Light curable resin composition for stereo-lithography and method for manufacturing three-dimensional objects

Abstract

To provide light curable resin compositions for three-dimensional modeling that enable modeling of objects with excellent heat resistance and sliding properties.SOLUTION: The mixture contains a radical polymerizable compound (A), polysilsesquioxane particles (B), and a curing agent (C), wherein the polysilsesquioxane particles (B) have at least polysilsesquioxane on the surface and the radical polymerizable compound (A) is a mixture of a multifunctional radical polymerizable compound (A-1) and a monofunctional radical polymerizable compound (A-2), and the composition shall contain at least 60% by mass of a multifunctional radical polymerizable compound (A-1), the ethylenically unsaturated group equivalent of the multifunctional radical polymerizable compound (A-1) is 250 g / eq. or more and less than 700 g / eq. The light curable resin composition shall contain 5 parts by mass to 30 parts by mass of polysilsesquioxane particles (B) per 100 parts by mass of the radical polymerization compound (A).SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a photocurable resin composition for three-dimensional modeling, and a method for producing a three-dimensional object using the same. [Background technology]

[0002] As an example of the use of liquid curable resin compositions, optical three-dimensional modeling (stereolithography) has been actively researched, in which a photocurable resin composition is cured layer by layer with light such as ultraviolet light and then stacked in sequence to produce a desired three-dimensional object. Since stereolithography can produce objects with higher accuracy than other methods, its applications are expanding beyond the production of prototypes for shape confirmation (rapid prototyping) to the production of working models and molds for functionality verification (rapid tooling). It is also expanding to the production of actual products (rapid manufacturing). In light of this, there are increasing demands for curable resin compositions, such as a curable resin composition capable of forming articles having sliding properties, which exhibit a low coefficient of friction and high abrasion resistance, and mechanical properties, such as high rigidity and heat resistance, comparable to those of general-purpose engineering plastics. Patent Document 1 discloses a technique for achieving high scratch resistance by containing a non-polymerizable resin and a radically polymerizable polyfunctional acrylate as an energy ray-curable composition. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] JP 2017-165964 A Summary of the Invention [Problem to be solved by the invention]

[0004] Depending on the application, objects to be used as actual products are desired to have not only a low coefficient of friction and high wear resistance (hereinafter, these two properties will be referred to as "slidability." Furthermore, when we say "high slidability" or "excellent slidability," it means that the object has both a low coefficient of friction and high wear resistance), but also high heat resistance. However, it is difficult to satisfy all of these physical properties at the same time. Although Patent Document 1 describes abrasion resistance such that the coating surface is not scratched even when palpated with a cotton swab, it does not take into consideration the coefficient of friction or heat resistance, and makes no disclosure thereabout. In order to solve the above problems, an object of the present invention is to provide a photocurable resin composition for three-dimensional modeling, which is capable of forming articles having excellent heat resistance and sliding properties. [Means for solving the problem]

[0005] The photocurable resin composition for three-dimensional object formation according to the present invention contains a radical polymerizable compound (A), polysilsesquioxane particles (B), and a curing agent (C), The polysilsesquioxane particles (B) have polysilsesquioxane at least on their surfaces, The radical polymerizable compound (A) contains at least a polyfunctional radical polymerizable compound (A-1) in an amount of more than 60 mass %, the polyfunctional radically polymerizable compound (A-1) has an ethylenically unsaturated group equivalent of 250 g / eq or more and less than 700 g / eq; The composition is characterized in that it contains 5 parts by mass or more and 30 parts by mass or less of the polysilsesquioxane particles (B) based on 100 parts by mass of the radical polymerizable compound (A). The present invention also provides a cured product obtained by curing the above-mentioned photocurable resin composition of the present invention. Furthermore, the present invention provides a method for manufacturing a three-dimensional object using a stereolithography method, comprising the steps of: disposing a photocurable resin composition in a layer; and curing the layered photocurable resin composition by irradiating the layered photocurable resin composition with light energy based on slice data of a model, The present invention provides a method for producing a three-dimensional object, wherein the photocurable resin composition is the photocurable resin composition of the present invention. Effect of the Invention

[0006] By using the photocurable resin composition for three-dimensional modeling according to the present invention, a model having excellent heat resistance and sliding properties can be provided. [Brief description of the drawings]

[0007] [Figure 1] FIG. 1 is a diagram illustrating an example of the configuration of a photo-fabrication apparatus. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0008] Hereinafter, an embodiment of the present invention will be described. Note that the embodiment described below is merely one embodiment of the present invention, and the present invention is not limited to these embodiments. In the present invention, a deflection temperature under load of 85°C or higher measured according to JIS K 7191 is considered to be good heat resistance, and a deflection temperature of 95°C or higher is considered to be excellent heat resistance. If the deflection temperature under load of the test piece is less than 85°C, the molded object may be deformed by exposure to high temperatures. In particular, when the molded object is used in a sliding portion, the temperature rises due to frictional heat and exceeds the softening point of the cured object, resulting in an increase in the coefficient of friction and a decrease in wear resistance.

[0009] The photocurable resin composition for three-dimensional modeling of the present invention (sometimes simply referred to as "curable resin composition" or "resin composition") contains a radical polymerizable compound (A), polysilsesquioxane particles (B), and a curing agent (C). The radical polymerizable compound (A) contains at least a multifunctional radical polymerizable compound (A-1), and is preferably a mixture of a multifunctional radical polymerizable compound (A-1) and a monofunctional radical polymerizable compound (A-2). Each component will be described in detail below.

[0010] <Polyfunctional radically polymerizable compound (A-1)> The polyfunctional radical polymerizable compound (A-1) contained in the photocurable resin composition of the present invention is a compound having two or more radical polymerizable functional groups in the molecule. Examples of the radical polymerizable functional group include ethylenically unsaturated groups. Examples of the ethylenically unsaturated group include (meth)acryloyl groups and vinyl groups. Examples of the polyfunctional radical polymerizable compound include (meth)acrylate-based compounds, vinyl ether group-containing (meth)acrylate-based compounds, (meth)acryloyl group-containing isocyanurate-based compounds, (meth)acrylamide-based compounds, urethane (meth)acrylate-based compounds, maleimide-based compounds, vinyl ether-based compounds, aromatic vinyl-based compounds, epoxy acrylates, and polyester acrylates. Among them, (meth)acrylate-based compounds and urethane (meth)acrylate-based compounds are preferred from the viewpoints of availability and curability.

[0011] In addition, as the polyfunctional radically polymerizable compound (A-1) of the present invention, a urethane (meth)acrylate compound having a urethane structure is preferable, since it is easy to synthesize and obtain, and the toughness and heat resistance of the resulting shaped object are high. In addition, a polyfunctional radical polymerizable compound having a polyether structure is preferred because it has a low viscosity, has good drainage during modeling, and can produce a highly accurate modeled object, whereas a polyfunctional radical polymerizable compound having a polyester structure or a polycarbonate structure is preferred because it can produce a modeled object with high toughness and heat resistance. Therefore, the polyfunctional radically polymerizable compound (A-1) is preferably a (meth)acrylate-based compound or a urethane (meth)acrylate-based compound having any one of a polyether structure, a polyester structure, and a polycarbonate structure.

[0012] The polyfunctional radical polymerizable compound (A-1) may be a single polyfunctional radical polymerizable compound listed above, or may contain two or more kinds. The polyfunctional radical polymerizable compound (A-1) in the present invention is a collective name for one or more polyfunctional radical polymerizable compounds contained in the photocurable resin composition.

[0013] Examples of the polyfunctional radical polymerizable compound having a urethane structure include those obtained by reacting a hydroxyl group-containing (meth)acrylate compound with a polyvalent isocyanate compound. Other examples include those obtained by reacting a hydroxyl group-containing (meth)acrylate compound with a polyvalent isocyanate compound with a polyol compound. Among them, in terms of realizing high toughness, those obtained by reacting a hydroxyl group-containing (meth)acrylate compound with a polyvalent isocyanate compound with a polyol compound are particularly preferred.

[0014] Examples of the hydroxyl group-containing (meth)acrylate compound include hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and 6-hydroxyhexyl (meth)acrylate, 2-hydroxyethyl acryloyl phosphate, 2-(meth)acryloyloxyethyl-2-hydroxypropyl phthalate, caprolactone-modified 2-hydroxyethyl (meth)acrylate, dipropylene glycol (meth)acrylate, fatty acid-modified glycidyl (meth)acrylate, and polyethylene glycol mono(meth)acrylate. acrylate, polypropylene glycol mono(meth)acrylate, 2-hydroxy-3-(meth)acryloyloxypropyl(meth)acrylate, glycerin di(meth)acrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate, pentaerythritol tri(meth)acrylate, caprolactone-modified pentaerythritol tri(meth)acrylate, ethylene oxide-modified pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, caprolactone-modified dipentaerythritol penta(meth)acrylate, ethylene oxide-modified dipentaerythritol penta(meth)acrylate, etc. These hydroxyl group-containing (meth)acrylate compounds may be used alone or in combination of two or more.

