Composition and method of making article

Abstract

The invention relates to a composition and a method of making an article. A photocurable composition includes a first component composed of a photocurable compound, a second component composed of a photopolymerization initiator, a third component composed of black particles, and a fourth component composed of non-black particles. The mass concentration of the fourth component in the composition is greater than 100 times of the mass concentration of the third component and less than 3000 times of the mass concentration of the third component.

Description

Technical Field

[0001] This disclosure relates to photocurable compositions. Background Technology

[0002] Photocurable compositions are used in stereolithography and other methods. PCT Japanese Patent Publication No. 2023-506819 discloses a composition for use in an additive manufacturing method that does not generate volatile organic compounds during the additive manufacturing process.

[0003] Photocurable compositions are expected to have good curability (easy curing). However, when a photocurable composition contains a photoinitiator, irradiation with an activation energy beam such as UV light decomposes the photoinitiator, leaving volatile organic compounds (VOCs) derived from the photoinitiator within the cured product. These VOCs are considered to be released from the cured product. From an environmental impact perspective, reducing these VOCs is desirable. While reducing the amount of photoinitiator can reduce VOCs, this also degrades the curability. Summary of the Invention

[0004] This disclosure provides techniques that allow photocurable compositions to advantageously achieve both curability and VOC reduction.

[0005] The first aspect of this disclosure provides

[0006] A photocurable composition comprising:

[0007] The first component is composed of photopolymerizable compounds;

[0008] The second component is composed of a photopolymerization initiator;

[0009] The third component consists of black particles; and

[0010] The fourth component consists of non-black particles.

[0011] in:

[0012] The fourth component comprises non-black particles with a particle size of 1 μm or larger and 20 μm or smaller, and

[0013] The mass concentration of the fourth component in the composition is greater than 200 times the mass concentration of the third component and less than 3000 times the mass concentration of the third component.

[0014] The second aspect of this disclosure provides

[0015] A photocurable composition comprising:

[0016] The first component is composed of photopolymerizable compounds;

[0017] The second component is composed of a photopolymerization initiator;

[0018] The third component consists of black particles; and

[0019] The fourth component consists of non-black particles.

[0020] in:

[0021] The first component contains a cyclized polymerizable compound.

[0022] The third component contains black particles with a pH below 4.0 or above 9.0, and

[0023] The fourth component contains non-black particles containing salt.

[0024] The third aspect of this disclosure provides

[0025] A photocurable composition comprising:

[0026] The first component is composed of photopolymerizable compounds;

[0027] The second component, consisting of a photopolymerization initiator; and

[0028] The third component, consisting of black particles,

[0029] in:

[0030] The first component comprises a cyclized polymerizable compound, and

[0031] The mass concentration of the third component in the composition is 0.01% by mass or more and less than 0.10% by mass.

[0032] A fourth aspect of this disclosure provides a method for manufacturing an article of article, the method comprising:

[0033] The step of forming a layer of the photocurable composition; and

[0034] The step of curing the layer of the composition by irradiation with light.

[0035] These steps are repeated to construct a layered object, and

[0036] The composition comprises:

[0037] The first component is composed of photopolymerizable compounds;

[0038] The second component is composed of a photopolymerization initiator;

[0039] The third component consists of black particles; and

[0040] The fourth component consists of non-black particles.

[0041] in:

[0042] The third component contains black particles with a pH below 4.0 or above 9.0.

[0043] The fourth component contains non-black particles containing salt.

[0044] The fifth aspect of this disclosure provides a method for manufacturing an article of article, the method comprising:

[0045] The step of forming a layer of the photocurable composition; and

[0046] The step of curing the layer of the composition by irradiation with light.

[0047] These steps are repeated to construct the stack, and

[0048] The composition comprises:

[0049] The first component is composed of photopolymerizable compounds;

[0050] The second component is composed of a photopolymerization initiator;

[0051] The third component consists of black particles; and

[0052] The fourth component consists of non-black particles.

[0053] in:

[0054] The mass concentration of the third component in the composition is 0.01% by mass or more and less than 0.10% by mass.

[0055] The fourth component comprises non-black particles containing flame retardants.

[0056] Further features of this disclosure will become apparent from the following description of exemplary embodiments with reference to the accompanying drawings. Attached Figure Description

[0057] Figure 1 This is a diagram illustrating additive manufacturing equipment using the free surface method.

[0058] Figure 2 This is a diagram illustrating additive manufacturing equipment using the constrained surface method. Detailed Implementation

[0059] In the following description, embodiments for carrying out this disclosure are described with reference to the accompanying drawings. In the following description and drawings, the same features are designated by the same reference numerals throughout the various figures.

[0060] Therefore, the same features are described by referring to multiple figures, and descriptions of features marked by the same figure references are appropriately omitted.

[0061] Hereinafter, the photocurable composition according to one embodiment will be referred to as composition X, and the product obtained by photocuring composition X will be referred to as cured product Y. The light used to cure composition X will be referred to as irradiation light. Irradiation light is typically ultraviolet (UV) light, but it can also be visible light. Irradiation light can include beams of multiple wavelengths, including an activation energy beam, and can impart different effects to composition X depending on the wavelength. Cured product Y is used to manufacture article Z. Composition X is suitable for method V of manufacturing article Z, which involves preparing composition X and curing composition X by irradiating composition X with light. Composition X is suitable for method W of manufacturing article Z, which includes constructing a (additive manufacturing) laminate by repeatedly forming layers of composition X and curing the layers of composition X by irradiation with light. Article Z is cured product Y as is, or cured product Y that has undergone necessary treatment. Article Z can be used in various devices.

[0062] Composition X according to one embodiment comprises at least component A, consisting of a photopolymerizable compound, component B, consisting of a photopolymerization initiator, and component C, consisting of black particles. Component A may be the main component of composition X and may be the main raw material of cured product Y. Component B promotes the polymerization of component A. The decomposition products of component B may include volatile organic compounds (VOCs). When component A contains a low-reactivity photopolymerizable compound, higher irradiation energy or a larger amount of component B is required for its polymerization, and the amount of VOC generation tends to increase. A representative example of a low-reactivity photopolymerizable compound is a cyclized polymerizable compound. During curing, the black particles constituting component C block light, inhibiting the decomposition of component B (photopolymerization initiator) and reducing the generation of VOCs originating from component C. Note that in this embodiment, VOC generation can be reduced as long as irradiation light is the cause; therefore, VOCs generated by irradiation light may also originate from components other than component C. Composition X of this embodiment may further comprise component D, consisting of non-black particles. The non-black particles constituting component D scatter the irradiated light during light irradiation, promoting the polymerization of component A (photopolymerizable compound) and the decomposition of component B, thus enabling the adjustment of the curability and VOC generation of composition X. Furthermore, by using the non-black particles constituting component D, the mechanical properties of composition X, such as viscosity and the strength of the cured product Y, as well as its flame retardancy, can be controlled. Additionally, composition X of this embodiment may also contain component E, which is not classified as any of components A to D.

[0063] In the following description, "concentration" means the mass concentration of composition X in an amount having a substantially uniform component distribution. An amount having a substantially uniform component distribution can be, for example, 1 mm. 3 That's all. In other words, by measuring 1mm... 3 By performing component analysis on the above composition X, the composition X and the mass concentration of the substances contained in composition X can be determined.

[0064] In the first embodiment, the mass concentration of component D in composition X can be greater than 100 times and less than 3000 times the mass concentration of component C. A smaller amount of component C compared to component D can reduce VOCs without significantly degrading the curability of composition X.

[0065] In a second embodiment, component C may contain black particles with a pH below 4.0 or above 9.0. Component D may contain non-black particles containing salt. Since the acidic black particles with a pH below 4.0 are attracted by the cations of the salt contained in the non-black particles, light scattering by the non-black particles can be suppressed. Alternatively, since the alkaline black particles with a pH above 9.0 are attracted by the anions of the salt contained in the non-black particles, light scattering by the non-black particles can be suppressed.

[0066] In the third embodiment, the mass concentration of component C in composition X can be greater than 0.01% by mass and less than 0.10% by mass. A small amount of component C can reduce the amount of VOC generated without significantly degrading the curability of composition X.

[0067] The first to third embodiments can be used when component A contains cyclized polymerizable compounds. This is because, even when the irradiation energy is increased, the increase in VOC generation can be suppressed due to the presence of low-reactivity photopolymerizable compounds.

[0068] The first to third embodiments can be used when component D contains non-black particles containing flame retardants. This is because non-black particles, as flame retardants, tend to scatter light, but component C can reduce the amount of VOCs generated.

[0069] Composition X, having at least one feature of the first to third embodiments, can be used in manufacturing methods V and W. In particular, in manufacturing method W, which stacks a plurality of cured layers, the curability of each layer of composition significantly affects productivity (build rate). It is possible to increase the curability of each layer of composition while reducing VOC generation.

[0070] When composition X contains sterically hindered cyclizable compounds or other substances that reduce polymerizability (reactivity), a larger amount of photopolymerization initiator needs to be added from a production standpoint. Therefore, adding 0.01% by mass or more but less than 0.1% by mass of carbon black to composition X reduces the amount of VOC components generated in the cured product X without excessively degrading reactivity. When the concentration of carbon black is 0.01% by mass or more, radiated UV light and the like are absorbed by the carbon black in the composition, thus reducing the amount of initiator decomposition in composition X. When the concentration of carbon black is less than 0.1% by mass, the polymerization reaction initiated by the decomposition of the photoinitiator near the irradiated surface is advanced, thus the reaction time is not excessively reduced.

[0071] Components A through E will now be described in detail.

[0072] Component A: Photopolymerizable compound

[0073] Photopolymerizable compounds possess the property of undergoing polymerization when attacked by a photoinitiator activated by irradiation with an activation energy beam having a specific wavelength. Examples of photopolymerizable compounds include free radical polymerizable compounds, cationic polymerizable compounds, and anionic polymerizable compounds. Examples of functional groups reacting during polymerization include acrylate and methacrylate groups for free radical polymerizable compounds, epoxy and oxetane groups for cationic polymerizable compounds, and acrylate, methacrylate, styrene, acrylonitrile, N-vinylpyrrolidone, acrylamide, conjugated diene, and vinyl ketone groups for anionic polymerizable compounds. Furthermore, photopolymerizable compounds include polyfunctional and monofunctional compounds.

