Photocurable resin composition

Abstract

Provided is a photocurable resin composition which can obtain a cured product exhibiting flame retardancy and having excellent mechanical strength, and which is suitable for a molding method involving photocuring. The photocurable resin composition is characterized by comprising a component (A): a radical cyclization polymerizable compound, a component (B): a polyfunctional radical polymerizable compound having a polyalkylene glycol skeleton and / or a diisocyanate skeleton, a component (C): a polyfunctional radical polymerizable compound, a component (D): ammonium polyphosphate, and a component (E): a radical polymerization initiator.

Description

Technical Field

[0001] The present invention relates to a method for producing a photocurable resin composition, a cured product and a product. Background Art

[0002] In recent years, against the background of diversification of molding materials and advancement of equipment technology, the use of additive manufacturing (AM) processes as a means of producing products has become increasingly widespread. These processes include molding processes called liquid layer photopolymerization processes (vat photopolymerization processes) or optical molding processes (stereolithography processes). This molding process, which forms a three-dimensional shape by curing a liquid photocurable resin with a laser beam or a lamp, is characterized in that the process can perform high-definition and high-precision molding. At the same time, the molded products produced by photocurable resins have high mechanical strength and environmental resistance. In addition, material properties such as flexural modulus, impact resistance and heat resistance, as well as flame retardancy as a multifunctionalization, are being improved.

[0003] PTL 1 describes that an ink containing a cyclopolymerizable monomer and an oligomer curable material can be used for molding using a 3D printer to obtain a molded product with mechanical properties similar to those of a thermoplastic resin. PTL 2 describes that a resin composition for stereolithography containing a urethane acrylate compound and a salt of a compound having a guanidine structure and an inorganic oxygen-containing acid or a condensate thereof as a flame retardant can be used to obtain a cured product having flame retardancy, heat resistance, and impact resistance.

[0004] Prior art literature

[0005] Patent Literature

[0006] PTL 1: Japanese Patent Application Publication No. 2020-505255

[0007] PTL 2: Japanese Patent Application Publication No. 2021-146689 Summary of the invention

[0008] Problem that the invention aims to solve

[0009] However, when a molded article produced from a photocurable resin is used in products such as electrical and electronic equipment, office automation equipment, cameras or computers, high flame retardancy that complies with IEC standards, ISO standards or national standards is required. Flame retardancy can be ensured by increasing the thickness of the component, but from the perspective of shape freedom, the thickness of the component needs to be reduced, and further flame retardancy is required for the molded material.

[0010] When flame retardant resins are made, halogen-free flame retardants or inorganic fillers are selected from the viewpoint of reducing environmental impact. However, in the case of resins with a high oxygen index such as acrylic resins, a large amount of halogen-free flame retardants or inorganic fillers must be added in order to exert flame retardancy, resulting in deterioration of the mechanical strength of the molded product.

[0011] An object of the present invention is to provide a photocurable resin composition which can provide a cured product having flame retardancy and excellent mechanical strength and is compatible with a molding process using photocuring.

[0012] Solutions for solving problems

[0013] After intensive research to achieve the above-mentioned object, the inventors have completed the present invention. That is, the photocurable composition of the present invention is a photocurable resin composition characterized by comprising the following:

[0014] Component (A): a free radical cyclization polymerizable compound;

[0015] Component (B): a polyfunctional free radical polymerizable compound having a polyalkylene glycol ether skeleton and / or a diisocyanate skeleton;

[0016] Component (D): ammonium polyphosphate; and

[0017] Component (E): a free radical polymerization initiator.