[0015] Examples of the polyisocyanate-based compound include aromatic polyisocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate, polyphenylmethane polyisocyanate, modified diphenylmethane diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, phenylene diisocyanate, and naphthalene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, and lysine diisocyanate. Examples of the polyisocyanate include aliphatic polyisocyanates such as isocyanate and lysine triisocyanate, alicyclic polyisocyanates such as hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, norbornene diisocyanate, and 1,3-bis(isocyanatomethyl)cyclohexane, as well as trimer compounds or polymer compounds of these polyisocyanates, allophanate-type polyisocyanates, biuret-type polyisocyanates, and water-dispersible polyisocyanates. These polyisocyanate compounds may be used alone or in combination of two or more.

[0016] Examples of the polyol-based compound include polyether-based polyols, polyester-based polyols, polycarbonate-based polyols, polyolefin-based polyols, polybutadiene-based polyols, (meth)acrylic-based polyols, polysiloxane-based polyols, etc. These polyol-based compounds may be used alone or in combination of two or more kinds. Examples of polyether polyols include alkylene structure-containing polyether polyols such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polybutylene glycol, and polyhexamethylene glycol, and random or block copolymers of these polyalkylene glycols. Examples of polyester-based polyols include condensation polymers of polyhydric alcohols and polycarboxylic acids, ring-opening polymers of cyclic esters (lactones), and reaction products of three components: polyhydric alcohols, polycarboxylic acids, and cyclic esters.

[0017] Examples of the polyhydric alcohol include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, trimethylene glycol, 1,4-tetramethylene diol, 1,3-tetramethylene diol, 2-methyl-1,3-trimethylene diol, 1,5-pentamethylene diol, neopentyl glycol, 1,6-hexamethylene diol, 3-methyl-1,5-pentamethylene diol, 2,4-diethyl-1,5-pentamethylene diol, glycerin, trimethylolpropane, trimethylolethane, cyclohexanediols (such as 1,4-cyclohexanediol), bisphenols (such as bisphenol A), and sugar alcohols (such as xylitol and sorbitol).

[0018] Examples of the polyvalent carboxylic acid include aliphatic dicarboxylic acids such as malonic acid, maleic acid, fumaric acid, succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, and dodecanedioic acid; alicyclic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid; and aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, orthophthalic acid, 2,6-naphthalenedicarboxylic acid, paraphenylenedicarboxylic acid, and trimellitic acid.

[0019] Examples of the cyclic ester include propiolactone, β-methyl-δ-valerolactone, and ε-caprolactone. Examples of polycarbonate-based polyols include reaction products of polyhydric alcohols and phosgene, and ring-opening polymers of cyclic carbonates (such as alkylene carbonates). Examples of the polyhydric alcohol include the polyhydric alcohols exemplified in the description of the polyester polyol, etc. Examples of the alkylene carbonate include ethylene carbonate, trimethylene carbonate, tetramethylene carbonate, hexamethylene carbonate, etc. The polycarbonate polyol may be any compound having a carbonate bond in the molecule and a hydroxyl group at the end, and may have an ester bond in addition to the carbonate bond.

[0020] Examples of the polyfunctional radically polymerizable compound (A-1) having a polyether structure, a polyester structure, or a polycarbonate structure include those obtained by reacting the above-mentioned polyether polyol, polyester polyol, or polycarbonate polyol with a (meth)acrylic acid chloride or a (meth)acrylic acid bromide.

[0021] In the present invention, the ethylenically unsaturated group equivalent of the polyfunctional radical polymerizable compound (A-1) contained in the photocurable resin composition is 250 g / eq or more and less than 700 g / eq. When the polyfunctional radical polymerizable compound (A-1) contained in the photocurable resin composition is a single compound, a polyfunctional radical polymerizable compound having an ethylenically unsaturated group equivalent of 250 g / eq or more and less than 700 g / eq is used. The ethylenically unsaturated group equivalent here is the value obtained by dividing the weight average molecular weight (Mw) of the polyfunctional radical polymerizable compound by the number of ethylenically unsaturated groups in one molecule. The smaller the ethylenically unsaturated group equivalent, the higher the crosslink density in the cured product after photocuring, and the more a molded object (article) with good heat resistance can be obtained. When the polyfunctional radical polymerizable compound (A-1) contains a plurality of polyfunctional radical polymerizable compounds, the ethylenically unsaturated group equivalent of each polyfunctional radical polymerizable compound is weighted averaged by the mass ratio contained in the polyfunctional radical polymerizable compound (A-1) to be the ethylenically unsaturated group equivalent of the polyfunctional radical polymerizable compound (A-1).Then, the polyfunctional radical polymerizable compounds are mixed and used so that the value is 250g / eq or more and less than 700g / eq.When the polyfunctional radical polymerizable compound (A-1) contains a plurality of polyfunctional radical polymerizable compounds, it is preferable that the mixture is a polyfunctional radical polymerizable compound having an ethylenically unsaturated group equivalent of 250g / eq or more and less than 700g / eq, and a polyfunctional radical polymerizable compound having an ethylenically unsaturated group equivalent of 700g / eq or more.

[0022] The smaller the ethylenically unsaturated group equivalent of the polyfunctional radical polymerizable compound (A-1), the more excellent the heat resistance of the molded object is, but the higher the crosslink density in the resin composition after photocuring. If the crosslink density is too high, the toughness of the molded object is significantly reduced, and the molded object may be damaged when the support material of the molded object is removed. In addition, the molded object may be damaged when it is fitted into another member or when the molded object is subjected to secondary processing. The support material is a part that is prepared to maintain the desired shape during the molding process, and is generally removed after the molding is completed.

[0023] On the other hand, the larger the ethylenically unsaturated group equivalent of the polyfunctional radical polymerizable compound (A-1), the smaller the crosslink density of the resin composition after photocuring, but the lower the heat resistance. If the heat resistance is low, when a molded object is used as a sliding member, the molded object will be deformed or the sliding properties will be deteriorated due to softening caused by frictional heat.

[0024] Therefore, from the viewpoint of obtaining a good balance of heat resistance, toughness, and moldability, the ethylenically unsaturated group equivalent of the polyfunctional radically polymerizable compound (A-1) is 250 g / eq or more and less than 700 g / eq, and from the viewpoint of excellent support removability of the obtained molded object, it is more preferable that the ethylenically unsaturated group equivalent is 400 g / eq or more and less than 700 g / eq.

[0025] The weight average molecular weight (Mw) of the polyfunctional radical polymerizable compound (A-1) of the present invention is a weight average molecular weight calculated based on the molecular weight of standard polystyrene. The weight average molecular weight was measured using a high performance liquid chromatography (Tosoh Corporation, high-speed GPC device "HLC-8220GPC") with a column: Shodex GPCLF-804 (exclusion limit molecular weight: 2×10 6 , Separation range: 300 to 2×10 6 )The two can be connected in series and measurements can be taken.

[0026] As the radical polymerizable compound (A) contained in the photocurable resin composition of the present invention, if the polyfunctional radical polymerizable compound (A-1) is contained in an amount of more than 60 mass %, the curability of the photocurable resin composition and the heat resistance of the obtained shaped object can be sufficiently obtained. That is, it is sufficient that the polyfunctional radical polymerizable compound (A-1) contained in the radical polymerizable compound (A) is more than 60 mass % and 100 mass % or less.

[0027] In addition, the radical polymerizable compound (A) is preferably a mixture containing a polyfunctional radical polymerizable compound (A-1) and a monofunctional radical polymerizable compound (A-2) described later, in terms of being able to properly adjust the viscosity of the photocurable resin composition. When the monofunctional radical polymerizable compound (A-2) is contained, the monofunctional radical polymerizable compound (A-2) is preferably 5 parts by mass or more and less than 40 parts by mass in a total of 100 parts by mass of the polyfunctional radical polymerizable compound (A-1) and the monofunctional radical polymerizable compound (A-2). If the monofunctional radical polymerizable compound (A-2) is 5 parts by mass or more, the viscosity of the photocurable resin composition can be properly maintained, and it can be suitably used in a three-dimensional modeling method. If the monofunctional radical polymerizable compound (A-2) is less than 25 parts by mass, the heat resistance of the shaped object obtained by curing the photocurable resin composition can be maintained higher. Therefore, in a total of 100 parts by mass of the polyfunctional radical polymerizable compound (A-1) and the monofunctional radical polymerizable compound (A-2), the amount of the monofunctional radical polymerizable compound (A-2) is preferably 5 parts by mass or more and less than 40 parts by mass, and more preferably 5 parts by mass or more and less than 25 parts by mass.

[0028] <Monofunctional radically polymerizable compound (A-2)> The monofunctional radical polymerizable compound (A-2) that may be included in the radical polymerizable compound (A) according to the present invention is a compound having one radical polymerizable functional group in the molecule. As described above, the photocurable resin composition contains the monofunctional radical polymerizable compound (A-2), thereby realizing a viscosity suitable for three-dimensional modeling. In addition, by adjusting the amount of the monofunctional radical polymerizable compound (A-2) added or by appropriately selecting the type, the mechanical properties of the model obtained by curing the photocurable resin composition can be adjusted to a desired range.