[0074] In component A, only one photopolymerizable compound may be used, or two or more photopolymerizable compounds may be used in combination. Furthermore, from the viewpoint of promoting the polymerization reaction of the photopolymerizable compound, the concentration of component A in composition X may be in the range of 50% by mass or more and 99% by mass or less.

[0075] When preparing composition X, the type and blending of photopolymerizable compounds are sometimes adjusted to improve the physical properties of the material. In this case, depending on the photopolymerizable compound selected, the reactivity of the photopolymerizable compound may be reduced due to the type of functional groups to be polymerized and the spatial structure of the compound itself.

[0076] Cyclopolymers

[0077] Examples of photopolymerizable compounds with low reactivity are cyclizable compounds. Cyclic polymerizable compounds are compounds that form cyclic structures through intramolecular polymerization. The content of cyclizable compounds can be set from the viewpoint of improving the material properties of the selected compound and suppressing excessive reactivity. Typically, the concentration of cyclizable compounds in composition X can be 10% by mass or more, 20% by mass or more, 80% by mass or less, or 50% by mass or less.

[0078] Examples of cyclizable polymerizable compounds include diallyl quaternary ammonium salts and 1,6-dienes such as 1,6-perfluorodiene and monofunctional 2-(allyloxymethyl)acrylic acid or its esters. From the viewpoint of compatibility with other polymerizable compounds and polymerization reactivity, 2-(allyloxymethyl)acrylic acid or its esters can be used. 2-(allyloxymethyl)acrylic acid and its esters are represented by the following general formula (1). The number of acryloyl groups in the cyclizable polymerizable compounds of the following general formula (1) is 1.

[0079]

[0080] In general formula (1), R represents hydrogen or a hydrocarbon group, and can be a hydrocarbon group with 1 or more but less than 4 carbon atoms. The hydrocarbon group can be saturated or unsaturated and can have substituents. The hydrocarbon group can be straight-chain, branched or cyclic, and can contain ether bonds.

[0081] Examples of hydrocarbon groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, vinyl, allyl, methylallyl, crotonyl, cyclopropyl, cyclobutyl, methoxymethyl, methoxyethyl, ethoxymethyl, ethoxyethyl, vinyloxyethyl, epoxy, and oxetanyl. Hydrocarbon groups can have 1 or more but less than 2 carbon atoms.

[0082] Examples of substituents that a hydrocarbon group may have include chain-like unsaturated hydrocarbon groups, such as vinyl, allyl, methyl allyl, and crotonyl; cyclic ether structures, such as epoxy, glycidyl, and oxetyl; alkoxy groups, such as methoxy, ethoxy, and methoxyethoxy; alkylthio groups, such as methylthio and ethylthio; acyl groups, such as acetyl and propionyl; acyloxy groups, such as acetoxy and propionyloxy; alkoxycarbonyl groups, such as methoxycarbonyl and ethoxycarbonyl; alkylthiocarbonyl groups, such as methylthiocarbonyl and ethylthiocarbonyl; halogen atoms, such as fluorine, chlorine, bromine, and iodine atoms; acylurea; amide; cyano; hydroxyl; and trimethylsilyl.

[0083] Commercially available products can also be used as cyclizable polymerizable compounds, and an example of such products is AOMA (manufactured by NIPPONSHOKUBAI CO.,LTD.). AOMA has a structure represented by the general formula (1), where R represents a methyl group.

[0084] Monofunctional free radical polymeric compounds

[0085] Examples of monofunctional radical polymerizable compounds include, but are not limited to, the following monofunctional (meth)acrylates: 4-tert-butylcyclohexanol (meth)acrylate, 3,3,5-trimethylcyclohexanol (meth)acrylate, isobornyl (meth)acrylate, cyclic trimethylolpropane acetal (meth)acrylate, 3-hydroxy-1-(meth)acryloyloxyadamantane, 1-adamantane (meth)acrylate, 2-methyl-2-adamantane (meth)acrylate, dicyclopentaenyl(meth)acrylate, 2-isopropylbenzoyl(meth)acrylate, tetrahydrodicyclopentadienyl(meth)acrylate, α-(meth)acryloyloxy-γ-butyrolactone, 2-hydroxy-o-phenylphenol propyl (meth)acrylate, acryloylmorpholine, diethylacrylamide, and isopropylacrylamide. Hydroxyethylacrylamide, Cyclohexyl methacrylate, Methyl methacrylate, 2-Ethylhexyl methacrylate, Lauryl methacrylate, Stearyl methacrylate, Isooctyl methacrylate, Tetrahydrofurfuryl methacrylate, Isobornyl methacrylate, Benzyl methacrylate, Phenoxyethyl methacrylate, Phenoxy polyethylene glycol methacrylate, Phenyl glycidyl methacrylate, Lauryl methacrylate, Isodecyl methacrylate, Stearyl methacrylate, Isooctyl methacrylate, Tridecyl methacrylate, Ethoxydiethylene methacrylate, Methoxydi-tripropylene glycol methacrylate, Tricyclodecane methacrylate, Dicyclopentadienoxyethyl methacrylate, Dicyclopentaenyl acrylate Acrylate), dicyclopentenoxyethyl acrylate, dicyclopentenoxy methacrylate, dicyclopentyl acrylate, and dicyclopentyl methacrylate.

[0086] Multifunctional free radical polymeric compounds

[0087] Examples of multifunctional radical polymerizable compounds include (meth)acrylate compounds, vinyl ether-containing (meth)acrylate compounds, isocyanurate compounds containing (meth)acryloyl groups, (meth)acrylamide compounds, urethane (meth)acrylate compounds, maleimide compounds, vinyl ether compounds, and aromatic vinyl compounds. Among these, (meth)acrylate compounds and urethane (meth)acrylate compounds are preferred from the viewpoint of availability and curability.

[0088] cationic polymeric compounds

[0089] Examples of cationic polymerizable compounds include, but are not limited to, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol AD ​​diglycidyl ether, hydrogenated bisphenol Z diglycidyl ether, cyclohexanediethanol diglycidyl ether, tricyclodecanediethanol diglycidyl ether, 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexane carboxylate, 3,4-epoxy-1-methylcyclohexyl-3,4-epoxy-1-methylcyclohexane carboxylate, and 6-methyl-3,4-epoxycyclohexylmethyl-6-methyl-3,4-epoxycyclohexane. Alkyl carboxyl esters, 3,4-epoxy-3-methylcyclohexylmethyl-3,4-epoxy-3-methylcyclohexane carboxyl esters, 3,4-epoxy-5-methylcyclohexylmethyl-3,4-epoxy-5-methylcyclohexane carboxyl esters, 2-(3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy)cyclohexane-metadioxane, bis(3,4- Epoxycyclohexylmethyl) adipate, 3,4-epoxy-6-methylcyclohexylcarboxylate, dicyclopentadiene diester, bis(3,4-epoxycyclohexanecarboxylate) ethylene ester, dioctyl hexahydrophthalate, di-2-ethylhexyl hexahydrophthalate, ε-caprolactone-modified 3',4'-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 1,2-epoxy-4-(2-epoxyethylene(oxiranyl))cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol, bis(3,4- Examples of cyclohexylene oxides include 2,2-bis(3,4-cyclohexylene oxide), 1,1-bis(3,4-cyclohexylene oxide), α-pinene oxide, campholenaldehyde, limonene oxide, limonene dioxide, 4-vinylcyclohexene oxide, 4-vinylcyclohexene dioxide, 3-hydroxymethyl-3-methyloxetane, 3-hydroxymethyl-3-ethyloxetane, 3-hydroxymethyl-3-propyloxetane, and 3-hydroxymethyl-3-n-butyloxetane.

[0090] Anionic polymeric compounds

[0091] Examples of anionic polymerizable compounds include, but are not limited to, epoxy compounds, lactone compounds, acrylic compounds, and methacrylic compounds.

[0092] Component B: Photopolymerization initiator

[0093] The photopolymerization initiator can be appropriately selected based on the curing conditions (irradiation wavelength and dosage) of the curable resin. Types of photopolymerization initiators include free radical photoinitiators, cationic photoinitiators, and anionic photoinitiators.

[0094] Materials that decompose to generate free radicals under irradiation with an activation energy beam, thereby curing photopolymerizable resins, are used as free radical photoinitiators. From an economic point of view, ultraviolet light with wavelengths of 300 nm to 450 nm can be used as the activation energy beam, and photopolymerization initiators that generate free radicals under irradiation with such wavelengths can be used.

[0095] Photopolymerization initiators decompose under irradiation with activation energy beams such as UV light, and VOCs derived from the initiator may remain inside the photocured material. These VOCs are believed to be released from the stereolithographic construct. Given recent trends in environmental awareness, reducing such VOCs is desirable. Reducing VOCs derived from this compound is particularly important when component D contains compounds with intramolecular trimethylbenzene.

[0096] The mass concentration of component B in composition X can be, for example, 0.1% by mass or more, or 0.5% by mass or more; in order to promote the reaction of component A even when component A has low reactivity, the mass concentration of component B can be 1% by mass or more. The mass concentration of component B in composition X can be, for example, 10% by mass or less, and from the viewpoint of reducing VOCs, the mass concentration of component B can be 5% by mass or less.

[0097] Photopolymerization initiators that generate free radicals using an activation energy beam of this wavelength can have aromatic rings. Examples include, but are not limited to, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-1-butanone, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenyl-prop-1-one, 4-phenylbenzophenone, 4-phenoxybenzophenone, 4,4'-diphenylbenzophenone, and 4,4'-diphenoxybenzophenone.

[0098] These compounds may contain acylphosphine oxide compounds, representative examples of which include bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide and 2,4,6-trimethylbenzoyl-diphenylphosphine oxide. As photopolymerization initiators, acylphosphine oxide compounds exhibit high photopolymerization initiation activity and photobleaching effect. The photobleaching effect is characterized by the following phenomenon: once the photopolymerization initiator decomposes by absorbing light, the decomposed photopolymerization initiator residue no longer absorbs ultraviolet light and can no longer prevent ultraviolet light from penetrating the interior. Therefore, acylphosphine oxide compounds possess excellent internal curing properties and can cure thick films.

