Exposure Time Formulations Nos. 39 to 43 of the examples in Table 1 were placed at a fixed distance from the light source, the exposure time was changed, and they were photopolymerized using Dymax BlueWave® 200. Before photopolymerization, it was measured using a UVA detector, and the light intensity was 3 mW / cm 2It was set to. Samples of each formulation were photopolymerized for 1.3, 2.5, 5.0, and 10 seconds. A UVA detector was placed under a glass Petri dish, and after recording the irradiation dose after the exposure time, the sample was added thereto. The sample on the Petri dish was photopolymerized for any of the above times, and the irradiation dose that passed through the sample and reached the UV detector was recorded. A decrease in the irradiation dose recorded by the UVA detector was observed with an increase in the amount of the light-reflecting material in the formulation and an increase in the exposure time. Similarly, samples with a large amount of the crystalline light-reflecting material cured faster than their equivalents containing the amorphous polymer microparticle dispersion. The photopolymerized formulations were also qualitatively evaluated based on the evaluation system described in Example 2.

Table 3

Examples

[0067] Printing of a Photopolymerizable Formulation Article A three-dimensional object of a rectangular cube was created in Solidworks (registered trademark). The three-dimensional object file was converted to an STL file. Formulation No. 33 was added to the ink bed of a B9Creator v1.2 SLA printer (B9Creations, LLC, 525 University Loop, Suite 115, Rapid City, SD 57701). The object was printed with a layer thickness of 30 μm, with the first 2 layers having an exposure time of 6 seconds and the subsequent layers having an exposure time of 3 seconds. The light intensity of the SLA printer was measured with a UVA detector to be 3 mW / cm 2 and was.

Examples

[0068] Photoprinting with and without a Reflective Material When a light-reflecting material is present, the exposure time to light required for the polymer resin to fully cure is shortened, and thus the total time required to photoprint the member is shortened. Formulation No. 5 of Examples 1 and 2 (M containing trimethylene carbonate, caprolactone, and glycolide monomer nTwo resin blends were created, one containing a custom dimethacrylate linear polymer of 2300 Daltons and PEG-DA575 (Sigma Aldrich) in a 50 / 50 (w / w) ratio, and the other containing 25% poly(glycolide) microparticles as a light-reflecting material. To each blend, a phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide (BAPO) photoinitiator at 0.5% by mass relative to the base polymer blend and 0.025% of D&C Violet dye were mixed. Using both resins, strip pieces (75×7.5×1 mm) were printed with a B9Creator DLP printer at a layer thickness of 50 μm and an exposure time of 1.75 seconds. The members printed with the resin containing the light-reflecting material fully cured with these printing parameters, while the members without the light-reflecting material were sticky to the touch and thus not fully cured. Printing was repeated with the resin without the light-reflecting material, extending the exposure time from 1.75 seconds to 7 seconds. At this point, the articles made with the resin without the light-reflecting material were equivalent to those made with the resin containing the light-reflecting material in 1.75 seconds. Thus, incorporating the light-reflecting material enabled a lower concentration of photoinitiator and a quarter of the printing time.

Example

[0069] Printed matter In SolidWorks 2016, a donut-shaped (ring-shaped) printed matter with an outer diameter of 10 mm, an inner diameter of 5 mm, and a height of 3 mm was designed. To a resin blend of Formulation No. 5 of Examples 1 and 2 and PEG-DA575 in a ratio of 50 / 50 (w / w), microparticle polyglycolide at 25% by mass relative to the base polymer blend as a light-reflecting material (particle size 5 - 20 μm), 0.25% BAPO photoinitiator, and 0.025% D&C Violet were mixed. After printing the members using a Wanhao Duplicator 7 mask DLP printer, they were rinsed with toluene and measured with calipers.