[0018] Effects of the Invention

[0019] According to the present invention, a molded product having high flame retardancy and high mechanical strength can be obtained by using a molding process using photocuring. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] [ Figure 1 ] is a schematic diagram showing an example of the structure of a forming device using the free liquid surface method. DETAILED DESCRIPTION

[0021] The present embodiment relates to a photocurable resin composition, which includes, for example: a free radical cyclization polymerizable compound (component (A)) that forms a polymer having a cyclic structure by free radical polymerization; a polyfunctional free radical polymerizable compound (component (B)) having a polyalkylene glycol ether skeleton and / or a diisocyanate skeleton; a polyfunctional free radical polymerizable compound (component (C)); ammonium polyphosphate (component (D)); and a free radical polymerization initiator (component (E)). Component (A) forms a copolymer structure by free radical polymerization. Component (B) also forms a copolymer structure by free radical polymerization. In the cured product after polymerization, the cyclic structure, especially the five-membered cyclic ether structure, formed by the polymerization of component (A) has the function of absorbing impact, thereby achieving impact resistance. In addition to the cyclic structure formed by the polymerization of component (A), when component (B) has the function of absorbing impact, further impact resistance is achieved. Component (C) forms a copolymer structure by free radical polymerization. Component (C) in turn forms crosslinking points by copolymerization with component (A) and component (B), and has the function of improving heat resistance. Component (D) has the function of exerting flame retardancy by promoting a stable carbonized layer mainly comprising polyphosphoric acid by a dehydration reaction during combustion. It has been found that since the composition contains a radical polymerizable compound having a polyalkylene glycol ether skeleton or a diisocyanate skeleton of component (B) and is preferably compatible with the compound, the dispersion stability of component (D) is improved, and high flame retardancy and impact resistance can be obtained.

[0022] <Component (A): Radical Cyclopolymerizable Compound>

[0023] The radical cyclopolymerizable compound is a compound that forms a cyclic structure by intramolecular polymerization. Specific examples thereof include 1,6-dienes such as diallyl quaternary ammonium salts, 1,6-perfluorodiene, or monofunctional 2-(allyloxymethyl)acrylic acid or its ester. From the viewpoint of compatibility with component (B) and component (C) or polymerization reactivity, monofunctional 2-(allyloxymethyl)acrylic acid or its ester is suitably used.

[0024] <Monofunctional 2-(allyloxymethyl)acrylic acid or its ester>

[0025] The monofunctional 2-(allyloxymethyl) acrylic acid or its ester is represented by the following general formula (1):

[0026] [Chemical formula 1]

[0027]

[0028] In the general formula (1), R is hydrogen or a hydrocarbon group, preferably hydrogen or a hydrocarbon group having 1 to 4 carbon atoms. The hydrocarbon group is a saturated or unsaturated hydrocarbon group which may have a substituent. The hydrocarbon group may be linear, branched or cyclic, and may have an ether bond.

[0029] Examples of hydrocarbon groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, vinyl, allyl, methallyl, crotyl, cyclopropyl, cyclobutyl, methoxymethyl, methoxyethyl, ethoxymethyl, ethoxyethyl, vinyloxyethyl, epoxy, and oxetanyl. Suitable hydrocarbon groups are particularly hydrocarbon groups having 1 to 2 carbon atoms.

[0030] Examples of the substituent which the hydrocarbon group optionally has include a chain unsaturated hydrocarbon group such as a vinyl group, an allyl group, a methallyl group or a crotyl group; a cyclic ether structure such as an epoxy group, a glycidyl group or an oxetanyl group; an alkoxy group such as a methoxy group, an ethoxy group or a methoxyethoxy group; an alkylthio group such as a methylthio group or an ethylthio group; an acyl group such as an acetyl group or a propionyl group; an acyloxy group such as an acetoxy group or a propionyloxy group; an alkoxycarbonyl group such as a methoxycarbonyl group or an ethoxycarbonyl group; an alkylthiocarbonyl group such as a methylthiocarbonyl group or an ethylthiocarbonyl group; a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom; a urea group; an amide group; a cyano group; a hydroxyl group; and a trimethylsilyl group.

[0031] Examples of the component (A) used include commercially available products such as AOMA (manufactured by NIPPON SHOKUBAI CO., LTD.).

[0032] The inclusion of a cyclic structure formed by polymerization of component (A) improves the impact resistance of the cured product. Therefore, based on the total amount of the photocurable resin composition, the content of component (A) is suitably 10% by mass or more and 45% by mass or less, preferably 20% by mass or more and 45% by mass or less, and more preferably 20% by mass or more and 40% by mass or less.