[0099] You can use only one photopolymerization initiator, or you can use a combination of two or more photopolymerization initiators.

[0100] The concentration of the photopolymerization initiator is appropriately adjusted depending on the type of polymerizable compound used, and can be in the range of 0.01 parts by mass to 10 parts by mass relative to 100 parts by mass of the polymerizable compound. If the concentration of the photopolymerization initiator is too low, curing will not occur even when the light intensity or irradiation time is increased. Conversely, if the concentration of the initiator is too high, there is a risk that the average molecular weight may decrease.

[0101] Furthermore, reactivity can decrease depending on the spatial structure and type of functional groups of the polymerizable compound used. An example is the use of monofunctional 2-(allyloxymethyl)acrylic acid or its esters. In this case, the concentration of the photoinitiator relative to 100 parts by mass of the polymerizable compound can be in the range of 2.00 parts by mass to 10.00 parts by mass, although this depends on the blending amount of the polymerizable compound. Moreover, the concentration of the photoinitiator also needs to be adjusted according to the transmittance of the material to the polymerizable compound. In particular, when composition X contains materials that absorb irradiated light, the concentration of the photoinitiator needs to be increased to improve curability. Note that the proportion of photoinitiator added can be appropriately selected based on the amount of activation energy beam and the additional heating temperature.

[0102] Furthermore, this ratio can be adjusted according to the target average molecular weight of the polymer to be obtained.

[0103] When adding a cationic polymerizable compound, a polymerization initiator, photoacid generator, and / or photobase generator that generates cationic species under light irradiation can be added to composition X to promote the polymerization reaction of the cationic polymerizable compound. Examples of polymerization initiators that generate cationic species under light irradiation include, but are not limited to, (4-methylphenyl)[4-(2-methylpropyl)phenyl]-iodonium hexafluorophosphate. Examples of photoacid generators include, but are not limited to, triarylhexafluoroantimony sulfonate, triphenylbenzoylmethylphosphonium tetrafluoroborate, triphenylhexafluoroantimony sulfonate, bis-[4-(diphenylsulfonyl)phenyl]sulfide bis-hexafluoroantimony sulfonate, bis-[4-(di-4′-hydroxyethoxyphenylsulfonyl)phenyl]sulfide bis-hexafluoroantimony sulfonate, bis-[4-(diphenylsulfonyl)phenyl]sulfide bis-hexafluorophosphate, and diphenyliodonium tetrafluoroborate.

[0104] When anionic polymerizable compounds are added, polymerization initiators, photoacid generators, and / or photobase generators that generate anionic species under light irradiation can be added to composition X to promote the polymerization reaction of the anionic polymerizable compounds. Examples of polymerization initiators that generate anionic species include o-nitrobenzylcarbamate derivatives, o-acyloxy derivatives, and o-carbamoyl oxime derivatives.

[0105] The concentration of the polymerization initiator that generates cationic species can be in the range of 0.01 parts by mass and 10.00 parts by mass relative to 100 parts by mass of the cationic polymerizable compound. The concentration of the polymerization initiator that generates anionic species can be in the range of 0.01 parts by mass and 10.00 parts by mass relative to 100 parts by mass of the anionic polymerizable compound.

[0106] Component C: Black particles

[0107] Black particles are used as light absorbers and have the effect of reducing the amount of initiator decomposition by reducing the amount of light entering the interior of composition X or the cured product Y located below composition X in additive manufacturing. Various black pigments can be used as black particles, examples of which include carbon black-based pigments such as carbon black and graphite, and metallic compound black pigments such as titanium black and iron black. A single black particle can be used, or two or more black particles can be used in combination. For example, black particles with a pH below 4.0 and black particles with a pH greater than 4 and less than 9 can be used in combination, or carbon black and titanium black can be used in combination.

[0108] From the viewpoint of reducing VOC generation, the concentration of component C in composition X can be 0.01% by mass or more. The concentration of component C in composition X can be 10% by mass or less, for example, 5% by mass or less; however, from the viewpoint of curability, this concentration can be less than 1.00% by mass, less than 0.50% by mass, or less than 0.10% by mass.

[0109] The particle size of the black particles is, for example, 1 nm or more, and may be 10 nm or more. The particle size of the black particles may be, for example, less than 10 μm, less than 1 μm, less than 500 nm, or less than 100 nm. When the particle size of the black particles is 10 μm or more, the specific surface area of ​​the black particles is small, and the light attenuation effect and VOC reduction effect may be insufficient; furthermore, the back side of the black particles relative to the irradiated light becomes insufficiently cured, thus making it difficult to properly cure composition X. Among the black particles contained in component C, those black particles having the above-mentioned particle sizes contribute to improving composition X, cured product Y, and manufacturing methods V and W. Component C may contain black particles with particle sizes outside the above-mentioned ranges. The average particle size of the black particles contained in component C may be the above-mentioned particle sizes.

[0110] When component D (non-black particles) is added to composition X, the types of non-black and black particles are appropriately combined to reduce VOC generation without excessively degrading reactivity. Specifically, a salt composed of anions and cations is used as a material contained in the non-black particles, and black particles with a pH below 4.0 or above 9.0 are used as black particles. According to this combination, the black particles aggregate on the surface of the non-black particles, reducing the scattering of light by the non-black particles and inhibiting the decomposition of component B, thus reducing VOC generation. An example of black particles with a pH below 4.0 or above 9.0 is carbon black.

[0111] For example, Coulombic interactions can occur between the positively charged portions of cations from salts originating from non-black particles and the negatively charged portions of acidic surface groups such as carboxyl or hydroxyl groups from carbon black at pH below 4.0. Alternatively, Coulombic interactions can occur between the negatively charged portions of anions from salts originating from non-black particles and the positively charged portions of chromene or pyranone structures from carbon black at pH above 9.0. By utilizing these Coulombic interactions, carbon black aggregates on the surface of non-black particles.

[0112] As a result, the black particles surrounding the non-black particles absorb the illumination light, thereby reducing the amount of light scattered from the non-black particles and thus reducing the amount of VOCs generated.

[0113] Examples of commercially available carbon black are as follows:

[0114] Products from Mitsubishi Chemical Corporation: MA7, MA8, MA11, MA14, MA77, MA100, MA100R, MA100S, MA220, MA230, MA600, MCF88, #5, #10, #20, #25, #30, #32, #33, #40, #44, #45, #47, #50, #52, #55, #650, #750, #850, #900, # 950, #960, #970, #980, #990, #1000, #2200, #2300, #2350, #2400, #2600, #2650, #3030, #3050, #3150, #3250, #3400, #3600, #3750, #3950, #4000, #4010, OIL7B, OIL9B, OIL11B, OIL30B and OIL31B;

[0115] Degussa AG's products include: Printex (registered trademark, also applicable below) 3, Printex 3OP, Printex 30, Printex 30OP, Printex 40, Printex 45, Printex 55, Printex 60, Printex 75, Printex 80, Printex 85, Printex 90, Printex A, Printex L, Printex G, Printex P, Printex U, Printex V, Special Black 550, Special Black 350, Special Black 250, Special Black 100, Special Black 6, Special Black 5, Special Black 4, Color Black FW1, Color Black FW2, Color Black FW2V, Color Black 18, Color Black FW200, Color Black S160 and Color Black S170;

[0116] Cabot Corporation products: Monarch (registered trademark, hereinafter also applicable) 120, Monarch 280, Monarch 460, Monarch 800, Monarch 880, Monarch 900, Monarch 1000, Monarch 1100, Monarch 1300, Monarch 1400, Monarch 4630, REGAL (registered trademark, hereinafter also applicable) 99, REGAL 99R, REGAL 415, REGAL 415R, REGAL 250, REGAL 250R, REGAL 330, REGAL 400R, REGAL 55R0, REGAL 660R, BLACK PEARLS 480, PEARLS 130, VULCAN (registered trademark, hereinafter also applicable) XC72R, ELFTEX (registered trademark) -8; and

[0117] Products of Columbian Carbon Company: RAVEN (registered trademark, the following also applies) 11, RAVEN 14, RAVEN 15, RAVEN 16, RAVEN 22, RAVEN 30, RAVEN 35, RAVEN 40, RAVEN 410, RAVEN 420, RAVEN 450, RAVEN 500, RAVEN 780, RAVEN 850, RAVEN 890H, RAVEN 1000, RAVEN 1020, RAVEN 1040, RAVEN 1060U, RAVEN 1080U, RAVEN 1170, RAVEN 1190U, RAVEN 1250, RAVEN1500, RAVEN 2000, RAVEN 2500U, RAVEN 3500, RAVEN 5000, RAVEN 5250, RAVEN 5750 and RAVEN 7000.

[0118] Examples of commercially available carbon black with a pH below 4.0 are as follows:

[0119] Products from Mitsubishi Chemical Corporation: MA7, MA8, MA11, MA14, MA77, MA100, MA100R, MA100S, MA220, MA230, #970, #1000, #2350 and #2650;

[0120] Products of Degussa AG: Special Black 550, Special Black 350, Special Black 250, Special Black 100, Special Black 6, Special Black 5 and Special Black 4;

[0121] Cabot Corporation products: Black Pearls and MONARCH 1300; and

[0122] Columbian Carbon Company's products include: RAVEN 14, RAVEN 1040, RAVEN 1060U, RAVEN 1080U, and RAVEN 3500.

[0123] Examples of commercially available carbon black with a pH of 9.0 or higher are as follows:

[0124] Products of Orion Engineered Carbons SA: PRINTEX 3, PRINTEX 25, PRINTEX 30, PRINTEX 35, PRINTEX 45, PRINTEX 55, PRINTEX 60, PRINTEX 75, PRINTEX 80, PRINTEX 85, PRINTEX 90, PRINTEX 95, PRINTEX 200, PRINTEX 300, PRINTEX A, PRINTEX F80, PRINTEXF85, PRINTEX FP, PRINTEX G, PRINTEX L, PRINTEX L6, PRINTEX P, PRINTEX 20L and PRINTEX30L.

[0125] Component D: Non-black particles

[0126] The non-black particles that make up component D are particles that absorb less light than the black particles of component C. They are usually white or colorless particles, but can also be colored particles.