[0029] Examples of the monofunctional radical polymerizable compound (A-2) include, but are not limited to, acrylamide compounds, (meth)acrylate compounds, maleimide compounds, styrene compounds, acrylonitrile compounds, vinyl ester compounds, N-vinyl compounds, conjugated diene compounds, vinyl ketone compounds, vinyl halide / vinylidene halide compounds, etc. Among these, acrylamide compounds, maleimide monomers, and N-vinyl compounds are particularly preferred in terms of excellent curability of the resin composition and heat resistance of the resulting shaped object.

[0030] Examples of acrylamide compounds include (meth)acrylamide, N-methyl(meth)acrylamide, N-isopropyl(meth)acrylamide, Nt-butyl(meth)acrylamide, N-phenyl(meth)acrylamide, N-methylol(meth)acrylamide, N,N-diacetone(meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N,N-dipropyl(meth)acrylamide, N,N-dibutyl(meth)acrylamide, N-(meth)acryloylmorpholine, N-(meth)acryloylpiperidine, N-[3-(dimethylamino)propyl]acrylamide, and Nt-octyl(meth)acrylamide.

[0031] Examples of the (meth)acrylate compounds include methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, i-octyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, 3-hydroxy-1-adamantyl (meth)acrylate, 3,5-Dihydroxy-1-adamantyl (meth)acrylate, 2-methyl-2-adamantyl (meth)acrylate, 2-ethyl-2-adamantyl (meth)acrylate, 2-isopropyl-2-adamantyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, glycidyl (meth)acrylate, 3-methyl-3-oxetanyl-methyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, (meth)acrylate, phenyl glycidyl (meth)acrylate, dimethylaminomethyl (meth)acrylate, phenyl cellosolve (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, biphenyl (meth)acrylate, 2-hydroxyethyl (meth)acryloyl phosphate, phenyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxypropyl (meth)acrylate, benzyl (meth)acrylate, butoxytriethylene glycol (meth) ) acrylate, 2-ethylhexyl polyethylene glycol (meth)acrylate, nonylphenyl polypropylene glycol (meth)acrylate, methoxydipropylene glycol (meth)acrylate, glycerol (meth)acrylate, trifluoromethyl (meth)acrylate, trifluoroethyl (meth)acrylate, tetrafluoropropyl (meth)acrylate, octafluoropentyl acrylate, polyethylene glycol (meth)acrylate, polypropylene glycol (meth)acrylate, allyl (meth)acrylate acrylate, 2,2,2-trifluoroethyl (meth)acrylate, 2,2,3,3-tetrafluoropropyl (meth)acrylate, 1H,1H,5H,octafluoropentyl (meth)acrylate, epichlorohydrin modified butyl (meth)acrylate, epichlorohydrin modified phenoxy (meth)acrylate, ethylene oxide (EO) modified phthalic acid (meth)acrylate, EO modified succinic acid (meth)acrylate, caprolactone modified 2-hydroxyethyl (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylate, N,Examples of such compounds include N-diethylaminoethyl (meth)acrylate, morpholino (meth)acrylate, EO-modified phosphate (meth)acrylate, methyl allyloxyacrylate (product name: AO-MA, manufactured by Nippon Shokubai Co., Ltd.), (meth)acrylates having an imide group (product name: M-140, manufactured by Toagosei Co., Ltd.), and monofunctional (meth)acrylates having a siloxane structure.

[0032] Examples of maleimide monomers include maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide, and cyclohexylmaleimide. Examples of the N-vinyl compound include N-vinylpyrrolidone, N-vinylcaprolactam, N-vinylimidazole, N-vinylmorpholine, and N-vinylacetamide.

[0033] Other monofunctional radical polymerizable compounds include, for example, styrene derivatives such as styrene, vinyltoluene, α-methylstyrene, chlorostyrene, styrenesulfonic acid and salts thereof, vinyl esters such as vinyl acetate, vinyl propionate, vinyl pivalate, vinyl benzoate, and vinyl cinnamate, and vinyl cyanide compounds such as (meth)acrylonitrile. These monofunctional radically polymerizable compounds may be used alone or in combination of two or more kinds.

[0034] <Polysilsesquioxane particles (B)> The polysilsesquioxane particles (B) contained in the photocurable resin composition of the present invention are contained as a solid lubricant in the cured product after photocuring of the photocurable resin composition of the present invention, and roll on the sliding surface without cracking. This allows the cured product to achieve a small friction coefficient. Therefore, the obtained cured product has high wear resistance and a low friction coefficient.

[0035] The polysilsesquioxane particles (B) used in the present invention may have polysilsesquioxane on the surface, and in order to maintain the particle shape, it is preferable that the polysilsesquioxane particles (B) do not substantially dissolve or swell in the radical polymerizable compound (A). Here, "does not substantially dissolve or swell" means that the average particle diameter of the polysilsesquioxane particles (B) does not change when the polysilsesquioxane particles (B) are mixed with the radical polymerizable compound (A).

[0036] Silsesquioxanes have different molecular structures such as cage type, ladder type, random type, etc., and different numbers of repeating units such as low molecular weight, oligomer, polymer, etc., but a random type polysilsesquioxane that is not dissolved in the radical polymerizable compound (A) and is a polymer type is preferred. Among the polymer type polysilsesquioxanes, those that do not show weight loss at 400°C in thermogravimetric analysis and do not melt are more preferred. From the viewpoint of ease of availability, it is sufficient that the main component is a structure having 3 siloxane bonds per silicon atom, and structures having 1, 2, or 4 oxygen bonds per silicon atom may be mixed.

[0037] As the polysilsesquioxane particles (B) used in the present invention, the particles that the whole particle is made of polysilsesquioxane, or the particles that have a core-shell structure with a core made of silicone rubber or the like and a shell made of polysilsesquioxane are preferably used.In addition, when the whole particle is made of polysilsesquioxane, or when the shell is made of polysilsesquioxane, the polysilsesquioxane contains a small amount of dimethylsiloxane in the manufacturing process, but this does not affect the present invention.

[0038] The average particle diameter of the polysilsesquioxane particles (B) used in the present invention is preferably 50 μm or less. In the stereolithography method, since layers are often laminated in units of 200 μm or less in thickness, if the average particle diameter is 50 μm or less, there is little possibility that unevenness will occur in the distribution of the polysilsesquioxane particles in the layer. On the other hand, if the average particle diameter of the polysilsesquioxane particles (B) is 0.5 μm or more, the viscosity of the photocurable resin composition is unlikely to increase significantly. That is, the average particle diameter of the polysilsesquioxane particles (B) is preferably 0.5 μm or more and 50 μm or less, and more preferably 0.7 μm or more and 5 μm or less because of ease of availability. In addition, the polysilsesquioxane particles (B) are preferably spherical because of ease of dispersion in the photocurable resin composition.

[0039] The average particle size of the polysilsesquioxane particles (B) refers to the arithmetic mean value of the sphere volume equivalent diameter measured by the Coulter counter method. The specific measurement principle of the Coulter counter method is as follows. A container containing an electrolyte with particles dispersed in it is divided into two by a wall with a single pore passing through it. Electrodes are placed on either side of the wall, and a constant current is passed between the electrodes. When the electrolyte is sucked in with a constant suction force on one side of the wall, the particles pass through the pore together with the electrolyte. At this time, the electrolyte in the pore decreases by an amount equivalent to the volume of the particles, and the electrical resistance of the pore increases in proportion to the amount of electrolyte reduced. Since the current flowing through the pore is constant, the voltage between the electrodes changes in proportion to the change in the electrical resistance of the pore. The volume of the particles is measured from the change in this voltage, and the spherical volume equivalent diameter of the particles is calculated from this volume, allowing the particle size distribution to be obtained.

[0040] A specific measurement method is, for example, as follows. First, polysilsesquioxane particles and sodium alkylbenzene sulfonate are mixed and added to an electrolyte such as Beckman Coulter's electrolyte ISOTON-II. Then, a dispersion process is performed using an ultrasonic disperser to prepare a sample. As a measuring device for the Coulter counter method, for example, a Beckman Coulter Multisizer 3 can be used, and a 200 μm aperture tube or a 400 μm aperture tube can be used. The sphere volume equivalent diameter and number of polysilsesquioxane particles are measured using a measuring device for the Coulter counter method, and the arithmetic average value of the sphere volume equivalent diameter is obtained from the results.

[0041] If the polysilsesquioxane particles (B) used in the present invention do not have a radical polymerizable functional group in the molecule, the affinity with the radical polymerizable compound (A) will not be too high, and the polysilsesquioxane particles (B) will be easily released onto the sliding surface when the cured product is slid. Therefore, it is preferable that the polysilsesquioxane particles (B) do not have a radical polymerizable functional group in the molecule, in that the cured product can achieve higher sliding properties. On the other hand, if the polysilsesquioxane particles (B) have a radical polymerizable functional group in the molecule, the affinity with the radical polymerizable compound (A) will be high, and the polysilsesquioxane particles will not easily settle in the photocurable resin composition. In addition, there is an advantage that the adhesion of the radical polymerizable compound (A) to the cured product is increased, and the cured product is less likely to crack. For these reasons, it is also preferable that the polysilsesquioxane particles (B) have a radical polymerizable functional group in the molecule.