Table 4

[0070] Hydrogel Formulations of poly(ethylene glycol) diacrylate (MW = 575 Da) in deionized (DI) water were prepared at a concentration of 5% (w / w) with or without additives. The additives included PEG12000 to impart viscosity and nylon microparticles as a light-reflecting material. All formulations contained Irgacure 651 photoinitiator at a concentration of 0.5% (w / w) based on the total amount of the acrylated polymer component. The groups for which the tests were conducted are shown in Table 4.

Table 5

Table 6

Table 7

Example

[0071] Photocuring of a blend obtained by mixing β-tricalcium phosphate (TCP) as a reflective material with formulation number 5 / PEG-DA575 The methacrylated formulation number 5 (M containing trimethylene carbonate, caprolactone, and glycolide monomers) of Examples 1 and 2 at a ratio of 50 / 50 (w / w) n=A blend of a custom dimethacrylate linear polymer of 2300 Daltons), PEG-DA575 (Sigma Aldrich), and a photocurable formulation containing 0.25% (w / w) BAPO as a photoinitiator, and optionally 25% (w / w) TCP was prepared. Both formulations were exposed to UV light (Dymax Blue Wave200 UV photocuring spot lamp system) at an intensity of 30 mW / cm 2 for 0.2, 0.5, and 1 second. The formulation without TCP did not start partial curing until 0.5 seconds, and a surface-cured film was formed at 1 second. In contrast, the formulation containing 25% TCP had its surface cured at 0.2 seconds and was almost completely cured at 1 second, indicating that the addition of TCP increased the curing rate. Another aspect of the present invention may be as follows. [1] A method for photopolymerizing printing an article, comprising a) a step of temporarily exposing a photopolymerizable composition to light, wherein the photopolymerizable composition comprises i. at least one photopolymerizable macromer component; ii. at least one light-reflecting material component suspended in the photopolymerizable composition; and iii. at least one photoinitiator component wherein the light-reflecting material component adjusts the irradiation amount requirement of the photopolymerizable composition when compared to the irradiation amount requirement of a composition not containing the light-reflecting material, and b) a step of forming a printed matter containing at least a polymerized macromer A method comprising. [2] The method according to [1] above, wherein the light-reflecting material component increases the polymerization rate on the surface of the photopolymerizable composition in contact with light as compared to the same photopolymerizable composition not containing the light-reflecting material component. [3] The method according to [1] above, wherein by incorporating a light-reflecting material component into a photopolymerizable composition, the macromer is surface-cured at a photoinitiator concentration lower than the concentration used in a photopolymerizable composition not containing the light-reflecting material component. [4] The method according to any one of [1] to [3] above, wherein the total concentration of the photoinitiator component is less than 1.0% by mass. [5] The method according to any one of [1] to [4] above, wherein the photopolymerizable composition further comprises a reactive diluent. [6] The method according to any one of [1] to [5] above, wherein the photopolymerizable composition further comprises a non-reactive diluent. [7] The method according to any one of [1] to [6] above, wherein the photopolymerizable composition further comprises a stabilizer. [8] The method according to [7] above, wherein the stabilizer is a free radical stabilizer. [9] The method according to any one of [1] to [8] above, wherein the light-reflecting material component comprises a particulate light-reflecting material.

[10] The method according to any one of [1] to [9] above, wherein the photopolymerizable composition further comprises an activator.

[11] The method according to any one of [1] to

[10] above, further comprising a secondary curing step including a step of curing the printed matter.

[12] The method according to any one of [1] to

[11] above, further comprising a step of rinsing the printed matter.