[0033] <Component (B): Polyfunctional radical polymerizable compound having a polyalkylene glycol ether skeleton and / or a diisocyanate skeleton>

[0034] Component (B) is a compound having either a polyalkylene glycol ether skeleton or a diisocyanate skeleton, preferably an oligomer. Component (B) preferably has two or more free radical polymerizable groups. The free radical polymerizable group is preferably a group having a carbon-carbon double bond, and more preferably a (meth)acryloyl group.

[0035] <Alkylene glycol ether>

[0036] In the polyalkylene glycol ether skeleton contained in component (B), the types of alkylene glycol include ethylene glycol, propylene glycol, tetramethylene glycol and neopentyl glycol, and compounds added by polyester, polycaprolactone modification or polycarbonate modification, forming a bond via an ether bond with an isocyanate group or a (meth) acrylic group, etc. From the viewpoint of impact resistance, the alkylene glycol ether desirably has a polyalkylene glycol structure containing two or more consecutive alkylene glycols.

[0037] Examples of the alkylene glycol ethers include diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, nonaethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, polytetraethylene glycol di(meth)acrylate, polyalkylene oxide adducts of dipentaerythritol penta(meth)acrylate, polyalkylene oxide adducts of dipentaerythritol hexa(meth)acrylate bisphenol A, ethoxylated pentaerythritol tetra(methacrylate) polycaprolactone-modified di(meth)acrylate, polycarbonate diol di(meth)acrylate, and polyester di(meth)acrylate.

[0038] <Compounds having a diisocyanate skeleton>

[0039] Among the compounds having a diisocyanate skeleton contained in the component (B), polyfunctional urethane (meth)acrylates can be suitably used.

[0040] <Multifunctional urethane (meth)acrylate>

[0041] The multifunctional urethane (meth) acrylate of component (B) is a compound having a urethane bond and a (meth) acryloyl group, preferably an oligomer. Component (B) is preferably difunctional. Examples of component (B) include substances obtained by reacting a hydroxyl-containing (meth) acrylate compound with a polyisocyanate compound; substances obtained by reacting an isocyanate-containing (meth) acrylate compound with a polyol compound; and substances obtained by reacting a hydroxyl-containing (meth) acrylate compound with a polyisocyanate compound and a polyol compound. Among these, from the viewpoint of providing high impact resistance, substances obtained by reacting a hydroxyl-containing (meth) acrylate compound with a polyisocyanate compound and a polyol compound are particularly preferred.

[0042] In order to achieve both heat resistance and impact resistance of the cured product, component (B) is preferably a polyester-based urethane (meth) acrylate comprising at least an isophorone diisocyanate skeleton, a 1,4-butanediol skeleton and / or a neopentyl glycol skeleton, wherein each skeleton is obtained by repeating a bond selected from the group consisting of an ester bond, an ether bond, a carbonate bond and a urethane bond, and wherein both ends of the oligomer are treated with a hydroxyl-containing (meth) acrylate. In order to improve the impact resistance of the cured product, component (B) is more preferably a polyester-based urethane (meth) acrylate comprising at least an isophorone diisocyanate skeleton, a 1,4-butanediol skeleton and / or a neopentyl glycol skeleton, wherein each skeleton is obtained by repeating a bond selected from the group consisting of an ester bond and a urethane bond, and wherein both ends of the oligomer are treated with a hydroxyl-containing (meth) acrylate.

[0043] The isophorone diisocyanate skeleton can form a urethane bond that helps improve impact resistance, and its cyclic skeleton is also expected to improve heat resistance. The neopentyl glycol skeleton forms a urethane bond with the isophorone diisocyanate skeleton, which helps improve impact resistance, and its two methyl groups restrict molecular movement, which helps improve heat resistance. The 1,4-butanediol skeleton forms a urethane bond with the isophorone diisocyanate skeleton, which helps improve impact resistance, and it suppresses the increase in the viscosity of the material and appropriately forms a repeating unit of a polyester bond, which helps achieve both heat resistance and impact resistance.