[0042] The polysilsesquioxane particles (B) used in the present invention may be chemically treated on the surface for the purpose of improving dispersibility in the photocurable resin composition, improving dispersion stability, preventing aggregation, etc. For example, a silane coupling agent treatment may be used. In addition, the surface after the above treatment may be grafted with a low molecular weight or a polymer. Alternatively, the surface of the polysilsesquioxane particles may be coated with a low molecular weight or a polymer.

[0043] The polysilsesquioxane particles (B) used in the present invention may be a single type of particle, or may contain a plurality of types of particles made of a plurality of different materials. The content of the polysilsesquioxane particles (B) in the photocurable resin composition of the present invention is 5 parts by mass or more and 30 parts by mass or less, and preferably 10 parts by mass or more and 20 parts by mass or less, relative to 100 parts by mass of the radical polymerizable compound. If the content of the polysilsesquioxane particles (B) is within this range, a viscosity applicable to a three-dimensional modeling method is obtained, and the slidability of the cured product obtained by curing the photocurable resin composition is also improved.

[0044] <Hardening agent (C)> It is more preferable to use a photoradical polymerization initiator as the curing agent (C). The photocurable resin composition of the present invention may contain a thermal radical polymerization initiator in addition to the photoradical polymerization initiator. When the photocurable resin composition contains a thermal radical polymerization initiator, the polymerization reaction can be promoted by performing a heat treatment after modeling by light irradiation, and the mechanical properties of the modeled object can be further improved.

[0045] [Photoradical polymerization initiator] Photoradical polymerization initiators are mainly classified into intramolecular cleavage type and hydrogen abstraction type. In the intramolecular cleavage type, a bond at a specific site is cut by absorbing light of a specific wavelength, and a radical is generated at the cut site, which acts as a polymerization initiator and starts the polymerization of the radically polymerizable compound (A). In the hydrogen abstraction type, a photoradical polymerization initiator absorbs light of a specific wavelength and becomes excited, and the excited species causes a hydrogen abstraction reaction from a hydrogen donor in the vicinity, generating a radical. Then, the generated radical acts as a polymerization initiator and starts the polymerization of the radically polymerizable compound (A). In the present invention, two or more types of photoradical polymerization initiators may be used in combination, or one may be used alone.

[0046] Known intramolecular cleavage type photoradical polymerization initiators include alkylphenone-based photoradical polymerization initiators, acylphosphine oxide-based photoradical polymerization initiators, and oxime ester-based photoradical polymerization initiators, which undergo α-cleavage of the bond adjacent to the carbonyl group to generate radical species.

[0047] Examples of the alkylphenone-based photoradical polymerization initiator include a benzyl methyl ketal-based photoradical polymerization initiator, an α-hydroxyalkylphenone-based photoradical polymerization initiator, and an aminoalkylphenone-based photoradical polymerization initiator. Specific examples of the compounds include a benzyl methyl ketal-based photoradical polymerization initiator, such as 2,2'-dimethoxy-1,2-diphenylethan-1-one (Irgacure(R) 651, manufactured by BASF), and an α-hydroxyalkylphenone-based photoradical polymerization initiator, such as 2-hydroxy-2-methyl-1-phenylpropan-1-one (Darocure(R) 1173, manufactured by BASF), 1-hydroxycyclohexyl phenyl ketone (Irgacure(R) 184, manufactured by BASF), 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one (Irgacure(R) 185, manufactured by BASF), and the like. Examples of the aminoalkylphenone-based photoradical polymerization initiator include 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one (Irgacure(R) 907, BASF), 2-benzylmethyl-2-dimethylamino-1-(4-morpholinophenyl)-1-butanone (Irgacure(R) 369, BASF), but are not limited to these.

[0048] Examples of acylphosphine oxide-based photoradical polymerization initiators include, but are not limited to, 2,4,6-trimethylbenzoyldiphenylphosphine oxide (Lucirin(R) TPO, manufactured by BASF), bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (Omnirad(R) 819, manufactured by IGM Resins), and the like.

[0049] Examples of oxime ester-based photoradical polymerization initiators include, but are not limited to, (2E)-2-(benzoyloxyimino)-1-[4-(phenylthio)phenyl]octan-1-one (Irgacure® OXE-01, manufactured by BASF). Examples of the hydrogen abstraction type photoradical polymerization initiator include anthraquinone derivatives such as 2-ethyl-9,10-anthraquinone and 2-t-butyl-9,10-anthraquinone, and thioxanthone derivatives such as isopropylthioxanthone and 2,4-diethylthioxanthone, but are not limited thereto.

[0050] The amount of the photoradical polymerization initiator contained in the photocurable resin composition of the present invention is preferably 0.1 parts by mass or more and 15 parts by mass or less relative to 100 parts by mass of the radical polymerizable compound. More preferably, it is 0.1 parts by mass or more and 10 parts by mass or less. Within this range, polymerization proceeds sufficiently, and at the same time, the transparency of the photocurable resin composition is sufficient, and uniform polymerization is obtained.

[0051] [Thermal radical polymerization initiator] The thermal radical polymerization initiator is not particularly limited as long as it generates radicals by heating, and any conventionally known compound can be used. For example, preferred examples include azo compounds, peroxides, and persulfates.

[0052] Examples of azo compounds include 2,2'-azobisisobutyronitrile, 2,2'-azobis(methylisobutyrate), 2,2'-azobis-2,4-dimethylvaleronitrile, and 1,1'-azobis(1-acetoxy-1-phenylethane). Examples of peroxides include benzoyl peroxide, di-t-butylbenzoyl peroxide, t-butyl peroxypivalate, and di(4-t-butylcyclohexyl)peroxydicarbonate. Examples of the persulfates include ammonium persulfate, sodium persulfate, potassium persulfate, and the like.

[0053] When a thermal radical polymerization initiator is used, the amount of the initiator added is preferably 0.1 to 15 parts by mass, more preferably 0.1 to 10 parts by mass, based on 100 parts by mass of the radical polymerizable compound (A). Within this range, an appropriate molecular weight and good physical properties can be obtained.

[0054] <Other ingredients> The photocurable resin composition of the present invention may contain various additives as other optional components within the scope of not impairing the object and effect of the present invention. Examples of additives include resins such as epoxy resins, polyurethanes, polybutadiene, polychloroprene, polyesters, styrene-butadiene block copolymers, polysiloxanes, petroleum resins, xylene resins, ketone resins, and cellulose resins, engineering plastics such as polycarbonates, modified polyphenylene ethers, polyamides, polyacetals, polyethylene terephthalates, polybutylene terephthalates, polyphenylsulfones, polysulfones, polyarylates, polyetherimides, polyetheretherketones, polyphenylene sulfides, polyethersulfones, polyamideimides, liquid crystal polymers, polytetrafluoroethylene, polychlorotrifluoroethylene, and polyvinylidene fluoride, reactive monomers and reactive oligomers such as fluorine-based oligomers, silicone-based oligomers, polysulfide-based oligomers, fluorine-containing monomers, and siloxane structure-containing monomers, soft metals such as gold, silver, and lead, and graphite. , molybdenum disulfide, tungsten disulfide, boron nitride, graphite fluoride, calcium fluoride, barium fluoride, lithium fluoride, silicon nitride, layered crystal structure substances such as molybdenum selenide, phenothiazine, paramethoxyphenol, 2,6-di-t-butyl-4-methylphenol, 2,2,6,6-tetramethylpiperidine 1-oxyl, 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl, 2-methyl-1,4-naphthoquinone, benzo Examples of suitable additives include polymerization inhibitors such as quinone, photosensitizers such as benzoin compounds, acetophenone compounds, anthraquinone compounds, thioxanthone compounds, ketal compounds, benzophenone compounds, tertiary amine compounds, and xanthone compounds, polymerization initiation aids, leveling agents, wettability improvers, surfactants, plasticizers, ultraviolet absorbers, silane coupling agents, inorganic fillers, pigments, dyes, antioxidants, flame retardants, thickeners, rheology adjusters, defoamers, organic solvents, and fluorescent brighteners.

[0055] <Photocurable resin composition> The photocurable resin composition of the present invention is produced by adding an appropriate amount of other optional components to the essential components of the radical polymerizable compound (A), the polysilsesquioxane particles (B), and the curing agent (C) as necessary. Specifically, these components are charged into a stirring vessel and stirred at a temperature of usually 30° C. to 120° C., preferably 50° C. to 100° C. The stirring time is usually 1 minute to 6 hours, preferably 10 minutes to 2 hours. The total content of the radical polymerizable compound (A) and the polysilsesquioxane particles (B) is preferably 75 parts by mass to 100 parts by mass, more preferably 90 parts by mass to 100 parts by mass, in 100 parts by mass of the photocurable resin composition excluding the curing agent (C). The remaining parts by mass, excluding the radical polymerizable compound (A) and the polysilsesquioxane particles (B), out of 100 parts by mass of the photocurable resin composition, are occupied by the curing agent (C) and the other components described above.