[13] The method according to any one of [1] to

[12] above, wherein the photopolymerizable composition further comprises a dye. 〔14〕The method according to any one of 〔1〕 to 〔13〕 above, wherein the photopolymerizable macromer component contains a monomer having an ethylenically unsaturated group or a macromer having a monomer unit (monomer) having an ethylenically unsaturated group. 〔15〕The method according to any one of 〔1〕 to 〔13〕 above, wherein the photopolymerizable macromer component contains a monomer having a thiol group or a macromer having a monomer unit (monomer) having a thiol group. 〔16〕The method according to any one of 〔1〕 to 〔13〕 above, wherein the photopolymerizable macromer component contains a monomer having an ethylenically unsaturated group or a macromer having a monomer unit (monomer) having an ethylenically unsaturated group, and a monomer having a thiol group or a macromer having a monomer unit (monomer) having a thiol group. 〔17〕The method according to any one of 〔1〕 to 〔16〕 above, wherein the photopolymerizable macromer component contains a macromer containing at least one monomer unit of a lactone monomer, glycolide, lactide, ε-caprolactone, trimethylene carbonate, p-dioxanone, 1,5-dioxepan-2-one, or morpholine-2,5-dione, or a combination thereof. 〔18〕The method according to any one of 〔1〕 to 〔17〕 above, wherein the light wavelength used for photopolymerization is 10 to 700 nm (UV light 10 to 400) (visible light 390 to 700). 〔19〕The method according to any one of 〔1〕 to 〔18〕 above, wherein the photopolymerizable composition photopolymerizes in a shorter time than the photopolymerizable composition not containing the reflective material under the same polymerization conditions. 〔20〕The method according to any one of 〔1〕 to 〔19〕 above, wherein the photopolymerizable composition photopolymerizes at a faster rate with the same exposure amount (mW / cm 2 ) than the photopolymerizable composition not containing the reflective material under the same polymerization conditions. 〔21〕The method according to any one of 〔1〕 to 〔20〕 above, wherein the concentration range of the photoinitiator component is about 0.01 to about 5.0% by mass. 〔22〕The method according to 〔1〕 above, wherein at least one photoinitiator absorbs at a wavelength reflected by at least one light reflective material. 〔23〕The method according to 〔1〕 above, wherein the curing depth is less than 150 microns. 〔24〕The method according to 〔1〕 above, wherein the light reflective material component constitutes about 5 to about 90% by mass of the photopolymerizable composition. 〔25〕The method according to 〔1〕 above, wherein the light-reflecting material component contains particulate light-reflecting materials having a size of less than 500 microns. 〔26〕The method according to 〔1〕 above, wherein the light-reflecting material component contains a light-reflecting material containing an organic compound, an inorganic compound, or a combination thereof. 〔27〕The method according to 〔1〕 above, wherein the light-reflecting material component contains a light-reflecting material that is a liquid. 〔28〕The method according to 〔1〕 above, wherein the light-reflecting material component contains a light-reflecting material that is a polymer. 〔29〕The method according to 〔1〕 above, wherein the light-reflecting material component contains a light-reflecting material that is absorbent or non-absorbent under physiological conditions. 〔30〕A polymer polymerized by the method according to any one of 〔1〕 to 〔29〕 above. 〔31〕An article produced by the method according to any one of 〔1〕 to 〔30〕 above. 〔32〕The article according to 〔31〕 above, which is a medical device. 〔33〕A non-toxic polymer article containing a photo-polymerizable biodegradable polymer and a non-toxic amount of a photoinitiator. 〔34〕A non-toxic polymer composition containing a photo-polymerizable macromer and a non-toxic amount of a photoinitiator. 〔35〕The composition according to 〔34〕 above, further containing a photo-polymerizable light-reflecting material. 〔36〕A photo-polymerizable composition comprising: i) at least one photo-polymerizable macromer component; ii) at least one light-reflecting material component containing a light-reflecting material suspended in the photo-polymerizable composition; and iii) at least one photoinitiator component wherein the light-reflecting material component adjusts the irradiation dose requirement of the photo-polymerizable composition when compared to the irradiation dose requirement of a photo-polymerizable composition not containing the light-reflecting material. 〔37〕The composition according to 〔36〕 above, wherein the light-reflecting material component increases the polymerization rate at the surface of the photo-polymerizable composition in contact with light as compared to the same photo-polymerizable composition not containing the light-reflecting material component. 〔38〕The composition according to 〔36〕 above, wherein by incorporating the light-reflecting material component into the photo-polymerizable composition, the macromer is surface-cured at a photoinitiator concentration lower than the concentration used in a photo-polymerizable composition not containing the light-reflecting material component. 〔39〕The composition according to 〔36〕 above, wherein the total concentration of the photoinitiator concentration is less than 1.0% by mass. 〔40〕The composition according to 〔36〕 above, wherein the photo-polymerizable composition further contains a reactive or non-reactive diluent, or both. 〔41〕The composition according to any one of 〔36〕 to 〔40〕 above, wherein the photo-polymerizable composition further contains a stabilizer. 〔42〕The composition according to 〔36〕, wherein the light-reflective material component contains a particulate light-reflective material. 