[0044] Urethane (meth) acrylate has a molecular weight distribution when preparing an oligomer and then performing (meth) acrylate. The molecular weight of the oligomer is not particularly limited, as long as both the heat resistance and the impact resistance of the cured product are achieved, and the molecular weight is preferably 400 or more and 30,000 or less. If the molecular weight of the oligomer is low, the impact resistance may be low, and if the molecular weight of the oligomer is high, the heat deformation temperature may be low. Therefore, the molecular weight of the oligomer is more preferably 1,000 or more and 10,000 or less, and even more preferably 4,000 or more and 8,000 or less.

[0045] The content of component (B) is not particularly limited, as long as the cured product realizes both heat resistance and impact resistance. However, if the content of component (B) is high, the viscosity of the photocurable resin composition may increase and the fluidity of the material may be low in optical three-dimensional forming or casting forming, which may lead to poor forming and increased bubble entrapment (bubble entrapment). Therefore, based on the total amount of the photocurable resin composition, the content of component (B) is preferably 10% by mass or more and 40% by mass or less. From the consideration of realizing both heat resistance and impact resistance and providing forming stability, the content of component (B) is more preferably 5% by mass or more and 35% by mass or less, and even more preferably 15% by mass or more and 35% by mass or less.

[0046] <Component (C): Polyfunctional radical polymerizable compound>

[0047] Component (C) is a polyfunctional free radical polymerizable compound different from component (B). Component (C) is also a free radical polymerizable compound different from component (A). The polyfunctional free radical polymerizable compound as component (C) has more than 2 free radical polymerizable groups in 1 molecule. The free radical polymerizable group is preferably a group having a carbon-carbon double bond, and more preferably a (meth) acryloyl group. The polyfunctional free radical polymerizable compound as component (C) preferably does not contain the polyalkylene glycol ether skeleton and / or diisocyanate skeleton contained in component (B). Specifically, the polyfunctional free radical polymerizable compound as component (C) preferably has less than 2 and less than 1 alkylene glycol ether in its side chain and does not contain a diisocyanate skeleton. In particular, the polyfunctional free radical polymerizable compound as component (C) preferably has neither a polyalkylene glycol ether skeleton nor a diisocyanate skeleton.

[0048] Examples of component (C) include ethylene glycol di(meth)acrylate, 1,3-butanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, dimethyloltricyclodecane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexamethylene di(meth)acrylate, neopentyl glycol hydroxypivalate di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, tri(acryloyloxyethyl)isocyanurate, tri(methacryloyloxyethyl)isocyanurate, ε-caprolactone-modified tri(2-acryloyloxyethyl)isocyanurate, di(meth)acrylate of ε-caprolactone adduct of neopentyl glycol hydroxypivalate, polyfunctional (meth)acrylate having a fluorine atom, and polyfunctional (meth)acrylate having a siloxane structure.

[0049] From the viewpoint of achieving both heat resistance and impact resistance of the stereolithography product, examples of component (C) suitably used also include compounds having an isocyanurate ring, such as an isocyanurate derivative represented by the following general formula (2).

[0050] [Chemical formula 2]

[0051]

[0052] X in the general formula (2) 1 ~X 3 There is no particular limitation, as long as both heat resistance and impact resistance of the cured product are achieved and optical three-dimensional molding or casting molding can be performed.1 ~X 3 Each is independently selected from a hydrogen atom and a (meth)acryloyl group, and may be the same as or different from each other. In order to achieve both heat resistance and impact resistance of the cured product, X 1 ~X 3 At least two of them are preferably (meth)acryloyl groups.

[0053] Y in the general formula (2) 1 ~Y 3 represents a caprolactone modified group (-C(=O)-(CH 2 ) 5 -O-), and a to c represent a number of 0 or more and less than 2. From the viewpoint of heat resistance, the average value of the sum of a to c is preferably 0 or more and less than 3 and more preferably 0 or more and 1 or less, and from the viewpoint of heat resistance and impact resistance, even more preferably 0 or more and 0.5 or less.