[0056] The viscosity of the photocurable resin composition of the present invention at 25° C. is preferably 50 mPa·s or more and 30,000 mPa·s or less, and more preferably 50 mPa·s or more and 10,000 mPa·s or less.

[0057] The photocurable resin composition of the present invention obtained as described above is suitable for use as a modeling material in a stereolithography method. That is, a modeled object having a desired shape can be manufactured by irradiating the photocurable resin composition of the present invention with a light energy beam in accordance with slice data generated from three-dimensional shape data of an article (modeling model) to be modeled, and supplying energy required for curing.

[0058] <Cured product> The cured product of the present invention can be obtained by curing the above-mentioned photocurable resin composition by irradiation with light energy rays. The cured product obtained from the photocurable resin composition of the present invention contains polysilsesquioxane particles (B), and therefore has a low coefficient of friction and high wear resistance. Specifically, the specific wear rate of the cured product of the present invention is 0.5 mm 3 N -1 km -1Preferably less than 0.3 mm 3 N -1 km -1 The coefficient of friction of the cured product is preferably less than 1.0, and more preferably less than 0.5. In the photocurable resin composition of the present invention, the ethylenically unsaturated group equivalent of the polyfunctional radically polymerizable compound (A-1) is 250 g / eq or more and less than 700 g / eq, and therefore the cured product obtained from such a photocurable resin composition has good heat resistance.

[0059] <Manufacturing method for three-dimensional objects> The photocurable resin composition of the present invention contains a photopolymerization initiator such as a photoradical polymerization initiator as the curing agent (C), and thus can be suitably used for the production (shaping) of a three-dimensional object using a stereolithography method. A three-dimensional object made of the photocurable resin composition of the present invention can be produced using a known stereolithography method. Specifically, the method includes a step of arranging the photocurable resin composition in layers, and a step of irradiating the layered photocurable resin composition with light energy based on slice data of a model to cure the composition. The method for manufacturing an article using a stereolithography method preferably further includes a step of subjecting the model obtained by irradiating the light energy to a heat treatment. The light energy is preferably light irradiated from a laser light source or a projector. A representative example of a preferred stereolithography method is a method having a step of sequentially curing the photocurable resin composition in layers based on slice data generated from three-dimensional shape data of the article to be modeled, and is roughly divided into two types: a free liquid level method and a regulated liquid level method.

[0060] FIG. 1 shows a configuration example of a photo-fabrication apparatus 100 using the free liquid surface method. The photo-fabrication apparatus 100 has a tank 11 filled with a liquid photo-curable resin composition 10. Inside the tank 11, a modeling stage 12 is provided so as to be drivable in the vertical direction by a drive shaft 13. The irradiation position of a light energy beam 15 for curing the photo-curable resin composition 10 emitted from a light source 14 is changed by a galvanometer mirror 16 controlled by a control unit 18 according to slice data, and the surface of the photo-curable resin composition 10 in the tank 11 is scanned. In FIG. 1, the scanning range is indicated by a thick dashed line.

[0061] The thickness d of the photocurable resin composition 10 cured by the light energy beam 15 is a value determined based on the settings at the time of generating the slice data, and affects the accuracy (reproducibility of the three-dimensional shape data of the object to be molded) of the obtained model 17. The thickness d is achieved by the control unit 18 controlling the drive amount of the drive shaft 13.

[0062] First, the control unit 18 controls the drive shaft 13 based on the settings, and the photocurable resin composition is supplied to the modeling stage 12 at a thickness d. The liquid photocurable resin composition on the modeling stage 12 is selectively irradiated with light energy rays based on slice data so as to obtain a cured layer having a desired pattern, and a cured layer is formed. Next, the modeling stage 12 is moved in the direction of the white arrow, and the uncured photocurable resin composition is supplied to the surface of the cured layer at a thickness d. Then, light energy rays 15 are irradiated based on the slice data, and a cured product integrated with the previously formed cured layer is formed. By repeating this layer-by-layer curing process, the desired three-dimensional model 17 can be obtained.

[0063] The three-dimensional object 17 thus obtained is taken out of the tank 11, and the unreacted photocurable resin composition remaining on the surface is removed, followed by washing as necessary. As the washing agent, an alcohol-based organic solvent, such as alcohols such as isopropyl alcohol and ethyl alcohol, can be used. In addition, a ketone-based organic solvent, such as acetone and methyl ethyl ketone, an organic solvent such as ethyl acetate, or an aliphatic organic solvent, such as terpenes, may be used. After washing with the washing agent, post-curing by light irradiation or heat irradiation may be performed as necessary. The post-curing can cure the unreacted photocurable resin composition that may remain on the surface and inside of the three-dimensional object 17, suppressing the stickiness of the surface of the three-dimensional object 17 and improving the initial strength of the three-dimensional object 17.

[0064] Examples of light energy rays used in the production include ultraviolet rays, electron beams, X-rays, and radiation. Among them, ultraviolet rays having a wavelength of 300 nm or more and 450 nm or less are preferably used from an economical point of view. As a light source that generates ultraviolet rays, ultraviolet lasers (e.g., Ar lasers, He-Cd lasers, etc.), mercury lamps, xenon lamps, halogen lamps, fluorescent lamps, etc. can be used. Among them, laser light sources are preferably used because they can shorten the modeling time by increasing the energy level, and because they have excellent light collecting properties, they can reduce the irradiation diameter and obtain high modeling accuracy. The light energy rays can be appropriately selected according to the type of radical polymerization initiator contained in the photocurable resin composition, and multiple combinations can also be used.

[0065] When a surface made of a photocurable resin composition is irradiated with light energy rays to form a cured layer having a predetermined shape pattern, the resin can be cured by a pointillist method or a line drawing method using light energy rays focused in a dotted or line shape. Alternatively, the resin can be cured by irradiating the active energy rays in a planar manner through a planar drawing mask formed by arranging a plurality of microscopic light shutters such as liquid crystal shutters or digital micromirror shutters.

[0066] Similarly, modeling by the regulated liquid level method is also preferable. In the optical modeling apparatus using the regulated liquid level method, the modeling stage 12 of the optical modeling apparatus 100 in FIG. 1 is provided so as to raise the model above the liquid level, and the light irradiation means is provided below the tank 11. A typical modeling example by the regulated liquid level method is as follows. First, the support surface of the support stage, which is provided so as to be freely raised and lowered, and the bottom surface of the tank containing the photocurable resin composition are set at a predetermined distance, and the photocurable resin composition is supplied between the support surface of the support stage and the bottom surface of the tank. Next, light is selectively irradiated from the bottom surface side of the tank containing the photocurable resin composition by a laser light source or a projector to the photocurable resin composition between the stage support surface and the bottom surface of the tank according to slice data. The photocurable resin composition between the stage support surface and the bottom surface of the tank is cured by the irradiation of light, and a solid cured resin layer is formed. After that, the support stage is raised, and the cured resin layer is peeled off from the bottom surface of the tank.

[0067] Next, the height of the support stage is adjusted so that the distance between the cured layer formed on the support stage and the bottom surface of the tank is a predetermined distance. Then, by selectively irradiating light in the same manner as above, a new cured resin layer is formed between the cured resin layer and the bottom surface of the tank, which is integrated with the previously formed cured resin layer. This process is then repeated a predetermined number of times, with or without changing the light irradiation pattern, to form a three-dimensional object in which multiple cured resin layers are stacked together.

[0068] <Application> The photocurable resin composition according to the present invention and the article which is the cured product thereof are not particularly limited in use. For example, they can be used for various purposes such as resins for 3D printers using stereolithography, sports goods, medical and nursing care products, custom-made products such as artificial limbs, dentures and bones, industrial machinery and equipment, precision instruments, electric and electronic equipment, electric and electronic parts, and building materials.

[0069] <Included configuration> The disclosure of this embodiment includes the following configuration. (Configuration 1) A composition comprising a radical polymerizable compound (A), polysilsesquioxane particles (B), and a curing agent (C), The polysilsesquioxane particles (B) have polysilsesquioxane at least on their surfaces, The radical polymerizable compound (A) contains at least a polyfunctional radical polymerizable compound (A-1) in an amount of more than 60 mass %, the polyfunctional radically polymerizable compound (A-1) has an ethylenically unsaturated group equivalent of 250 g / eq or more and less than 700 g / eq; A photocurable resin composition for three-dimensional modeling, comprising 5 parts by mass or more and 30 parts by mass or less of the polysilsesquioxane particles (B) per 100 parts by mass of the radical polymerizable compound (A).

[0070] (Configuration 2) the radical polymerizable compound (A) is a mixture of the polyfunctional radical polymerizable compound (A-1) and the monofunctional radical polymerizable compound (A-2), The photocurable resin composition for three-dimensional modeling according to configuration 1, characterized in that, in a total of 100 parts by mass of the polyfunctional radical polymerizable compound (A-1) and the monofunctional radical polymerizable compound (A-2), the monofunctional radical polymerizable compound (A-2) is 5 parts by mass or more and less than 40 parts by mass. (Configuration 3) The photocurable resin composition for three-dimensional modeling according to configuration 2, characterized in that, in a total of 100 parts by mass of the polyfunctional radical polymerizable compound (A-1) and the monofunctional radical polymerizable compound (A-2), the monofunctional radical polymerizable compound (A-2) is 5 parts by mass or more and less than 25 parts by mass. (Configuration 4) The photocurable resin composition for three-dimensional modeling according to the configuration 2 or 3, characterized in that the monofunctional radically polymerizable compound (A-2) is selected from the group consisting of an acrylamide-based compound, an N-vinyl compound, and a maleimide-based compound.