〔43〕The composition according to 〔36〕, wherein the photopolymerizable composition further contains an activator. 〔44〕The composition according to 〔43〕, wherein the light-reflective material component contains an activator. 〔45〕The composition according to 〔43〕, wherein the light-reflective material is an activator. 〔46〕The composition according to 〔43〕, wherein the light-reflective material contains an activator. 〔47〕The composition according to 〔43〕, wherein the photopolymerizable macromer component contains an activator. 〔48〕The composition according to 〔43〕, wherein the photopolymerizable macromer contains an activator. 〔49〕The composition according to 〔43〕, wherein the reactive diluent contains the activator. 〔50〕The composition according to 〔43〕, wherein the non-reactive diluent contains the activator. 〔51〕The composition according to any one of 〔36〕 to 〔50〕, wherein the photopolymerizable composition further contains a dye. 〔52〕The composition according to any one of 〔36〕 to 〔51〕, wherein the photopolymerizable macromer component contains a monomer having an ethylenically unsaturated group, or a macromer having a monomer unit (monomer) having an ethylenically unsaturated group, or a monomer having a thiol group, or a macromer having a monomer unit (monomer) having a thiol group, or a combination of a monomer having an ethylenically unsaturated group, or a macromer having a monomer unit (monomer) having an ethylenically unsaturated group and a monomer having a thiol group, or a macromer having a monomer unit (monomer) having a thiol group. 〔53〕The composition according to any one of 〔36〕 to 〔52〕, wherein the photopolymerizable macromer component contains a macromer containing at least one monomer unit of a lactone monomer, glycolide, lactide, ε-caprolactone, trimethylene carbonate, p-dioxanone, 1,5-dioxepan-2-one, or morpholine-2,5-dione, or a combination thereof. 〔54〕The composition according to any one of 〔36〕 to 〔53〕, wherein the photopolymerizable composition polymerizes when exposed to a light wavelength of 10 to 700 nm (UV light 10 to 400) (visible light 390 to 700). 〔55〕The composition according to any one of 〔36〕 to 〔54〕, wherein the photopolymerizable composition photopolymerizes in a shorter time than a photopolymerizable composition not containing the reflective material under the same polymerization conditions. 〔56〕The composition according to any one of 〔36〕~〔55〕, wherein the photopolymerizable composition photopolymerizes in a shorter time than a photopolymerizable composition not containing the reflective material under the same polymerization conditions. 〔57〕The composition according to any one of 〔36〕~〔56〕, wherein the photopolymerizable composition photopolymerizes at a faster rate at the same exposure amount (mW / cm 2 ) than a photopolymerizable composition not containing the reflective material under the same polymerization conditions. 〔58〕The composition according to any one of 〔36〕~〔57〕, wherein the photopolymerizable composition photopolymerizes at a faster rate at the same exposure amount (mW / cm 2 ) than a photopolymerizable composition not containing the reflective material under the same polymerization conditions. 〔59〕The composition according to any one of 〔36〕~〔58〕, wherein the photoinitiator absorbs at a wavelength reflected by the light-reflecting material. 〔60〕The composition according to any one of 〔36〕~〔59〕, wherein the light-reflecting material component constitutes about 5 to about 65% by mass of the photopolymerizable composition. 〔61〕The composition according to any one of 〔36〕~〔60〕, wherein the light-reflecting material component includes a light-reflecting material that is absorbent or non-absorbent under physiological conditions. 〔62〕The composition according to any one of 〔36〕~〔61〕, wherein the light-reflecting material component includes a light-reflecting material that polymerizes with at least one of a photopolymerizable macromer, a diluent, a light-reflecting material, or a combination thereof. 〔63〕A stereolithography photopolymerizable composition, i) at least one photopolymerizable macromer component; ii) at least one light-reflecting material component including a light-reflecting material suspended in the photopolymerizable composition; and iii) at least one photoinitiator component wherein the light-reflecting material component adjusts the irradiation amount requirement of the composition when compared with the irradiation amount requirement of a composition not containing the light-reflecting material. 〔64〕A photopolymerizable composition for continuous liquid interface production, i) at least one photopolymerizable macromer component; ii) at least one light-reflecting material component including a light-reflecting material suspended in the photopolymerizable composition; and iii) at least one photoinitiator component wherein the light-reflecting material component adjusts the irradiation amount requirement of the composition when compared with the irradiation amount requirement of a composition not containing the light-reflecting material. 〔65〕A DLP (Digital Light Processing) photopolymerizable composition, i) at least one photopolymerizable macromer component; ii) at least one light-reflecting material component containing a light-reflecting material suspended in the photopolymerizable composition; and iii) at least one photoinitiator component A DLP photopolymerizable composition, which contains the above components and in which the irradiation amount requirement of the composition is adjusted when the light-reflecting material component is compared with the irradiation amount requirement of the composition not containing the light-reflecting material.