[0127] Non-black particles function as light scatterers, scattering the irradiated light entering the composition X, and thus can be a factor affecting curability; however, non-black particles can also increase the amount of initiator decomposed. For example, irradiated light scattered by non-black particles imparts energy to unintended areas of composition X. Therefore, the amount of VOCs generated increases depending on the type, shape, and amount of non-black particles. Here, the scattering of irradiated light by non-black particles is typically due to diffuse reflection and diffraction by the particles; alternatively, scattering can be caused by the refractive difference between the non-black particles and the surrounding matrix material. Therefore, non-black particles can be transparent with respect to irradiated light.

[0128] When the direction of illumination light becomes non-uniform due to forward scattering (diffraction scattering) and backscattering (diffuse reflection), excessive energy may be applied to the intersections of the illumination beams. Furthermore, when illumination light that has already passed through the matrix materials (components A and B) of composition X is backscattered by non-black particles, the illumination light re-irradiates the matrix, thus exposing composition X to double energy. This phenomenon can sometimes improve the curability of composition X, but it may increase VOC generation due to the decomposition of VOC sources such as component B. There may also be instances where illumination light passing through the matrix materials (components A and B) of composition X is laterally scattered by non-black particles. When lateral scattering occurs near the boundary between the build area and the non-build area in stereolithography, curing may advance in the non-build area and may affect build accuracy.

[0129] Non-black particles function as flame retardants to impart flame retardancy to cured products composed of photopolymerizable compounds or as fillers to adjust mechanical properties. When manufacturing article Z, such as laminates manufactured by method W, flame retardancy is typically required. When component D contains non-black particles containing flame retardants, the flame retardancy of both cured product Y and article Z can be improved. Note that when composition X contains black particles used to impart flame retardancy or high mechanical strength, these black particles are treated as component C.

[0130] Non-black particles can act as colorants or colorants to adjust the color of composition X and cured product Y. To enable the non-black particles to function as colorants or colorants, the concentration of component C can be less than 0.1% by mass. When the concentration of component C exceeds 0.1% by mass, composition X and cured product Y become almost completely black, making color adjustment difficult.

[0131] The concentration of component D in composition X can be less than 50% by mass, for example less than 40% by mass, less than 30% by mass, and less than 25% by mass.

[0132] Composition X may be free of component D, or the concentration of component D may be 0.01% by mass or more. The concentration of component D may be, for example, 1.00% by mass or more, 5% by mass or more, 10% by mass or more, and 15% by mass or more.

[0133] The concentration of component D in composition X can be greater than 100 times (D / C>100) and greater than 200 times (D / C>200) the concentration of component C in composition X. In other words, the concentration of component C in composition X can be less than 1 / 100 and less than 1 / 200 the concentration of component D in composition X. Even when the amount of component C is less than that of component D, a VOC reduction effect of component C can be obtained, and to ensure curability, the amount of component C can be less than that of component D. When the concentration of component C is 0.01% by mass, the relationship D / C>100 is satisfied as long as the concentration of component D is greater than 1.00% by mass. When the concentration of component C is less than 0.10% by mass, the relationship D / C>100 is satisfied as long as the concentration of component D is 10% by mass or more.

[0134] The concentration of component D in composition X can be less than 3000 times (D / C < 3000) and less than 2000 times (D / C < 2000) the concentration of component C in composition X. In other words, the concentration of component C in composition X can be greater than 1 / 3000 and greater than 1 / 2000 of the concentration of component D in composition X. Since the amount of VOC can increase with the increase of the amount of component D, the amount of component C can be increased according to the increase of the amount of component D. When the concentration of component C is 0.01% by mass or more, the relationship D / C < 3000 is satisfied as long as the concentration of component D is less than 30% by mass.

[0135] The particle size of non-black particles can be, for example, 10 nm or more, 500 nm or more, and 1 μm or more. The particle size of non-black particles can be, for example, 100 μm or less, 50 μm or less, and 20 μm or less. When the particle size of non-black particles is too small, their dispersibility may deteriorate. Note that when the particle size of non-black particles is too large, it becomes difficult to properly cure composition X. Non-black particles containing component D with the aforementioned particle sizes contribute to improving composition X, cured product Y, and manufacturing methods V and W. Component D may contain non-black particles with particle sizes outside the aforementioned ranges. The average particle size of the non-black particles contained in component D may be the aforementioned particle sizes.

[0136] Component C may contain black particles with a small particle size. Component D may contain non-black particles with a large particle size. Here, the large particle size is larger than the small particle size, but the large particle size can be more than 10 times, more than 100 times, less than 2000 times, and less than 1000 times the small particle size. The particle size of the black particles with a small particle size contained in component C can be from 10 to 100 nm. The particle size of the non-black particles with a large particle size contained in component D can be from 1 to 20 μm.

[0137] Examples of substances contained in non-black particles include salts, oxides, resins, rubber, inorganic fibers, and organic fibers.

[0138] A salt is a compound that has both anions and cations, and in which the anions and cations are ionically bonded. Salts can be normal salts, acidic salts, or basic salts. Salts can be inorganic salts or organic salts.

[0139] Salts composed of anions and cations are selected as non-black particles and used in combination with acidic or basic black particles. In this way, Coulombic interactions are induced between the cationic portions originating from the surface of the non-black particles and the negatively charged portions of surface acidic groups such as carboxyl or hydroxyl groups originating from the surface of the black particles. In other cases, Coulombic interactions are induced between the anionic portions originating from the surface of the non-black particles and the positively charged portions of chromene or pyranone structures originating from the surface of the black particles. As a result, black particles aggregate on the surface of the non-black particles and suppress light scattering. Simultaneously, direct illumination light other than scattered light is absorbed by the black particles. Consequently, the initiator near the light-illuminated surface is selectively decomposed, reducing the amount of VOCs generated.

[0140] Anions can be monatomic ions such as chloride ions or polyatomic ions such as oxoanions. Salts can contain oxoanions. Salts containing oxoanions are called oxoacid salts. Examples of oxoacid salts include phosphates, borates, silicates, carbonates, sulfates, and stannates.

[0141] Salts can have polyoxoanions. Polyoxoanions have an oxoanionic polymer as their backbone. The polymer has a chain or ring structure. Salts have cations bonded to the oxoanionic polymer, represented by the following general formula (2). In general formula (2), oxo- represents an oxoanion and cat+ represents a cation.

[0142]

[0143] Salts containing polyoxyanions are called polyoxyacid salts. Examples of polyoxyacid salts include polysilicates, polyborates, polyphosphates, and polystannates. Polyphosphates are phosphates containing adjacent phosphorus atoms bonded to other phosphorus atoms via oxygen atoms in a polymerization mode; they are a type of polyoxyacid salt. Examples of polyphosphates include ammonium polyphosphate, aluminum polyphosphate, melamine polyphosphate, and piperazine polyphosphate.

[0144] Cations can be monatomic ions such as metal ions or polyatomic ions such as ammonium ions. When the cation of a salt is a metal ion, the salt is a metal salt, and when the cation of a salt is an ammonium ion, the salt is an ammonium salt.

[0145] Examples of salts include ammonium phosphate, sodium borate, calcium silicate, aluminum silicate, clay, diatomaceous earth, calcium carbonate, magnesium carbonate, calcium sulfate, and barium sulfate.

[0146] The polyoxyacid salt forms a structure in which abundant cations exist on the surface of non-black particles when cations are added to the outside of the chain or cyclic polymer. This induces a stronger interaction with black particles at a pH below 4.0. Therefore, when component D contains non-black particles containing the polyoxyacid salt, component C can contain black particles at a pH below 4.0.

[0147] Non-black particles may contain ammonium polyphosphate. Ammonium polyphosphate is an ammonium salt of a phosphate polymer represented by the following general formula (3). Ammonium polyphosphate is a halogen-free flame retardant and is used to impart flame retardancy to the cured product Y. The polymer molecular weight is from about 800 to 200,000, but there are no particular limitations. The crystal structure of ammonium polyphosphate is type I, type II, type III, type IV and type V, but any type can be used.

[0148]

[0149] From the viewpoint of dispersion stability in composition X in its uncured state, the number-average particle size of the flame retardant can be, for example, 10 nm or more, 500 nm or more, and 1 μm or more. The number-average particle size of the flame retardant can also be, for example, less than 100 μm, less than 50 μm, and less than 20 μm. If the flame retardant can be extracted, the number-average particle size can be measured using a laser diffractometer. In the cured state containing the flame retardant, the particle size can be measured from a cross-sectional SEM image, and its average value can be calculated. The flame retardant can be used regardless of whether it has undergone surface treatment, but untreated flame retardants can also be used.

[0150] The concentration of the flame retardant in composition X can be, for example, 5% by mass or more, 10% by mass or more, and 15% by mass or more, and can be, for example, 40% by mass or less, 30% by mass or less, and 25% by mass or less. When the concentration of the flame retardant is low, the flame retardancy may deteriorate, and when the concentration of the flame retardant is high, the impact resistance may deteriorate.

[0151] Examples of oxides contained in non-black particles include, but are not limited to, silicon oxides (silicon dioxide), titanium oxides (titanium dioxide), and aluminum oxides (alumina). Examples of resins contained in non-black particles include, but are not limited to, acrylic, polystyrene, and nylon. Examples of rubbers contained in non-black particles include, but are not limited to, butadiene rubber, styrene-butadiene rubber copolymer, acrylonitrile-butadiene copolymer rubber, saturated rubber obtained by hydrogenating or partially hydrogenating these diene rubbers, cross-linked butadiene rubber, isoprene rubber, chloroprene rubber, natural rubber, silicone rubber, ethylene / propylene / diene monomer ternary polymer rubber, acrylic rubber, acrylic / silicone composite rubber, etc. Examples of organic fibers contained in component D include, but are not limited to, nylon fibers and cellulose nanofibers, etc.

[0152] Non-black particles containing silica, alumina, and calcium carbonate can be used as fillers. Fibers can also be used as fillers. Phosphorus compounds and boron compounds can be used as flame retardants. Non-black particles containing rubber can be used as elastomers. Titanium dioxide can be used as a white pigment.

[0153] Component E: Components other than components A through D

[0154] Solvents, polymerization inhibitors, photosensitizers, light stabilizers, heat stabilizers, oxidation inhibitors, chain transfer agents, curing aids, etc., may be added to composition X in this embodiment, provided that widespread performance degradation of the cured product does not occur.