[0071] (Configuration 5) 5. The photocurable resin composition for three-dimensional object formation according to any one of configurations 1 to 4, wherein the polysilsesquioxane particles (B) are entirely made of polysilsesquioxane. (Configuration 6) The photocurable resin composition for three-dimensional modeling according to any one of configurations 1 to 4, wherein the polysilsesquioxane particles (B) have a core-shell structure, and the shell of the core-shell structure is made of polysilsesquioxane. (Configuration 7) 7. The photocurable resin composition for three-dimensional modeling according to any one of configurations 1 to 6, wherein the polysilsesquioxane is a random type polysilsesquioxane. (Configuration 8) 8. The photocurable resin composition for three-dimensional modeling according to any one of configurations 1 to 7, wherein the average particle diameter of the polysilsesquioxane particles (B) is 0.7 μm or more and 5.0 μm or less.

[0072] (Configuration 9) The photocurable resin composition for three-dimensional modeling according to any one of structures 1 to 8, wherein the polyfunctional radical polymerizable compound (A-1) is a single polyfunctional radical polymerizable compound having an ethylenically unsaturated group equivalent of 250 g / eq or more and less than 700 g / eq. (Configuration 10) The photocurable resin composition for three-dimensional modeling according to any one of structures 1 to 9, characterized in that the polyfunctional radical polymerizable compound (A-1) contains a plurality of types of polyfunctional radical polymerizable compounds, and the ethylenically unsaturated group equivalent weighted average of the ethylenically unsaturated group equivalents of each compound is 250 g / eq or more and less than 700 g / eq by mass ratio. (Configuration 11) The photocurable resin composition for three-dimensional modeling according to claim 10, characterized in that the polyfunctional radical polymerizable compound (A-1) contains a polyfunctional radical polymerizable compound having an ethylenically unsaturated group equivalent of 700 g / eq or more. (Configuration 12) The photocurable resin composition for three-dimensional modeling described in any one of structures 1 to 11, characterized in that the polyfunctional radically polymerizable compound (A-1) has an ethylenically unsaturated group equivalent of 400 g / eq or more and less than 700 g / eq.

[0073] (Configuration 13) The photocurable resin composition for three-dimensional modeling according to any one of structures 1 to 12, characterized in that the polyfunctional radically polymerizable compound (A-1) is a (meth)acrylate-based compound or a urethane (meth)acrylate-based compound having any one of a polyether structure, a polyester structure, and a polycarbonate structure. (Configuration 14) 14. The photocurable resin composition for three-dimensional object formation according to any one of configurations 1 to 13, wherein the curing agent (C) contains at least a photoradical polymerization initiator.

[0074] (Configuration 15) 15. A cured product obtained by curing the photocurable resin composition according to any one of claims 1 to 14. (Configuration 16) Specific wear volume is 0.5mm 3 N -1 km -1 16. The cured product according to claim 15, wherein the cured product has a viscosity of less than 1000 s. (Configuration 17) 17. The cured product according to claim 15 or 16, having a coefficient of friction of less than 1.0.

[0075] (Configuration 18) A method for manufacturing a three-dimensional object using a photolithography method, comprising the steps of: disposing a photocurable resin composition in a layer; and curing the layered photocurable resin composition by irradiating the layered photocurable resin composition with light energy based on slice data of a model, 15. A method for producing a three-dimensional object, wherein the photocurable resin composition is the photocurable resin composition according to any one of claims 1 to 14. (Configuration 19) 19. The method for producing a three-dimensional object according to configuration 18, further comprising a step of subjecting the shaped object obtained by the step of irradiating light energy to hardening, to a heat treatment. (Configuration 20) 20. The method for manufacturing a three-dimensional object according to claim 18, wherein the light energy is light emitted from a laser light source or a projector. EXAMPLES

[0076] EXAMPLES In order to explain the present invention in detail, examples are given below, but the present invention is not limited to these examples.

[0077] <Ingredients> The components used in the examples and comparative examples are as follows.

[0078] [Polyfunctional radically polymerizable compound (A-1)] Table 1 shows the polyfunctional radically polymerizable compound (A-1) used in the examples and comparative examples.

[0079] [Table 1]

[0080] [Polysilsesquioxane particles (B)] B-1: Silicone composite powder KMP-600 manufactured by Shin-Etsu Chemical Co., Ltd. It is a composite particle with a core-shell structure, and the main component of the core is a crosslinked polydimethylsiloxane (silicone rubber). The shell is a random type polysilsesquioxane with methyl groups as organic substituents, and contains a trace amount of dimethylsiloxane. It does not substantially dissolve or swell in either the multifunctional radical polymerizable compound (A-1) or a mixture of the multifunctional radical polymerizable compound (A-1) and the monofunctional radical polymerizable compound (A-2). It is a spherical particle with an average particle diameter of 5.0 μm and a shell thickness of 70 nm. B-2: Silicone composite powder X-52-7030 manufactured by Shin-Etsu Chemical Co., Ltd. It is a composite particle with a core-shell structure, and the main component of the core is a crosslinked polydimethylsiloxane (silicone rubber). The shell is made of random-type polysilsesquioxane with methyl groups as organic substituents, and contains a trace amount of dimethylsiloxane. It does not substantially dissolve or swell in either the multifunctional radical polymerizable compound (A-1) or a mixture of the multifunctional radical polymerizable compound (A-1) and the monofunctional radical polymerizable compound (A-2). It is a spherical particle with an average particle diameter of 0.8 μm and a shell thickness of 25 nm. B-3: Shin-Etsu Silicone "Silicone Resin Powder X-52-1621" The whole is made of random polysilsesquioxane having methyl groups as organic substituents, and contains a small amount of dimethylsiloxane. It does not substantially dissolve or swell in the polyfunctional radical polymerizable compound (A-1) or a mixture of the polyfunctional radical polymerizable compound (A-1) and the monofunctional radical polymerizable compound (A-2). In addition, the thermal weight loss is not observed at 400°C, and the particles are spherical and do not melt, and the average particle size is 5.0 μm. B-4: Shin-Etsu Silicone "Silicone Resin Powder X-52-854" The whole is made of random polysilsesquioxane having methyl groups as organic substituents, and contains a small amount of dimethylsiloxane. It does not substantially dissolve or swell in the polyfunctional radical polymerizable compound (A-1) or a mixture of the polyfunctional radical polymerizable compound (A-1) and the monofunctional radical polymerizable compound (A-2). In addition, the thermal weight loss is not observed at 400°C, and the particles are spherical and do not melt, with an average particle size of 0.7 μm.

[0081] (Method of measuring average particle size) First, 5 mg of polysilsesquioxane particles were mixed with 2 ml of sodium alkylbenzene sulfonate and added to 100 ml of electrolyte (ISOTON-II) manufactured by Beckman Coulter. After that, the sample was prepared by dispersing the particles for about 5 minutes using an ultrasonic disperser. A Beckman Coulter Multisizer 3 was used as the measuring device for the Coulter counter method, with a 200 μm or 400 μm aperture. The spherical volume equivalent diameter and number of polysilsesquioxane particles were measured using the above device, and the average particle diameter (arithmetic mean value of spherical volume equivalent diameter) was calculated from the results.

[0082] [Hardening agent (C)] C-1: Omnirad819 (IGM Resins, photoradical polymerization initiator, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide)

[0083] [Monofunctional radically polymerizable compound (A-2)] Table 2 shows the monofunctional radically polymerizable compound (A-2) used in the examples and comparative examples.

[0084] [Table 2]

[0085] [Other components (D)] D-1: Merck's "4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl" D-2: "4-Methoxyphenol" manufactured by Tokyo Chemical Industry D-3: Shin-Etsu Silicone "Silicone Rubber Powder KMP-597" The particles are spherical particles with a crosslinked structure of dimethylsiloxane, and have an average particle size of 5.0 μm. These particles absorb the polyfunctional radical polymerizable compound (A-1) or a mixture of the polyfunctional radical polymerizable compound (A-1) and the monofunctional radical polymerizable compound (A-2) and swell. The average particle size was measured in the same manner as for the polysilsesquioxane particles (B). D-4: Sigma-Aldrich "PSS-octamethyl substituted" The main component is a cage-type silsesquioxane, which has a methyl group as an organic substituent. This compound dissolves in both the polyfunctional radical polymerizable compound (A-1) and a mixture of the polyfunctional radical polymerizable compound (A-1) and the monofunctional radical polymerizable compound (A-2).