[66] A photopolymerizable ink composition, a) at least one photopolymerizable macromer component; b) at least one light-reflecting material component containing a light-reflecting material suspended in the photopolymerizable composition; c) at least one photoinitiator component; d) a reactive diluent; and e) a stabilizer A photopolymerizable ink composition, which contains the above components and in which the irradiation amount requirement of the photopolymerizable composition is adjusted when the light-reflecting material component is compared with the irradiation amount requirement of the photopolymerizable composition not containing the light-reflecting material.

[67] A photopolymerizable ink composition, a) at least one photopolymerizable macromer component; b) at least one light-reflecting material component containing a light-reflecting material suspended in the photopolymerizable composition; c) at least one photoinitiator component; d) a reactive diluent; and e) a stabilizer A photopolymerizable ink composition, which contains the above components and in which the irradiation amount requirement of the photopolymerizable composition is adjusted when the light-reflecting material component is compared with the irradiation amount requirement of the composition not containing the light-reflecting material.

[68] A light-reflecting material, which contains at least one of an inorganic solid, an organic compound, a crystalline organic compound, a crystalline amino acid and / or its derivative, a crystalline fatty acid and / or its derivative, a crystalline peptide, or a combination thereof, such that when added to a photopolymerizable ink formulation, the irradiation amount requirement of the ink formulation is adjusted as compared with the irradiation amount requirement of the ink formulation not containing the light-reflecting material.

[69] The material according to the above

[68] , wherein the inorganic compound is titanium dioxide, zinc oxide, barium sulfate, tricalcium phosphate, dicalcium phosphate, monocalcium phosphate, dicalcium pyrophosphate, tricalcium phosphate, hydroxyapatite, apatite, and tetracalcium phosphate, or a combination thereof. 〔70〕The material according to the above

[68] , wherein the organic compound includes aliphatic polymers and copolymers of polyester, polyurethane, polyether, polyanhydride, polyamide, polycarbonate, polyketone, polyethylene, polypropylene, polyvinyl alcohol, polytetrafluoroethylene, polyvinyl chloride, polyimide, and polyhydroxyalkanoate, or combinations thereof. 〔71〕The material according to the above