[0155] The concentration of the polymerization inhibitor in composition X can be in the range of 0.01% by mass or more and 1.00% by mass or less. Furthermore, only one polymerization inhibitor can be used alone, or two or more polymerization inhibitors can be used in combination. Specifically, considering the reduction of coloration, hydroquinone polymerization inhibitors can be used in combination. Examples of polymerization inhibitors include hydroquinone-based inhibitors such as hydroquinone, hydroquinone monomethyl ether, hydroquinone monoethyl ether, hydroquinone monopropyl ether, hydroquinone monobutyl ether, hydroquinone monopentyl ether, hydroquinone monohexyl ether, hydroquinone monooctyl ether, and hydroquinone monoheptyl ether, as well as phenolic polymerization inhibitors with substituents such as 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate. However, since hydroquinone-based inhibitors such as hydroquinone and benzoquinone-based inhibitors such as benzoquinone can yellow due to UV irradiation, such inhibitors can be used to form film-cured products such as coatings. Examples of polymerization inhibitors used as polymerization inhibitors during reaction or storage include, but are not limited to, those inhibitors described above.

[0156] The concentration of the photosensitizer in composition X can be in the range of more than 0.01% by mass and less than 10.00% by mass. Examples of photosensitizers include benzophenone, 4,4-diethylaminobenzophenone, 1-hydroxycyclohexylphenyl ketone, p-(dimethylamino)benzoate isoamyl ester, 4-(dimethylamino)benzoate methyl ester, benzoin, benzoin ethyl ether, benzoin isobutyl ether, benzoin isopropyl ether, 2,2-diethoxyacetophenone, methyl o-benzoylbenzoate, 2-hydroxy-2-methyl-1-phenylprop-1-one, and acylphosphine oxide.

[0157] In some cases, the light stabilizer acts as a photosensitizer, in which case the photosensitizer does not need to be added. The concentration of the light stabilizer in composition X can be in the range of more than 0.01% by mass and less than 10.00% by mass. The light stabilizer can be any compound that does not extensively affect the properties of the cured product, examples of which include benzotriazole compounds such as 2-(2H-benzotriazole-2-yl)-p-cresol, 2-(2H-benzotriazole-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol, 2-[5-chloro(2H)-benzotriazole-2-yl]-4-methyl-6-(tert-butyl)phenol, 2-(2H-benzotriazole-2-yl)-4,6-di-tert-pentylphenol, 2-(2H-benzotriazole-2-yl)-4-(1,1 ,3,3-Tetramethylbutyl)phenol, 2,2'-methylenebis[6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol and 2-(2H-benzotriazol-2-yl)-6-dodecyl-4-methylphenol, etc., cyanoacrylate compounds such as ethyl 2-cyano-3,3-diphenylacrylate and 2-ethylhexyl 2-cyano-3,3-diphenylacrylate, etc., triazine compounds, and benzophenone compounds such as oxybenzone and 2,2'-4,4'-tetrahydrobenzophenone, etc.

[0158] The concentration of the heat stabilizer in composition X can be in the range of more than 0.01% by mass and less than 10.00% by mass. Heat stabilizers can be any compound that does not extensively affect the properties of the cured product, and examples include pentaerythritol tetra[3-(3,5-di-tert-butyl-4-hydroxyphenyl)]propionate, octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, C7-C9 alkyl esters having a 3,5-bis(1,1-dimethylethyl)-4-hydroxyphenylpropionate side chain, hindered phenolic compounds such as 4,6-bis(octylthiomethyl)-o-cresol, 4,6-bis(dodecylthiomethyl)-o-cresol, ethylene bis(oxyethylene)bis[3-(5-tert-butyl-4-hydroxy-m-tolyl)propionate and hexamethylene bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, phosphorus compounds such as tris(2,4-di-tert-butylphenyl)phosphite, and sulfur compounds such as di-octadecyl-3,3'-thiopropionate.

[0159] The concentration of the oxidation inhibitor in composition X can be in the range of more than 0.01% by mass and less than 10.00% by mass. The oxidation inhibitor can be any compound that does not extensively affect the properties of the cured product, and examples include hindered amine compounds such as bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate and bis(1,2,2,6,6-pentamethyl-4-piperidinyl)[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]butylmalonate.

[0160] The total concentration of chain transfer agent and curing aid in composition X can be in the range of more than 0.01% by mass and less than 10.00% by mass. Examples of chain transfer agents and curing aids include β-mercaptopropionic acid, 2-ethylhexyl-3-mercaptopropionate, n-octyl-3-mercaptopropionate, methoxybutyl-3-mercaptopropionate, stearyl-3-mercaptopropionate, 1-butanethiol, cyclohexanethiol, cyclohexyl 3-mercaptopropionate, 1-decylthiol, 2,4-diphenyl-4-methyl-1-pentene, 1-dodecylthiol, dodecyl 3-mercaptopropionate, and 2-ethylhexyl mercaptoacetic acid. Ester, 2-ethylhexyl 3-mercaptopropionate, ethyl mercaptoacetate, 1-hexadecylthiol, hexyl 3-mercaptopropionate, 2-mercaptoethanol, 3-mercapto-1,2-propanediol, mercaptoacetic acid, sodium 2-mercaptoethanesulfonate, 3-mercaptopropionic acid, methyl mercaptoacetate, mercaptosuccinic acid, methyl 3-mercaptopropionate, octadecyl 3-mercaptopropionate, octyl 3-mercaptopropionate, 1-octadecyl mercaptoacetate, 1-octadecyl mercaptoacetate, tridecyl 3-mercaptopropionate Thiophenol, polyfunctional thiols such as bis(2-mercaptoethyl) sulfide, 3,6-dioxa-1,8-octanedithiol, trimethylolpropane tris(3-mercaptopropionate), 1,4-butanediol bis(thioglycolate), pentaerythritol tetra(3-mercaptopropionate), 1,4-benzylthiophenol, 3,7-dithia-1,9-nonanol, DL-1,4-dimercapto-2,3-butanediol, 1,5-dimercaptonaphthalene, and dithioerythritol Ethyl dithioglycolate, pentaerythritol tetramercaptoacetate, tri-[(3-mercaptopropionyloxyethyl)-isocyanurate, tetraethylene glycol bis(3-mercaptopropionate), dipentaerythritol hexa(3-mercaptopropionate), 3,3'-thiodipropionic acid, dithiodipropionic acid and lauryl thiopropionic acid (dodecyl thiopropionic acid), as well as commercially available products such as TS-G, C3TS-G, TA-G and LDAIC (manufactured by Shikoku Chemicals Corporation), and Karenz MTPE1, BD1, NR1 and TPMB (manufactured by Showa Denko KK), etc.

[0161] Preparation method of composition X

[0162] There are no particular limitations on the preparation method of composition X. The simplest method is to weigh all materials and then stir the weighed materials. However, to address the risk of polymerization, a polymerization inhibitor may be added appropriately. When it is difficult to mix the materials uniformly by heating alone, all materials can be dissolved in a solvent such as acetone, and the solvent can be distilled off to prepare composition X. Alternatively, stirring can be performed using an ultrasonic homogenizer, ball mill, disc mill, planetary centrifugal mixer (Awatori Rentaro manufactured by THINKYCORPORATION (registered trademark) and MAZERUSTAR manufactured by KURABO INDUSTRIES LTD. (registered trademark)), or a disperser combining three-dimensional motion and automatic forward and reverse rotation (Mazemazeman manufactured by Misugi Co., Ltd. (registered trademark)). These stirring methods can be performed multiple times or in combination. Heating may be performed during stirring.

[0163] Manufacturing method of the product

[0164] In the curing step of composition X, there are no particular limitations on the shape of the cured product and the curing method.

[0165] Examples of curing methods include methods involving applying composition X to a substrate and then irradiating the applied composition X with light, methods involving casting composition X into a mold and then irradiating the cast composition X with light, and optical three-dimensional construction methods (stereolithography) involving stacking thin film cured materials layer by layer.

[0166] There are no particular limitations on the method of applying composition X to a substrate. For example, contact transfer coating equipment such as a roller coater, reverse coater, bar coater, or slot coater, or non-contact coating equipment such as a spin coater or curtain flow coater can be used to apply composition X to the substrate to the desired film thickness to form a coating film. When using the composition X disclosed herein for stereolithography, any stereolithography method and equipment known in the art can be used. For example, the method may involve repeatedly forming a cured layer by photocuring composition X to a specific thickness. A representative example of stereolithography involves a method that repeatedly supplies composition X to a specific thickness and then cures composition X at that specific thickness, based on slice data generated from three-dimensional shape data (three-dimensional model) of the manufactured object.

[0167] Stereolithography is broadly classified into free-plane and confined-plane methods. In both methods, the step of forming a layer of composition X involves placing the layer of composition X between a stage in the liquid composition X and the liquid surface of composition X. In the curing step, light is irradiated through the liquid surface of composition X. The layer of composition X can be referred to as the layer of the composition. The cured layer of composition X can be referred to as the cured layer. The cured product Y obtained by additive manufacturing is a stack of multiple cured layers. The thickness of a layer of composition or cured layer can be, for example, 1 μm or more, 10 μm or more, and, for example, less than 1 mm or less than 100 μm, and composition X is suitable for layers of composition with such thicknesses. When using extremely thick layers of composition, longer irradiation times or higher irradiation intensities are required for the necessary curing.

[0168] Figure 1 An example structure of an additive manufacturing apparatus 100 employing the free-surface method is shown. The additive manufacturing apparatus 100 includes a tank 11 containing a raw material liquid 10 composed of a liquid composition X. A build stage 12 is disposed inside the tank 11 and is capable of being driven vertically via a drive shaft 13. An activation energy beam 15, used for curing the raw material liquid 10 and emitted from a light source 14, has its irradiation position changed by a galvanometer 16 to scan the surface of the tank 11. Figure 1 In the image, the scanning range is indicated by a bold dashed line. The current mirror 16 is controlled by the controller 18 based on the slice data.

[0169] The thickness d of the layer (layer of composition) of the raw material liquid 10 composed of composition X, cured by the activation energy beam 15, is a value determined based on the settings during the generation of slice data, and affects the accuracy of the article to be obtained (the reproducibility of the three-dimensional shape data of the constructed article). The thickness d is achieved by controlling the drive amount of the drive shaft 13 through the controller 18.