[0086] <Example 1> [Preparation of photocurable resin composition] Photocurable resin compositions were prepared by mixing the components according to the recipes shown in Tables 3 to 5, heating to 75° C. and stirring for 2 hours with a stirrer. The numerical values ​​for each component in the tables are parts by mass. The contents of the polyfunctional radical polymerizable compound (A-1) and the monofunctional radical polymerizable compound (A-2) shown in Tables 3 and 4 indicate the contents of the polyfunctional radical polymerizable compound (A-1) and the monofunctional radical polymerizable compound (A-2) in a total of 100 parts by mass of the polyfunctional radical polymerizable compound (A-1) and the monofunctional radical polymerizable compound (A-2) in parts by mass. The amount of the polysilsesquioxane particles (B) added indicates the amount of the polysilsesquioxane particles (B) added to the total of 100 parts by mass of the polyfunctional radical polymerizable compound (A-1) and the monofunctional radical polymerizable compound (A-2) in parts by mass.

[0087] Example 1 contains multiple types of polyfunctional radical polymerizable compounds as the polyfunctional radical polymerizable compound (A-1), and is a mixture of polyfunctional radical polymerizable compounds having an ethylenically unsaturated group equivalent of 250 g / eq or more and less than 700 g / eq and less than 250 g / eq.

[0088] [Preparation of test piece X] A test piece was prepared from the prepared photocurable resin composition by the following method. First, a mold with a length of 80 mm, a width of 10 mm, and a thickness of 4 mm was sandwiched between two pieces of quartz glass, and the photocurable resin composition was poured into the mold. The poured photocurable resin composition was irradiated with 5 mW / cm2 ultraviolet light by an ultraviolet irradiator (manufactured by HOYA CANDEO OPTRONICS, product name "LIGHT SOURCE EXECURE3000"). 2The two surfaces of the mold were irradiated with ultraviolet light for 360 seconds each to obtain a cured product. The total energy irradiated to cure the photocurable resin composition was 3600 mJ / cm 2 The obtained cured product was placed in a heating oven at 50°C for 1 hour and then placed in a heating oven at 100°C for 2 hours for heat treatment to obtain a test piece X having a length of 80 mm, a width of 10 mm and a thickness of 4 mm. Test piece X was used to determine the deflection temperature under load, which will be described later.

[0089] [Preparation of test piece Y] The prepared photocurable resin composition was used to model a three-dimensional rectangular parallelepiped shape of 30 mm x 30 mm x 4 mm using a 3D printer (DWS-020X, a photolithography device using a controlled liquid surface method). The model was produced by stacking 30 mm x 4 mm x 50 μm thick cured layers to a height of 30 mm. The obtained model was washed with isopropanol and the support was removed. Then, the test piece Y was produced by irradiating ultraviolet light for 30 minutes using a UVCuring Unit M (DWS), placing it in a heating oven at 50 ° C for 1 hour, and then placing it in a heating oven at 100 ° C for 2 hours for heat treatment. The test piece Y was used to evaluate the modeling property and sliding property described later.

[0090] [evaluation] (Formability) The success or failure of the moldability was evaluated by evaluating the error in the shape of 30 mm x 30 mm x 4 mm as the dimensional error of the above-mentioned test piece Y. The evaluation criteria are as follows. If evaluation criterion B is satisfied, it is judged that good moldability has been obtained, and if evaluation criterion A is satisfied, it is judged that excellent moldability has been obtained. The dimensions of each side were measured before the heat treatment in the heating oven described above. The results are shown in Tables 3 to 5. A: Dimensional error is within |±3|%. B: The dimensional error is greater than |±3|%. C: Printing is not possible, or the printed object is damaged when removing the supports.

[0091] (Deflection temperature under load) The deflection temperature under load was measured in accordance with JIS K 7191 under the conditions shown below. Measuring device: Toyo Seiki 3M-2 Test environment: 23℃±2℃, humidity 50%±5%RH Test piece: Test piece X, placed so that the surface measuring 80 mm in length and 10 mm in width is the bottom surface. Bending stress: 1.8MPa Initial temperature: 30℃, held for 5 minutes Heating rate: 120℃ / h

[0092] The strain of test piece X was measured when the temperature was increased at a heating rate of 120°C / h, and the temperature at which the strain increased by 0.34 mm from the initial value was taken as the deflection temperature under load, which was used as an index of heat resistance. The evaluation criteria for heat resistance are shown below. If evaluation criterion B is satisfied, it is judged that good heat resistance has been obtained, and if evaluation criterion A is satisfied, it is judged that excellent heat resistance has been obtained. The results are shown in Tables 3 to 5. A: Above 95℃. B: 85℃ or higher but less than 95℃. C: Less than 85°C.

[0093] (Sliding properties) To evaluate the sliding properties, the friction coefficient and specific wear rate were measured. The measurement conditions were in accordance with JIS K 7218 A method. The details are shown below. Measuring device: A&D friction and wear tester MODEL EMF-III-F Test environment: 23℃±2℃, humidity 50%±5%RH Test piece: Test piece Y (size 30mm x 30mm, thickness 4mm) Mating material: S45C, ring shape, surface roughness approx. 0.8μmRa, contact area 2cm 2 Load: 50N Sliding speed: 50cm / s Test duration: 100 minutes Sliding distance: 3km

[0094] (1) Specific wear rate The counter material was pressed against the 30 mm x 30 mm surface of test piece Y with the above load and slid at the above speed. The sliding was stopped after 100 minutes, and the wear weight was measured from the weight of test piece Y before and after the sliding. The wear volume was calculated from the measured wear weight and the specific gravity of test piece Y. The calculated wear volume was divided by the sliding distance and load to obtain the specific wear amount (unit: mm 3 N -1 km -1 ) was used as an index of wear resistance. The evaluation criteria for wear resistance are shown below. If the wear depth exceeded 1.5 mm within 100 minutes after the start of sliding, the measurement limit was marked with an evaluation of C. It was determined that good wear resistance had been obtained if evaluation criterion B was met, and excellent wear resistance had been obtained if evaluation criterion A was met. The results are shown in Tables 3 to 5. A: 0.3 mm 3 N -1 km -1 less than. B: 0.3 mm 3 N -1 km -1 More than 0.5mm 3 N -1 km -1 less than. C: 0.5 mm 3 N -1 km -1 The end.

[0095] (2) Friction coefficient The coefficient of friction was determined by dividing the average value of the friction force for 10 seconds before and after 60 minutes from the start of sliding by the load. The evaluation criteria for the coefficient of friction are as follows. If evaluation criterion B is satisfied, it is judged that a good coefficient of friction has been obtained, and if evaluation criterion A is satisfied, it is judged that an excellent coefficient of friction has been obtained. The results are shown in Tables 3 to 5. A: Less than 0.5. B: 0.5 or more and less than 1.0. C: 1.0 or higher.

[0096] <Examples 2 to 17 and Comparative Examples 1 to 7> Except for changing the type or content of each component as shown in Tables 3 to 5, curable resin compositions were prepared in the same manner as in Example 1 and evaluated in the same manner as in Example 1. The results are shown in Tables 3 to 5. Comparative Example 1 is an example containing multiple types of polyfunctional radical polymerizable compounds as the polyfunctional radical polymerizable compound (A-1) like Example 1, but is a mixture of polyfunctional radical polymerizable compounds having an ethylenically unsaturated group equivalent of less than 250 g / eq. In addition, in Examples 2 to 17 and Comparative Examples 2 to 7, the polyfunctional radical polymerizable compound (A-1) is a mixture containing a polyfunctional radical polymerizable compound having an ethylenically unsaturated group equivalent of 700 g / eq or more, and the mixing ratio is adjusted so that the ethylenically unsaturated group equivalent is 250 g / eq or more and less than 700 g / eq.

[0097] [Table 3]

[0098] [Table 4]

[0099] [Table 5]

[0100] As can be seen from Tables 3 to 5, Examples 1 to 17 according to the present invention all had good moldability. In addition, the deflection temperature under load of test piece X, which was prepared by curing the photocurable resin composition of the present invention, was 85°C or higher, and the friction coefficient of test piece Y was less than 1.0, and the specific wear amount was 0.5 mm 3 N -1 km -1 That is, it was confirmed that by using the photocurable resin composition according to the present invention, an article having both good heat resistance and high sliding properties can be obtained.

[0101] In the results of Table 3, in Comparative Example 1 in which the polyfunctional radical polymerizable compound (A-1) had an ethylenically unsaturated group equivalent of less than 250 g / eq, when removing the support part of the three-dimensional object, the object also had some chipping, and it was not possible to produce a three-dimensional object of the desired shape. On the other hand, in Comparative Example 2 in which the polyfunctional radical polymerizable compound (A-1) had an ethylenically unsaturated group equivalent of 700 g / eq or more, it was not possible to exceed the standard B for the heat resistance evaluation. From these results and the results of Examples 1 to 17, it was confirmed that the ethylenically unsaturated group equivalent of the polyfunctional radical polymerizable compound (A-1) is preferably 250 g / eq or more and less than 700 g / eq.