[68] , wherein the organic compound includes aromatic polymers and copolymers of polyester, polyurethane, polyether, polyanhydride, polyketone, polyamide, polycarbonate, and polyimide, or combinations thereof. 〔72〕The material according to the above

[68] , wherein the organic compound includes natural-derived polymers and derivatives of cyclodextrin, starch, hyaluronic acid, deacetylated hyaluronic acid, chitosan, trehalose, cellobiose, maltotriose, maltohexaose, chitohexaose, agarose, chitin50, amylose, glucan, heparin, xylan, pectin, galactan, glycosaminoglycan, dextran, aminated dextran, cellulose, hydroxyalkylcellulose, carboxyalkylcellulose, fucoidan, chondroitin sulfate, sulfated polysaccharides, mucopolysaccharides, gelatin, zein, collagen, alginic acid, agar, carrageenan, guar gum, gum arabic, ghatti gum, karaya gum, konnyaku gum, tamarind gum, tara gum, tragacanth gum, locust bean gum, pectin, xanthan gum, or combinations thereof. 〔73〕The material according to the above

[68] , wherein the crystalline organic compound includes crystalline aliphatic and aromatic polymers, and combinations thereof. 〔74〕The material according to the above

[68] , wherein the crystalline organic compound includes crystalline natural-derived polymers and derivatives, and combinations thereof. 〔75〕The material according to the above

[68] , including crystalline amino acids and their derivatives, and combinations thereof. 〔76〕The material according to the above

[68] , wherein the crystalline fatty acids include palmitic acid, ascorbyl palmitate, lauric acid, glycerol monolaurate, myristic acid, capric acid, and combinations thereof.

Claims

1. A method for photopolymer printing an article, comprising: a) a step of temporarily exposing a photopolymerizable composition to light, wherein the photopolymerizable composition comprises: i. at least one photopolymerizable biodegradable macromer component, wherein the photopolymerizable biodegradable macromer component comprises a macromer comprising at least one monomer unit of a lactone monomer, glycolide, lactide, ε-caprolactone, trimethylene carbonate, p-dioxanone, 1,5-dioxepan-2-one, or morpholine-2,5-dione, or a combination thereof; ii. at least one light-reflecting material component suspended in the photopolymerizable composition, wherein the light-reflecting material is a biodegradable light-reflecting material, and the light-reflecting material comprises polyglycolide particles, absorbent phosphate ceramic microparticles, amorphous polylactide copolymer particles, or semi-crystalline polylactide particles; and iii. at least one photoinitiator component and a step, and b) a step of forming a printed article comprising at least a biodegradable polymerized macromer A method comprising the steps of:

2. The method according to claim 1, wherein the total concentration of the photoinitiator component is less than 1.0% by mass.

3. The method according to any one of claims 1 to 2, wherein the photopolymerizable composition further comprises a reactive diluent, a non-reactive diluent, both a reactive diluent and a non-reactive diluent, a dye, or a stabilizer.

4. The method according to any one of claims 1 to 2, further comprising the following curing step of further curing the printed article.

5. The method according to any one of claims 1 to 2, wherein the light wavelength used for photopolymerization is 10 to 700 nm.

6. The method according to any one of claims 1 to 2, wherein the photopolymerizable composition photopolymerizes in a shorter time than a photopolymerizable composition not containing the reflective material under the same polymerization conditions.

7. The photopolymerizable composition photopolymerizes at a faster rate with the same exposure amount (mW / cm 2 ) than the photopolymerizable composition not containing the reflective material under the same polymerization conditions. The method according to any one of claims 1 to 2.

8. The method according to any one of claims 1 to 2, wherein the concentration range of the photoinitiator component is 0.01 to 5.0% by mass.

9. The method according to claim 1, wherein at least one photoinitiator absorbs at a wavelength reflected by at least one light-reflecting material.