[0170] First, the controller 18 controls the drive shaft 13 based on settings and supplies a raw material liquid 10 of thickness d, composed of composition X, onto the stage 12. Based on slice data, the liquid composition X on the stage 12 is irradiated with an activation energy beam 15, resulting in a cured layer with the desired pattern, thus forming a cured layer. Next, the stage 12 is moved in the direction of the blank arrow, supplying an uncured composition X of thickness d onto the surface of the cured layer. Then, the activation energy beam 15 is emitted based on the slice data, resulting in a cured material integrated with the previously formed cured layer. By repeating this layer-by-layer curing step, a laminate 17, which serves as the desired three-dimensional built object, can be obtained.

[0171] When a cured layer with a specific geometric pattern is formed by irradiating the liquid surface of composition X with an activation energy beam, light energy rays focused into points or lines are used, allowing the resin to be cured in points or lines. Alternatively, the resin can be cured by area irradiation with an activation energy beam through an area lithography mask formed by an array of multiple micro-shutters, such as liquid crystal shutters or digital micromirror shutters.

[0172] Similar to the free surface method, objects can also be constructed using the constrained surface method. Figure 2 An example structure of an additive manufacturing apparatus 200 employing the constrained surface method is shown. Figure 2 The additive manufacturing equipment 200 employing the confined surface method shown has the following structure: wherein the equipment is configured with Figure 2 The additive manufacturing apparatus 200 shown has a stage 23 for lifting the buildup 9 upwards relative to the liquid surface, and a light irradiation unit is arranged below the tank 25. The additive manufacturing apparatus 200 includes a tank 25 containing a raw material liquid 21 composed of a liquid composition X. The buildup stage 23 is disposed inside the tank 25 and can move vertically up and down via a lifting device 24 and a controller 31. An activation energy beam 30 for curing the raw material liquid 21 composed of composition X is emitted from a light source 28 by the controller 31 and magnified by a lens unit 29. Subsequently, the irradiation area is controlled by a liquid crystal shutter 26 controlled by the controller 31 according to the buildup data. The activation energy beam 30 passing through the liquid crystal shutter 26 passes through a peelable permeable membrane 27, causing the raw material liquid 21 composed of composition X to cure.

[0173] The thickness d of the layer (layer of composition) of the raw material liquid 21 composed of composition X, cured by the activation energy beam 30, is a value determined based on the settings during the generation of construction data, and affects the accuracy of the desired article (the reproducibility of the three-dimensional shape data of the constructed article). The thickness d is achieved by the controller 31 controlling the vertical movement of the construction stage 23 via the lifting device 24. Here, on the surface of the laminate 9, in a direction perpendicular to the movement direction of the construction stage 23, irregularities are formed at specific intervals according to the thickness d.

[0174] First, the controller 31 controls the lifting device 24 based on the following settings: the construction surface of the construction stage 23 is positioned at a specific distance from the release permeable membrane 27, and a layer of feed liquid composed of composition X is supplied between the construction surface of the construction stage 23 and the release permeable membrane 27. Next, an activation energy beam 30 is emitted from below the tank 25 containing the feed liquid 21 composed of composition X. By irradiating with the activation energy beam 30, the feed liquid 21 composed of composition X between the construction surface of the construction stage 23 and the release permeable membrane 27 becomes solidified, thereby forming a solidified layer.

[0175] After the activation energy beam 30 is emitted in a specified amount and the raw material liquid 21 composed of composition X is cured, the construction stage 23 moves upward to separate the cured layer from the peelable permeable membrane 27.

[0176] Next, the height of the build stage 23 is adjusted so that the cured layer formed below the build stage 23 is at a predetermined distance from the release permeable membrane 27. Then, as before, a layer of feed liquid 21 composed of composition X is supplied between the cured layer and the release permeable membrane 27. According to the build data, a new cured layer is formed between the previous cured layer and the release permeable membrane 27 by irradiation with an activation energy beam 30. This step is repeated multiple times to obtain a laminate 9 in which multiple cured layers are integrally stacked.

[0177] Here, the light source can be, for example, an LED light, a laser light source, or a projector. When using a laser light source, the amount of light used per unit area and the illumination level are controlled by the scanning rate, and there is no need to set up an LCD shutter 26. In addition, a digital micromirror shutter can be used in addition to or instead of the LCD shutter 26.

[0178] The laminates 17 and 9 thus obtained are discharged from tanks 11 and 25, respectively, to remove unreacted composition X remaining on the surface, and then post-processed as needed to obtain the target article.

[0179] Examples of post-processing include washing, post-curing, machining, grinding, and assembly. Washing agents can be alcohol-based organic solvents, such as alcohols like isopropanol and ethanol. Other examples of washers that can be used include ketone-based organic solvents such as acetone, ethyl acetate, and methyl ethyl ketone, as well as aliphatic organic solvents such as terpenes.

[0180] After washing, post-curing can be performed as needed through light and heat irradiation or both. Post-curing can cure any unreacted composition X that may remain on or inside the structure, reduce the tackiness of the 3D structure's surface, and improve the initial strength of the 3D structure.

[0181] Examples of activation energy beams include ultraviolet (UV) light, electron beams, X-rays, radiation, and high frequencies. Among these, UV light with wavelengths from 300 nm to 450 nm is highly versatile, and examples of its light sources include UV lasers (e.g., diode-pumped solid-state lasers, Ar lasers, He-Cd lasers), high-pressure mercury lamps, ultra-high-pressure mercury lamps, mercury lamps, xenon lamps, halogen lamps, metal halide lamps, UV LEDs (light-emitting diodes), and fluorescent lamps. UV lasers, in particular, possess excellent focusing properties, which can increase energy levels and shorten build-up time, and achieve high build-up accuracy.

[0182] The method for evaluating the curability of composition X will now be described in detail.

[0183] A silicone rubber sheet with an opening is tightly attached to a glass substrate, and composition X is injected into the opening while preventing air bubbles from entering. A 405 nm UV light source is fixed vertically at a predetermined distance from the surface of the substrate, such that the center of the light source is aligned with the center of the irradiated surface. After UV irradiation, a stepped-cured sample with varying curing thicknesses under different irradiation energies is prepared by masking the substrate with a UV shielding film. The irradiation energy can be calculated as the product of the irradiation intensity and the irradiation time.

[0184] After irradiation, the uncured portion of composition X was wiped with ethanol-saturated gauze, and the thickness of the cured composition X was measured with a thickness gauge to an accuracy of 1 μm. The film thickness was determined as the average of the values ​​measured on the two samples.

[0185] The thickness of composition X is proportional to the logarithm of the irradiation energy. Therefore, data is plotted on the horizontal axis representing the irradiation energy converted to a logarithmic axis and the vertical axis representing the thickness of composition X to calculate the logarithmic approximation. From the obtained logarithmic approximation, the irradiation energy required to form a thickness of 50 μm is calculated, and the irradiation intensity is calculated to be 3 mW / cm². 2 The required irradiation time. Composition X with a shorter required irradiation time is evaluated as composition X with excellent curing properties.

[0186] Measuring the amount of VOCs

[0187] In this disclosure, the VOCs generated from the stereolithographic constructs are organic compounds that are detected in the range from n-hexane to n-hexadecane by gas chromatography with a nonpolar column, conforming to JIS C 9913:2008. The method for measuring the amount of such VOCs generated is as follows.

[0188] A construct with dimensions of 3 mm × 4 mm × 10 mm was prepared using the above construction method, and then washed and subjected to secondary curing to prepare a sample for VOC measurement. The mass of the sample was measured using an electronic balance or an ultra-micro balance.

[0189] The amount of VOC generated from the sample is evaluated according to JIS C 9913:2008.

[0190] The specific description is as follows.

[0191] The microchamber is used as a VOC sampling device, with a sampling tube connected to the microchamber. The sample is then placed in a chamber inside the microchamber, which is maintained at 85°C to 95°C. One sample is placed here. Next, N2 gas is introduced into the chamber of the microchamber at a flow rate of 100 mL / min for 11 minutes to sample the VOCs generated from the sample into the sampling tube.

[0192] Next, the sampling tube is placed in a thermal desorption apparatus and heated to 280°C to desorb the VOCs in the sampling tube. The desorbed VOCs are then introduced into a GC-MS connected to the thermal desorption apparatus to measure the VOC composition.

[0193] Toluene is used as a calibrating agent, and chloroform is used as a solvent to prepare toluene solutions.

[0194] Next, toluene is sampled by injecting a toluene solution into a sampling tube under an N2 gas flow using a micro-syringe and flow controller used for the calibration curve preparation tool. Note that the solvent is not limited to chloroform, as long as it does not affect the toluene being measured.

[0195] Toluene D8 is used as an internal standard. Note that the internal standard is not limited to toluene D8, as long as it does not affect the VOC to be measured. The internal standard can be added using the automatic addition function of the thermal desorption device, or it can be added to the chamber of the microchamber simultaneously with the sample to be measured. For obtaining an internal standard with excellent accuracy, addition via the automatic addition function of the thermal desorption device can be used.

[0196] The calibration curve was determined as follows. The peak areas of toluene and toluene D8 were obtained from the total ion chromatography (TIC) results of toluene added in a specific amount. Next, the peak area of ​​toluene was divided by the peak area of ​​toluene D8 to determine the toluene / toluene D8 area ratio. Then, a regression line was plotted from the relationship between the amount of toluene added and the area ratio, and this was assumed to be the calibration curve.

[0197] The amount of VOC generated from the sample is determined as follows. The peak area of ​​the relevant component is obtained from the TIC results of a specific sample. Next, the peak area of ​​that component is divided by the peak area of ​​toluene D8 to determine the area ratio.

[0198] When the relevant component is toluene, the area ratio value is substituted into the aforementioned calibration curve to obtain the amount of toluene (ng). The amount of toluene is divided by the unit mass of the sample to determine the VOC content of toluene (ng / g).

[0199] When the relevant component is not toluene, perform the following steps.

[0200] The peak area of ​​the relevant component is divided by the peak area of ​​toluene D8 to determine the value of the relevant component / toluene D8 area ratio. Then, it is assumed that the calibration curve determined from the relationship between the amount of toluene and the toluene / toluene D8 area ratio is the same as the calibration curve determined from the relationship between the amount of the relevant component and the value of the relevant component / toluene D8 area ratio.