[0054] The content of component (C) is not particularly limited, as long as the heat resistance and impact resistance of the cured product are achieved and optical three-dimensional forming or casting forming can be performed. If the content of component (C) is high, the impact resistance of the cured product may deteriorate, and if the content of component (C) is low, the heat deformation temperature of the cured product may deteriorate, and in some cases, the elastic modulus of the cured product at room temperature may deteriorate. In addition, the viscosity of the photocurable resin composition also varies according to the content of component (C). Therefore, based on the total amount of the photocurable resin composition, the content of component (C) is preferably 5% by mass or more and 50% by mass or less. In order to further achieve both the heat resistance and impact resistance of the cured product and in order to further make it more suitable for optical three-dimensional forming or casting forming, the content of component (C) is more preferably 20% by mass or more and 40% by mass or less. When such high heat resistance is not required, for example, when the cured product is used at room temperature, component (C) is not necessary. If component (C) is not included, the content of component (C) is 0% by mass. That is, the content of component (C) is 0% by mass or more.

[0055] <Component (D): ammonium polyphosphate>

[0056] The ammonium polyphosphate as component (D) is an ammonium salt of a phosphoric acid polymer, and its polymer molecular weight is not particularly limited, and is about 800 to 200,000. Depending on its production method, component (D) can adopt a crystal structure of type I, type II, type III, type IV or type V, and any type thereof can be used.

[0057] From the viewpoint of dispersion stability in a liquid in an uncured state, the number average particle size of component (D) is preferably 0.01 μm or more and 100 μm or less, and particularly preferably 0.01 μm or more and 20 μm or less. When ammonium polyphosphate can be extracted, the number average particle size can be measured with a laser diffraction type particle size distribution measuring device. When ammonium polyphosphate is included in the cured product, the particle sizes of multiple particles can be measured separately from their cross-sectional SEM images and can be calculated as an average value. Component (D) can be used regardless of whether it is surface treated, but from the viewpoint of the combination of component (D) with component (A), component (B) and component (C), component (D) that is not surface treated can be appropriately used.

[0058] Based on the total amount of the photocurable resin composition, the content of component (D) is preferably 10% by mass or more and 30% by mass or less, and more preferably 15% by mass or more and 25% by mass or less. If the content of component (D) is low, flame retardancy may deteriorate, and if the content of component (D) is high, impact resistance may deteriorate.

[0059] <Component (E): Radical Polymerization Initiator>

[0060] The radical polymerization initiator as the component (E) can be appropriately selected according to the curing conditions (eg, irradiation wavelength or irradiation amount) of the curable resin.

[0061] Examples of the polymerization initiator that generates free radicals by light irradiation include, but are not limited to, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-1-butanone, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, 4-phenylbenzophenone, 4-phenoxybenzophenone, 4,4'-diphenylbenzophenone, and 4,4'-diphenoxybenzophenone.

[0062] Examples of polymerization initiators that generate free radicals by heating include, but are not limited to, azo compounds such as azobisisobutyronitrile (AIBN); and peroxides such as benzoyl peroxide, tert-butyl peroxypivalate, tert-butyl peroxyneohexanoate, tert-hexyl peroxyneohexanoate, tert-butyl peroxyneodecanoate, tert-hexyl peroxyneodecanoate, cumyl peroxyneohexanoate, or cumyl peroxyneodecanoate.

[0063] The free radical polymerization initiator can be used alone or in combination of two or more thereof. Based on 100 parts by mass of the free radical polymerizable compound, the addition amount of the free radical polymerization initiator is preferably 0.01 parts by mass or more and 10.00 parts by mass or less. The addition ratio of the free radical polymerization initiator can be selected according to the light irradiation amount and even according to the additional heating temperature. The addition ratio of the free radical polymerization initiator can also be adjusted according to the target average molecular weight of the polymer obtained.

[0064] <Monofunctional radical polymerizable compound>

[0065] To the photocurable resin composition of the present embodiment, a monofunctional radical polymerizable compound other than the component (A) may be added to such an extent that the properties of the cured product do not significantly deteriorate.