10. The method according to claim 1, wherein the curing depth is less than 150 microns.

11. The method according to claim 1, wherein the light-reflecting material component constitutes 5 to 90% by mass of the photopolymerizable composition.

12. The method according to claim 1, wherein the light-reflective material component comprises particulate light-reflective material having a size of less than 500 microns.

13. The method according to any one of claims 1 to 12, wherein the article is a medical device.

14. The method according to claim 2, wherein the photoinitiator is a non-toxic amount of photoinitiator and the article is a non-toxic polymeric article.

15. A photopolymerizable composition i) at least one photopolymerizable biodegradable macromer component, wherein the photopolymerizable biodegradable macromer component comprises a macromer comprising at least one monomer unit of a lactone monomer, glycolide, lactide, ε-caprolactone, trimethylene carbonate, p-dioxanone, 1,5-dioxepan-2-one, or morpholine-2,5-dione, or a combination thereof; ii) at least one light-reflective material component comprising a light-reflective material suspended in the photopolymerizable composition, wherein the light-reflective material is a biodegradable light-reflective material, and the light-reflective material comprises polyglycolide particles, absorbent phosphate ceramic microparticles, amorphous polylactide copolymer particles, or semi-crystalline polylactide particles; and iii) at least one photoinitiator component A photopolymerizable composition comprising.

16. The composition according to claim 15, wherein the total concentration of the photoinitiator concentration is less than 1.0% by mass.

17. The composition according to claim 15, wherein the photopolymerizable composition further comprises a reactive diluent, a non-reactive diluent, both a reactive diluent and a non-reactive diluent, a dye, or a stabilizer.

18. The composition according to claim 15, wherein the light-reflective material component comprises particulate light-reflective material.

19. The composition according to any one of claims 15 to 18, wherein the photopolymerizable composition polymerizes when exposed to a light wavelength of 10 to 700 nm.

20. The composition according to any one of claims 15 to 18, wherein the photopolymerizable composition photopolymerizes in a shorter time than a photopolymerizable composition not containing the reflective material under the same polymerization conditions.

21. The photopolymerizable composition photopolymerizes at a faster rate with the same exposure amount (mW / cm 2 ) than the photopolymerizable composition not containing the reflective material under the same polymerization conditions. The composition according to any one of claims 15 to 18.

22. The composition according to any one of claims 15 to 18, wherein the photoinitiator absorbs at a wavelength reflected by the light-reflective material.

23. The composition according to any one of claims 15 to 18, wherein the light-reflective material component constitutes 5 to 65% by mass of the photopolymerizable composition.

24. The composition according to any one of claims 15 to 18, wherein the light-reflective material component contains a light-reflective material that polymerizes with at least one of a photopolymerizable biodegradable macromer, a diluent, a light-reflective material, or a combination thereof.

25. The composition according to any one of claims 15 to 24, wherein the composition is a stereolithography photopolymerizable composition, a continuous liquid interface production photopolymerizable composition, or a DLP (Digital Light Processing) photopolymerizable composition.

26. A photopolymerizable ink composition, a) at least one photopolymerizable biodegradable macromer component, wherein the photopolymerizable biodegradable macromer component contains a macromer containing at least one monomer unit of a lactone monomer, glycolide, lactide, ε-caprolactone, trimethylene carbonate, p-dioxanone, 1,5-dioxepan-2-one, or morpholine-2,5-dione, or a combination thereof; b) at least one light-reflective material component containing a light-reflective material suspended in the photopolymerizable composition, wherein the light-reflective material is a biodegradable light-reflective material, and the light-reflective material contains polyglycolide particles, absorbent ceramic phosphate microparticles, amorphous polylactide copolymer particles, or semi-crystalline polylactide particles; c) at least one photoinitiator component; d) a reactive diluent; and e) a stabilizer The photopolymerizable ink composition containing.

27. A polymer obtained by polymerizing the composition according to any one of claims 15 to 26.

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