[0201] The values ​​of the relevant component / toluene D8 area ratio are then substituted into the aforementioned calibration curve to obtain the toluene equivalent (ng). This toluene equivalent is divided by the unit mass of the sample to determine the VOC content of the relevant component (ng / g).

[0202] VOC components generated by photopolymerization initiators are defined as decomposition products derived from the initiator that were not generated before the photopolymerization initiator was irradiated with an activation energy beam.

[0203] application

[0204] The composition X disclosed herein can be used in three-dimensional additive manufacturing methods, particularly stereolithography.

[0205] Furthermore, stereolithographic constructs obtained through 3D printing have wide applications in the field of optical 3D construction. There are no particular limitations on application areas; representative examples include industrial products such as electrical and electronic equipment, office automation (OA) appliances, cameras, and computers. Other examples include prototype models, design models, working models, base models for mold fabrication, direct molds for prototype molds, repair parts, housings, and parts for industrial products. In particular, stereolithographic constructs using composition X exhibit very low strain and generate minimal VOCs from the photopolymerization initiator; therefore, stereolithographic constructs can be used to manufacture housings and parts for industrial products.

[0206] The device equipped with article Z made of composition X may, in addition to article Z, be equipped with at least one component selected from thermoplastic resin components, thermosetting resin components, and metal components. Article Z, components made of thermoplastic resin, and components made of thermosetting resin can be used in a variety of applications, including outer packaging, wiring boards, connectors, pipes, caps, bases, cams, guides, gears, bottles, and boxes. When multiple thermoplastic resin components are present, from a flame-retardant point of view, the thermoplastic resin used for at least some of these components may be PC-ABS resin. Article Z can be used for a variety of purposes, such as adhesives and sealing materials. Metal components can be used for a wide variety of purposes, such as housings, rollers, and heat sinks. In addition to article Z, the device may also be equipped with at least one of electrical components, optical components, and mechanical components. Electrical components include, for example, circuit boards, integrated circuit components, sensors, displays, or motors. Optical components include, for example, light sources, lenses, or mirrors. Mechanical components include, for example, rollers, gears, or reinforcing components. Various types of devices can be constructed by combining at least one of the aforementioned thermoplastic resin components, thermosetting resin components, metal components, electrical components, optical components, and mechanical components. Devices can be printing devices or office devices such as inkjet printers, laser printers, scanners, copiers, or multifunction printers. Devices can be video devices such as cameras, monitors, or projectors. Devices can be optical devices such as interchangeable lenses and binoculars. Devices can be medical devices such as X-ray machines, CT scanners, MRI machines, or endoscopes. Devices can be industrial devices such as exposure equipment, film-forming equipment, or robots. Devices can be any of various mobile and transportation devices such as automobiles, airplanes, and ships. Article Z can be used as part of various components and assemblies of these devices. Article Z can replace PC-ABS resin already used in components and assemblies requiring flame retardancy and mechanical strength. In this case, non-black particles containing flame retardants can be used as component D of composition X.

[0207] Example

[0208] Samples No. 1 to No. 10 of Composition X are shown in Table 1. Samples No. 11 to No. 21 of Composition X are shown in Table 2. Tables 1 and 2 show the mass concentrations (in mass %) of components A to D in Composition X. Additionally, "Component D / Component C" indicates the factor by which the concentration of component D in Composition X is greater than the concentration of component C in Composition X. Here, it is assumed that samples No. 1 to No. 21 of Composition X do not contain components other than A to D.

[0209] Table 1

[0210]

[0211] Table 2

[0212]

[0213] The components in these embodiments are as follows:

[0214] Component A: Photopolymerizable compound

[0215] • A-1: ​​Cyclic polymerizable composition

[0216] 2-(allyloxy)methyl acrylate (trade name: FX-AO-MA, manufactured by NIPPON SHOKUBAI CO.,LTD.)

[0217] A-2: A multifunctional free radical polymeric compound

[0218] Multifunctional carbamate acrylate (trade name: UA-160TM manufactured by Shin Nakamura Chemical Co., Ltd.)

[0219] A-3: Multifunctional free radical polymeric compound

[0220] Tris(2-acryloyloxyethyl) isocyanurate (trade name: A9300S manufactured by Shin Nakamura Chemical Co., Ltd.)

[0221] Component B: Photopolymerization initiator

[0222] • Bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (trade name: Omnirad 819 manufactured by IGM Resins)

[0223] Component C: Black particles

[0224] C-1: Carbon black, pH: 3.5, particle size: 24nm

[0225] (Product name: MA100 manufactured by Mitsubishi Chemical Corporation)

[0226] C-2: Carbon black, pH: 8, particle size: 24nm

[0227] (Product name: #44 manufactured by Mitsubishi Chemical Corporation)

[0228] Component D: Non-black particles

[0229] • D-1: Ammonium polyphosphate, particle size: 8μm

[0230] (Product name: Exolit AP 423 manufactured by Clariant AG)

[0231] D-2: Sodium polyborate, particle size: 1 to 10 μm

[0232] (Product name: Best Boron (particle size: 50 to 200 μm) manufactured by Soufa Inc., pulverized)

[0233] • D-3: Calcium carbonate, particle size: 10 to 20 μm

[0234] (Product name: Calcium carbonate manufactured by Kishida Chemical Co., Ltd.)

[0235] • D-4: Silica, particle size: 9.5μm

[0236] (Product name: HS-207 manufactured by NIPPON STEEL Chemical & Material Co., Ltd.)

[0237] Using an electronic balance (model "GF-2002" manufactured by A&D Company, Limited), the three components A and B were weighed according to the blending amounts shown in Tables 1 and 2. The resulting mixture was stirred under heating for more than 3 hours using a mixing rotor (model "VMRC-5" manufactured by AS ONE Corporation). Using an electronic precision balance (trade name "AX-200" manufactured by SHIMADZUCORPORATION), the resulting mixture, component C, and component D were weighed into a planetary centrifugal mixing vessel according to the blending amounts shown in Tables 1 and 2. The mixture was stirred at 2000 rpm for 5 minutes using a planetary centrifugal mixer (model "ARV-310P" manufactured by THINKYCORPORATION) to obtain resin composition X.

[0238] Curing time measurement

[0239] For each of the prepared compositions X, the position of the light source was adjusted using an ultraviolet irradiator (EX250 manufactured by HOYA CANDEO OPTRONIC SCORPORATION), and the irradiation time was varied so that the irradiation energy (= irradiation intensity × irradiation time) was 7.05 mW / cm². 2 11.75mW / cm 2 18.8mW / cm 2 23.5mW / cm 2 28.2mW / cm 2 35.3mW / cm 2 and 47mW / cm 2After irradiation, the uncured portion of composition X was wiped with ethanol-saturated gauze, and the thickness of the cured film was measured using a thickness gauge (543-390B manufactured by Mitutoyo Corporation). Measurements were taken from two samples of each composition X, and the average value was calculated. This measurement data was plotted on the horizontal axis representing the irradiation energy converted to a logarithmic axis and the vertical axis representing the thickness of composition X to calculate a logarithmic approximation. From the obtained logarithmic approximation, the irradiation energy required to form a thickness of 50 μm was calculated, and the irradiation intensity was calculated to be 3 mW / cm². 2 The necessary irradiation time.

[0240] Solidification evaluation

[0241] Based on the relationship between irradiation energy (=irradiation intensity × irradiation time) and cured thickness, the time required to form a thickness of 50μm was determined, and this time was used as an indicator of curability. The evaluation criteria for better curability with shorter time are explained below.

[0242] A: Less than 3 seconds.

[0243] B: More than 3 seconds but less than 5 seconds.

[0244] C: More than 5 seconds but less than 10 seconds.

[0245] D: More than 10 seconds but less than 16 seconds.

[0246] E: More than 16 seconds.

[0247] Preparation method of solidified material for VOC measurement

[0248] The above composition X was used to fabricate stereolithographic constructs using a 3D printer (trade name: "MQ4K" manufactured by SUMAOPAI). The irradiation time for each 50 μm thick layer was set to 3 seconds for Grade A curing, 10 seconds for Grade C curing, 16 seconds for Grade D curing, and 35 seconds for Grade E curing. Layers were stacked in the width direction of the test piece to prepare cured products. The cured products were washed with an organic solvent and then subjected to a secondary curing treatment for 1 hour using a secondary curing device (trade name: "Formcure" manufactured by Formlabs).

[0249] In addition, the obtained cured material was placed in a 100°C heating oven and heated for 1 hour to obtain a cured material for VOC measurement.

[0250] Measuring the amount of VOCs

[0251] A construct with dimensions of 3 mm × 4 mm × 10 mm was prepared, and then washed and subjected to secondary curing to prepare a sample for VOC measurement. The mass of the sample was measured using a precision balance.

[0252] A microchamber (trade name: “M-CTE250”, manufactured by Markes International Ltd.) was used as the VOC sampling device, and a “Tenax TA” (trade name), also manufactured by Markes International Ltd., was used as the sampling tube. The sample was then placed inside the chamber of the microchamber, which was maintained at 90°C. The VOC measurement sample was a virgin construct and had not been cut or damaged. N2 gas was introduced into the chamber at a flow rate of 100 mL / min for 11 minutes to sample the VOCs generated from the sample into the sampling tube. Additionally, the calibration substance was prepared by dissolving toluene in chloroform. Next, the toluene-containing solution was injected into the sampling tube under an N2 gas flow using a microsyringe and a flow controller for calibration curve preparation tools to sample the toluene.

[0253] Next, the sampling tube was placed in a thermal desorption apparatus (trade name: "Centri" manufactured by Markes International Ltd.) and heated to 280°C to desorb the VOCs from the sampling tube. The desorbed VOCs were condensed in a cold trap at -10°C and then heated to 300°C for introduction into GC / MS (trade name: "JMS-Q1600GC" manufactured by JEOL Ltd.). Toluene D8 was used as an internal standard, and 0.15 ng was added using the automatic titration function of the thermal desorption apparatus. The GC oven was heated from 40°C to 300°C at a heating rate of 10°C / min. The carrier gas was pure He (purity ≥ 99.9995%), and the column used (trade name: "HP-5" manufactured by Agilent Technologies Inc.) was 30 m long with an inner diameter of 320 μm and a film thickness of 0.25 μm. The GC-IF temperature was set to 270°C. An EI was used as the MS ion source, with the ionization current set to 30 μA, the ionization energy set to 70 eV, and the ionization temperature set to 230 °C. Next, VOC components were measured in the range of m / z = 50 to 600.