[0066] Examples of the monofunctional radical polymerizable compound other than component (A) include the following monofunctional (meth)acrylates. Examples of the monofunctional (meth)acrylate include, but are not limited to, 4-tert-butylcyclohexanol (meth)acrylate, 3,3,5-trimethylcyclohexanol (meth)acrylate, isobornyl (meth)acrylate, cyclic trimethylolpropane formal (meth)acrylate, 3-hydroxy-1-(meth)acryloyloxyadamantane, 1-adamantyl (meth)acrylate, 2-methyl-2-adamantyl (meth)acrylate, dicyclopentenyl (meth)acrylate, 2-isopropyladamantan-2-yl (meth)acrylate, tetrahydrodicyclopentadienyl (meth)acrylate, α-(meth)acryloyloxy-γ-butyrolactone, 2-hydroxy-o-phenylphenol propyl (meth)acrylate, acryloylmorpholine, diethylacrylamide, isopropylacrylamide, hydroxyethylacrylamide, cyclohexyl (meth)acrylate, methyl (meth)acrylate, 2-(meth)acrylate. -ethylhexyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, isooctyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, isobornyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxypolyethylene glycol (meth)acrylate, phenyl glycidyl (meth)acrylate, lauryl (meth)acrylate, isodecyl (meth)acrylate, stearyl (meth)acrylate, isooctyl (meth)acrylate, tridecyl (meth)acrylate, ethoxydiethylene glycol (meth)acrylate, methoxyditripropylene glycol (meth)acrylate, tricyclodecane (meth)acrylate, dicyclopentadienyloxyethyl (meth)acrylate, dicyclopentenyl acrylate, dicyclopentenyloxyethyl acrylate, dicyclopentenyloxymethacrylate, dicyclopentyl acrylate and dicyclopentyl methacrylate.

[0067] A single type of monofunctional free radical polymerizable compound may be added to the extent that the mechanical properties of the cured product are not deteriorated, or a plurality of types of monofunctional free radical polymerizable compounds may be combined. To the extent that the mechanical properties of the cured product are not deteriorated, the content of the monofunctional free radical polymerizable compound is preferably 5% by mass or more and 30% by mass or less based on the total amount of the photocurable resin composition.

[0068] <Other polymerizable compounds>

[0069] Other polymerizable materials may be added to adjust the viscosity or provide functionality. Other polymerizable compounds are not particularly limited, and examples thereof include cationic polymerizable compounds such as monofunctional or difunctional or higher-functional epoxy or oxetane compounds.

[0070] Examples of monofunctional or difunctional or higher functional epoxy and oxetane 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, cyclohexanedimethanol diglycidyl ether, tricyclodecane dimethanol diglycidyl ether, 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexanecarboxylate, 3,4-epoxy-1-methylcyclohexyl 3,4-epoxy-1-methylcyclohexanecarboxylate, 6-methyl -3,4-epoxycyclohexylmethyl-6-methyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-3-methylcyclohexylmethyl-3,4-epoxy-3-methylcyclohexanecarboxylate, 3,4-epoxy-5-methylcyclohexylmethyl-3,4-epoxy-5-methylcyclohexanecarboxylate, 2-(3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy)cyclohexane-m-dioxane, bis(3,4-epoxycyclohexylmethyl)adipate, 3,4-epoxy-6-methylcyclohexanecarboxylate, Dicyclopentadiene diepoxide, ethylenebis(3,4-epoxycyclohexanecarboxylate), dioctyl epoxyhexahydrophthalate, di-2-ethylhexyl epoxyhexahydrophthalate, ε-caprolactone-modified 3',4'-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate, 1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol, bis(3,4-epoxycyclohexyl)methane, 2,2-bis(3,4-epoxycyclohexyl)propane, 1, 1-bis(3,4-epoxycyclohexyl)ethane, alpha-pinene oxide, campholenealdehyde, limonene monoxide, limonene dioxide, 4-vinylcyclohexene monoxide, 4-vinylcyclohexene dioxide, 3-hydroxymethyl-3-methyloxetane, 3-hydroxymethyl-3-ethyloxetane, 3-hydroxymethyl-3-propyloxetane, 3-hydroxymethyl-3-n-butyloxetane and 3-hydroxymethyl-3-propyloxetane.