[0102] In the results of Table 4, Comparative Example 3, in which no polysilsesquioxane particles (B) were added, failed to satisfy the evaluation criteria B for the coefficient of friction and abrasion resistance. In addition, Comparative Example 4, in which the amount of polysilsesquioxane particles (B) added was 35 parts by mass, failed to produce a three-dimensional object because the viscosity of the photocurable resin composition increased. From these results and the results of Examples 1 to 17, it was confirmed that the amount of polysilsesquioxane particles (B) added is preferably 5 to 30 parts by mass relative to a total of 100 parts by mass of the polyfunctional radical polymerizable compound (A-1) and the monofunctional radical polymerizable compound (A-2).

[0103] Comparative Example 5, in which polysiloxane particles D-3 (main component having siloxane bonds with two oxygen atoms per silicon atom) was used instead of polysilsesquioxane particles (B), and Comparative Example 6, in which cage-type silsesquioxane compound D-4 having a methyl group as a substituent, were used, were unable to satisfy the abrasion resistance evaluation criterion B. From these results and the results of Examples 1 to 17, it was confirmed that random-type polysilsesquioxanes, which are mainly composed of silsesquioxanes with three oxygen atoms per silicon atom and which are not dissolved in the radical polymerizable compound (A), are preferred.

[0104] Comparative Example 7, in which the amount of monofunctional radical polymerizable compound (A-2) added was 45 parts by mass, failed to satisfy the heat resistance evaluation criterion B. On the other hand, in Example 8, in which the monofunctional radical polymerizable compound (A-2) was not added and only the polyfunctional radical polymerizable compound (A-1) was used as the radical polymerizable compound (A), the viscosity of the photocurable resin composition was high, and the moldability was evaluated as B. From this result and the results of Examples 1 to 7 and 9 to 17, it was confirmed that the amount of monofunctional radical polymerizable compound (A-2) added is preferably 5 parts by mass or more and less than 40 parts by mass.

[0105] In the results in Table 3, the heat resistance evaluations of Examples 2 and 3 in which the monofunctional radical polymerizable compound (A-2) was an acrylamide-based compound or a maleimide-based compound were A, whereas the heat resistance evaluation of Example 4 in which the monofunctional radical polymerizable compound (A-2) was an acrylate was B. Therefore, it was confirmed that acrylamide-based compounds and maleimide-based compounds are more preferable as the monofunctional radical polymerizable compound (A-2).

[0106] In addition, the wear resistance evaluation and friction coefficient evaluation of Example 2, in which the average particle size of the polysilsesquioxane particles (B) is 5.0 μm, are both A, whereas the evaluations of Example 5, in which the average particle size is 0.8 μm, and Example 14, in which the average particle size is 0.7 μm, are both B. The three-dimensional object obtained by the present invention has a surface roughness on the order of microns. Therefore, the larger the polysilsesquioxane particles (B), the easier it is to roll on the sliding surface, and therefore it is believed that Example 2, which uses the polysilsesquioxane particles (B) with a larger average particle size, received a higher evaluation in terms of sliding properties than Example 5 and Example 14.

[0107] In addition, in the case of modeling using a 3D printer, if the average particle size of the added polysilsesquioxane particles (B) is not small enough relative to the thickness of the laminate, it is expected to affect the adhesion of the laminate interface. Although it depends on the specifications of the device used for modeling and the modeling conditions, in consideration of the results of Examples 1 to 17, it is considered that the average particle size of the polysilsesquioxane particles (B) is preferably 5.0 μm or less.

[0108] In addition, the moldability evaluation and heat resistance evaluation of Example 10, in which the amount of polysilsesquioxane particles (B) added was 10 parts by mass, and Example 11, in which the amount of polysilsesquioxane particles (B) added was 5 parts by mass, were A, while the evaluations of Example 12, in which the amount of polysilsesquioxane particles (B) added was 30 parts by mass, were both B. When a core-shell structure having a core made of soft silicone rubber is used as the polysilsesquioxane particles (B), the viscosity of the photocurable resin composition increases as the amount added increases, and the molding accuracy decreases. Furthermore, the heat resistance also decreases as the amount added increases. Therefore, it is preferable to use polysilsesquioxane particles (B) in a range of 30 parts by mass or less. [Explanation of symbols]

[0109] 10: photocurable resin composition, 11: tank, 12: modeling stage, 13: drive shaft, 14: light source, 15: light energy beam, 16: galvanometer mirror, 17: modeled object, 18: control unit, 100: optical modeling device

Claims

1. A composition comprising a radical polymerizable compound (A), polysilsesquioxane particles (B), and a curing agent (C), The polysilsesquioxane particles (B) have polysilsesquioxane at least on their surfaces, The radical polymerizable compound (A) contains at least a polyfunctional radical polymerizable compound (A-1) in an amount of more than 60 mass %, the polyfunctional radically polymerizable compound (A-1) has an ethylenically unsaturated group equivalent of 250 g / eq or more and less than 700 g / eq; A photocurable resin composition for three-dimensional modeling, comprising 5 parts by mass or more and 30 parts by mass or less of the polysilsesquioxane particles (B) per 100 parts by mass of the radical polymerizable compound (A).

2. the radical polymerizable compound (A) is a mixture of the polyfunctional radical polymerizable compound (A-1) and the monofunctional radical polymerizable compound (A-2), The photocurable resin composition for three-dimensional modeling according to claim 1, characterized in that, in a total of 100 parts by mass of the polyfunctional radical polymerizable compound (A-1) and the monofunctional radical polymerizable compound (A-2), the monofunctional radical polymerizable compound (A-2) is 5 parts by mass or more and less than 40 parts by mass.

3. The photocurable resin composition for three-dimensional modeling according to claim 2, characterized in that the monofunctional radical polymerizable compound (A-2) is 5 parts by mass or more and less than 25 parts by mass in a total of 100 parts by mass of the polyfunctional radical polymerizable compound (A-1) and the monofunctional radical polymerizable compound (A-2).

4. The photocurable resin composition for three-dimensional object formation according to claim 2, characterized in that the monofunctional radical polymerizable compound (A-2) is selected from the group consisting of an acrylamide-based compound, an N-vinyl compound, and a maleimide-based compound.

5. 2. The photocurable resin composition for three-dimensional object formation according to claim 1, wherein the polysilsesquioxane particles (B) are entirely made of polysilsesquioxane.

6. 2. The photocurable resin composition for three-dimensional object formation according to claim 1, wherein the polysilsesquioxane particles (B) have a core-shell structure, and the shell of the core-shell structure is made of polysilsesquioxane.

7. The photocurable resin composition for three-dimensional object formation according to claim 1 , wherein the polysilsesquioxane is a random type polysilsesquioxane.

8. 2. The photocurable resin composition for three-dimensional object formation according to claim 1, wherein the polysilsesquioxane particles (B) have an average particle size of 0.7 μm or more and 5.0 μm or less.

9. The photocurable resin composition for three-dimensional object formation according to claim 1, characterized in that the polyfunctional radical polymerizable compound (A-1) is a single polyfunctional radical polymerizable compound having an ethylenically unsaturated group equivalent of 250 g / eq or more and less than 700 g / eq.

10. The photocurable resin composition for three-dimensional modeling according to claim 1, characterized in that the polyfunctional radical polymerizable compound (A-1) contains a plurality of types of polyfunctional radical polymerizable compounds, and the ethylenically unsaturated group equivalent weighted average of the ethylenically unsaturated group equivalents of each compound is 250 g / eq or more and less than 700 g / eq by mass ratio.

11. The photocurable resin composition for three-dimensional object formation according to claim 10, characterized in that the polyfunctional radical polymerizable compound (A-1) contains a polyfunctional radical polymerizable compound having an ethylenically unsaturated group equivalent of 700 g / eq or more.

12. The photocurable resin composition for three-dimensional modeling according to claim 1, characterized in that the polyfunctional radically polymerizable compound (A-1) has an ethylenically unsaturated group equivalent of 400 g / eq or more and less than 700 g / eq.

13. The photocurable resin composition for three-dimensional object formation according to claim 1, characterized in that the polyfunctional radical polymerizable compound (A-1) is a (meth)acrylate-based compound or a urethane (meth)acrylate-based compound having any one of a polyether structure, a polyester structure, and a polycarbonate structure.

14. 2. The photocurable resin composition for three-dimensional object formation according to claim 1, wherein the curing agent (C) contains at least a photoradical polymerization initiator.

15. A cured product obtained by curing the photocurable resin composition according to claim 1 .

16. Specific wear volume is 0.5 mm 3 ・N -1 ・km -1 The cured product according to claim 15, characterized in that it is less than

17. 16. The cured product according to claim 15, characterized in that it has a coefficient of friction of less than 1.

0.

18. A method for manufacturing a three-dimensional object using a photolithography method, comprising the steps of: disposing a photocurable resin composition in a layer; and curing the layered photocurable resin composition by irradiating the layered photocurable resin composition with light energy based on slice data of a model, A method for producing a three-dimensional object, comprising the step of: forming a photocurable resin composition comprising the photocurable resin composition according to claim 1 ;

19. The method for manufacturing a three-dimensional object according to claim 18, further comprising a step of subjecting the shaped object obtained by the step of curing the shaped object by irradiating the shaped object with light energy to a heat treatment.

20. The method for manufacturing a three-dimensional object according to claim 18, wherein the light energy is light emitted from a laser light source or a projector.

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