[0254] The calibration curve for detecting VOC levels was plotted using toluene and toluene D8 using the method described above, to obtain the VOC level (ng / g).

[0255] The VOC components derived from the photopolymerization initiator, namely bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, added to the photopolymerizable composition X, are 1,3,5-trimethylbenzene, 2,4,6-trimethylbenzaldehyde, 2,4,6-trimethylbenzoic acid, and ethyl 2,4,6-trimethylbenzoate, which are substances having a trimethyl structure.

[0256] Evaluation of VOC generation from photopolymerization initiators

[0257] The amount of VOCs originating from the decomposition components of the photopolymerization initiator generated from the surface of the stereolithographic construct is determined. From a VOC perspective, the evaluation criteria for lower VOC levels are explained below.

[0258] A: Less than 200 ng / g.

[0259] B: 200 ng / g or more but less than 500 ng / g.

[0260] C: Above 500ng / g and less than 1000ng / g.

[0261] D: 1000 ng / g or more but less than 2000 ng / g.

[0262] E: 2000ng / g or more.

[0263] Tables 1 and 2 show that Nos. 1 to 19, which contain component C, produce less VOC compared to Nos. 20 and 21, which do not contain component C. Furthermore, among Nos. 3 to 20, which contain component D, Nos. 3 to 10 and 13, which combine component C-1 (composed of carbon black with a pH below 4.0) with components D-1, D-2, or D-3 (composed of non-black particles containing salt), produce less VOC compared to Nos. 12, 14, and 16 to 19 (using component C-2) and Nos. 11, 15, and 16 (using component D-4).

[0264] When non-black particles are included in composition X, the particles cause scattering of light such as UV light, and a wider area is exposed, increasing the amount of VOC components derived from the photopolymerization initiator. Combining non-black particles containing salt with black particles having a pH below 4.0 creates a deviation in the distribution of black particles. Therefore, the degree of degradation in curability is less when black particles are added compared to the case without non-black particles containing salt. Furthermore, degradation in curability was observed with increasing concentration of component C; however, in compositions No. 1 to No. 12 with low amounts of component C, sufficiently high curability was achieved while also sufficiently reducing VOC generation.

[0265] As described above, according to the composition X of this disclosure, even when containing low-reactive polymerizable compounds and non-black particles, it is possible to obtain cured product Y without excessively deteriorating the curability of composition X, while reducing the amount of VOC generated.

[0266] This disclosure is not limited to the above-described embodiments, and many modifications and variations can be made to the embodiments within the technical concept of this disclosure. For example, at least two of the above embodiments and modifications can be used in combination. Furthermore, the effects described in the embodiments are only the most desired effects of the embodiments of this disclosure, and the effects of the embodiments of this disclosure are not limited to the effects described in the embodiments.

[0267] The disclosure in this specification includes not only what is explicitly disclosed herein, but also all matters that may be understood from this specification and the accompanying drawings. The disclosure in this specification includes a complementary set of the various concepts described herein. That is, for example, although the instruction "A is B" is omitted, the phrase "A is B" in the specification is considered to also disclose "A is not B" in the specification. This is because the presence of the phrase "A is B" presupposes that the case of "A is not B" is considered.

[0268] For specific numerical ranges illustrated as examples in this specification, the designation "e to f" (where e and f each represent a number) means "above e and / or below f". Furthermore, for any specific numerical range illustrated as examples, if both the range of i to j and the range of m to n (where i, j, m, and n each represent a number) are described, the combination of the lower and upper limits is not limited to the combination of i and j or the combination of m and n. For example, multiple combinations of lower and upper limits can be combined. That is, when both the range of i to j and the range of m to n are described, the range of i to n and / or the range of m to j can also be studied, provided there is no contradiction. Additionally, "above e" means e or greater than e (exceeding e), and values ​​greater than e can be used instead of e. Furthermore, "below f" means f or less than f (below f), and values ​​less than f can be used instead of f.

[0269] The technologies disclosed in this specification can contribute to the realization of sustainable societies, such as decarbonized circular societies.

[0270] This disclosure provides techniques that allow photocurable compositions to advantageously achieve both curability and VOC reduction.

[0271] While this disclosure has been described with reference to exemplary embodiments, it should be understood that this disclosure is not limited to the disclosed exemplary embodiments. The scope of the appended claims should be given the broadest interpretation to cover all such modifications and equivalent structures and functions.

Claims

1. A photocurable composition comprising: The first component is composed of photopolymerizable compounds; The second component is composed of a photopolymerization initiator; The third component consists of black particles; and The fourth component consists of non-black particles. in: The fourth component contains non-black particles with a particle size of 1 μm or larger and 20 μm or smaller. The mass concentration of the fourth component in the composition is greater than 200 times the mass concentration of the third component and less than 3000 times the mass concentration of the third component.

2. A photocurable composition comprising: The first component is composed of photopolymerizable compounds; The second component is composed of a photopolymerization initiator; The third component consists of black particles; and The fourth component consists of non-black particles. in: The first component contains a cyclized polymerizable compound. The third component contains black particles with a pH below 4.0 or above 9.

0. The fourth component contains non-black particles containing salt.

3. A photocurable composition comprising: The first component is composed of photopolymerizable compounds; The second component, consisting of a photopolymerization initiator; and The third component, consisting of black particles, in: The first component comprises a cyclized polymerizable compound, and The mass concentration of the third component in the composition is 0.01% by mass or more and less than 0.10% by mass.

4. The composition according to claim 3, further comprising a fourth component consisting of non-black particles.

5. The composition according to claim 1, 2 or 4, wherein: The third component contains black particles with a pH below 4.0, and The fourth component contains non-black particles containing polyoxyacid salts.

6. The composition according to claim 1, 2 or 4, wherein the fourth component comprises non-black particles containing a flame retardant.

7. The composition according to any one of claims 1 to 3, wherein the mass concentration of the second component in the composition is more than 1% by mass and less than 5% by mass.

8. The composition according to claim 1 or 2, wherein the mass concentration of the third component in the composition is 0.01% by mass or more and less than 0.10% by mass.

9. The composition according to claim 1, 2 or 4, wherein the mass concentration of the fourth component in the composition is 10% by mass or more and 30% by mass or less.

10. The composition according to claim 1, 2 or 4, wherein: The third component comprises black particles with a first particle size. The fourth component comprises non-black particles with a second particle size, and The second particle size is more than 10 times the first particle size and less than 2000 times the first particle size.

11. The composition of claim 1, wherein the first component comprises a cyclized polymerizable compound.

12. The composition according to any one of claims 1 to 3, wherein the first component comprises a monofunctional 2-(allyloxymethyl)acrylic acid or an ester thereof represented by general formula (1):

13. The composition according to claim 12, wherein in the general formula (1), R represents a hydrocarbon group having 1 or more and 4 or fewer hydrogen atoms.

14. The composition according to any one of claims 1 to 3, wherein the second component comprises a compound having trimethylbenzene in its molecule.

15. The composition according to any one of claims 1 to 3, wherein the second component comprises an acylphosphine oxide compound.

16. The composition according to any one of claims 1 to 3, wherein the third component comprises carbon black.

17. The composition according to any one of claims 1 to 3, wherein the third component comprises black particles with a particle size of 10 nm or more and 1 μm or less.

18. The composition according to claim 1, 2 or 4, wherein the fourth component comprises non-black particles with a particle size of 1 μm or more and 20 μm or less.

19. A method for manufacturing an article of articles, the method comprising: Prepare the composition according to any one of claims 1 to 18; and The composition is cured by irradiating it with light.

20. A method for manufacturing an article of articles, the method comprising: The step of forming a layer of the composition according to any one of claims 1 to 18; and The step of curing the layer of the composition by irradiation with light. These steps are repeated to build the stack.

21. The method of claim 20, wherein During the layer-forming step, a layer of the composition is formed between a build platform disposed in a liquid of the composition and the liquid surface of the composition, and during the curing step, the composition is irradiated with light through the liquid surface.

22. A method for manufacturing an article of articles, the method comprising: The step of forming a layer of a photocurable composition; and The step of curing the layer of the composition by irradiation with light. These steps are repeated to construct the stack, and The composition comprises: The first component is composed of photopolymerizable compounds; The second component is composed of a photopolymerization initiator; The third component consists of black particles; and The fourth component consists of non-black particles. in: The third component contains black particles with a pH below 4.0 or above 9.0, and The fourth component contains non-black particles containing salt.

23. A method for manufacturing an article, comprising: The step of forming a layer of a photocurable composition; and The step of curing the layer of the composition by irradiation with light. These steps are repeated to construct the stack, and The composition comprises: The first component is composed of photopolymerizable compounds; The second component is composed of a photopolymerization initiator; The third component consists of black particles; and The fourth component consists of non-black particles. in: The mass concentration of the third component in the composition is 0.01% by mass or more and less than 0.10% by mass, and The fourth component comprises non-black particles containing flame retardants.

24. The method according to claim 22 or 23, wherein: The third component contains black particles with a pH below 4.0, and The fourth component contains non-black particles containing polyoxyacid salts.

25. The method of claim 22 or 23, wherein the fourth component comprises non-black particles containing ammonium polyphosphate.

26. The method of claim 22 or 23, wherein the first component comprises a cyclized polymerizable compound.

27. The method of claim 22 or 23, wherein the second component comprises a compound having trimethylbenzene in its molecule.

28. The method according to claim 22 or 23, wherein the mass concentration of the third component in the composition is 0.01% by mass or more and less than 0.10% by mass.

29. The method according to claim 22 or 23, wherein the mass concentration of the fourth component in the composition is 10% by mass or more and 30% by mass or less.

30. The method according to claim 22 or 23, wherein During the layer-forming step, a layer of the composition is formed between a build platform disposed in a liquid of the composition and the liquid surface of the composition, and during the curing step, the composition is irradiated with light through the liquid surface.

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