[0071] The content of other polymerizable compounds is within a range that does not impair the mechanical properties of the cured product and is suitably 5% by mass or more and 30% by mass or less based on the total amount of the photocurable resin composition.

[0072] When a cationic polymerizable compound is added, a polymerization initiator, a photoacid generator or a photobase generator that generates cationic species by light irradiation can be added to the photocurable resin composition to promote the polymerization reaction of the cationic polymerizable compound. Suitable examples of polymerization initiators that generate cationic species by light irradiation include, but are not limited to, iodonium (4-methylphenyl) [4-(2-methylpropyl) phenyl]-hexafluorophosphate. Examples of photoacid generators include, but are not limited to, triarylsulfonium hexafluoroantimonate, triphenylphenacylphosphonium tetrafluoroborate, triphenylsulfonium hexafluoroantimonate, bis-[4-(diphenylsulfonium) phenyl] sulfide bis-hexafluoroantimonate, bis-[4-(di-4'-hydroxyethoxyphenylsulfonium) phenyl] sulfide bis-hexafluoroantimonate, bis-[4-(diphenylsulfonium) phenyl] sulfide bis-hexafluoroantimonate, bis-[4-(diphenylsulfonium) phenyl] sulfide bis-hexafluorophosphate and diphenyliodonium tetrafluoroborate.

[0073] The amount of the polymerization initiator that generates cations added is preferably in the range of 0.01 parts by mass or more and 10.00 parts by mass or less based on 100 parts by mass of the cationically polymerizable compound.

[0074] <Other additives>

[0075] To the photocurable resin composition of the present embodiment, a polymerization inhibitor, a photosensitizer, a light stabilizer, a heat stabilizer, an antioxidant, a chain transfer agent, a curing aid, or the like may be added to such an extent that the performance of the cured product is not significantly deteriorated.

[0076] Examples of polymerization inhibitors include hydroquinone-based polymerization 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 or hydroquinone monoheptyl ether, and phenol-based polymerization inhibitors with substituents such as 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate. However, hydroquinone-based polymerization inhibitors such as hydroquinone and benzoquinone-based polymerization inhibitors such as benzoquinone may cause yellowing when UV irradiated, and are therefore suitable when obtaining a thin film cured product such as a coating. Examples of polymerization inhibitors for reaction or preservation include but are not limited to those described above. Based on the total amount of the photocurable resin composition, the addition amount of the polymerization inhibitor is preferably in the range of 0.01% by mass or more and 1.00% by mass or less. The polymerization inhibitor can be used alone or in combination with two or more thereof. Considering low coloring, specifically, a combination of hydroquinone-based polymerization inhibitors is preferably used.

[0077] Examples of photosensitizers include benzophenone, 4,4-diethylaminobenzophenone, 1-hydroxycyclohexylphenylketone, isoamyl p-dimethylaminobenzoate, methyl 4-dimethylaminobenzoate, benzoin, benzoin ethyl ether, benzoin isobutyl ether, benzoin isopropyl ether, 2,2-diethoxyacetophenone, methyl o-benzoylbenzoate, 2-hydroxy-2-methyl-1-phenylpropane-1-one, and acylphosphine oxide. Based on the total amount of the photocurable resin composition, the amount of the photosensitizer added is preferably in the range of 0.01% by mass or more and 10.00% by mass or less.

[0078] The light stabilizer is not particularly limited as long as the light stabilizer does not significantly affect the performance of the cured product. Examples of light stabilizers 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-amylphenol, 2-(2H-benzotriazole-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol, Phenol, 2,2'-methylenebis[6-(2H-benzotriazol-2-yl)]-4-(1,1,3,3-tetramethylbutyl)phenol or 2-(2H-benzotriazol-2-yl)-6-dodecyl-4-methylphenol; cyanoacrylate compounds such as 2-cyano-3,3-diphenylacrylate or 2-ethylhexyl 2-cyano-3,3-diphenylacrylate; triazine compounds; and benzophenone compounds such as octabenzophenone or 2,2',4,4'-tetrahydrobenzophenone. Light stabilizers can sometimes act as photosensitizers. In this case, it is not necessary to add a photosensitizer. The amount of light stabilizer added is preferably in the range of 0.01 mass % or more and 10.00 mass % or less based on the total amount of the photocurable resin composition.

[0079] The heat stabilizer is not particularly limited as long as the heat stabilizer does not significantly affect the properties of the cured product. Examples of the heat stabilizer include alkyl esters having 7 to 9 carbon atoms in the side chain of pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)]propionate, octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, or 3,5-bis(1,1-dimethylethyl)-4-hydroxyphenylpropionic acid; hindered phenol compounds such as 4,6-bis(octylthiomethyl)-o-cresol, 4,6-bis(dodecylthiomethyl)-o-cresol, ethylenebis(oxyethylene)bis[3-(5-tert-butyl-4-hydroxy-m-tolyl)]propionate, or hexamethylenebis[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 bis(octadecyl)-3,3'-thiodipropionate. The amount of the heat stabilizer added is preferably in the range of 0.01% by mass or more and 10.00% by mass or less based on the total amount of the photocurable resin composition.

[0080] The antioxidant is not particularly limited as long as the antioxidant does not significantly affect the performance of the cured product. Examples of antioxidants include hindered amine compounds, such as bis(2,2,6,6-tetramethyl-4-piperidinyl)sebacate or bis(1,2,2,6,6-pentamethyl-4-piperidinyl)[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]butylmalonate. Based on the total amount of the photocurable resin composition, the amount of the antioxidant added is preferably in the range of 0.01 mass % or more and 10.00 mass % or less.

[0081] 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-butyl mercaptan, cyclohexanethiol, cyclohexyl 3-mercaptopropionate, 1-decyl mercaptan, 2,4-diphenyl-4-methyl-1-pentene, 1-dodecyl mercaptan, dodecyl 3-mercaptopropionate, 2-ethylhexyl thioglycolate, 2-ethylhexyl 3-mercaptopropionate, ethyl mercaptoacetate, 1-hexadecyl mercaptan, hexyl 3-mercaptopropionate, 2-mercaptoethanol, 3-mercapto-1,2-propylene glycol, mercaptoacetic acid, sodium 2-mercaptoethanesulfonate, 3-mercaptopropionic acid, methyl mercaptoacetate, mercaptoate), mercaptosuccinic acid, methyl 3-mercaptopropionate, octadecyl 3-mercaptopropionate, octyl 3-mercaptopropionate, 1-octanethiol, 1-octadecylthiol, tridecyl 3-mercaptopropionate and thiophenol; and as multifunctional thiols, bis(2-mercaptoethyl)sulfide, 3,6-dioxa-1,8-octanedithiol, trimethylolpropane tris(3-mercaptopropionate), 1,4-butanediol bis(thioglycolate), pentaerythritol tetrakis(3-mercaptopropionate), 1,4-benzenethiol, 3,7-dithia-1,9-nonanol, DL-1, 4-dimercapto-2,3-butanediol, 1,5-dimercaptonaphthalene, dithioerythritol, ethylenebisthioglycolate, pentaerythritol tetrakis(thioglycolate), tris[(3-mercaptopropionyloxyethyl)-isocyanurate, tetraethylene glycol bis(3-mercaptopropionate), dipentaerythritol hexa(3-mercaptopropionate), 3,3'-thiodipropionic acid, dithiodipropionic acid, and laurylthiopropionic acid (dodecylthiopropionic acid); and TS-G, C3TS-G, TA-G, and LDAIC (manufactured by SHIKOKUCHEMICALS CORPORATION) as commercially available products, and Karenz MTPE1, BD1, NR1, and TPMB (manufactured by Showa Denko KK). The amount of the chain transfer agent or curing aid added is preferably in the range of 0.01% by mass or more and 10.00% by mass or less based on the total amount of the photocurable resin composition.

[0082] Pigments or fillers can also be added to adjust viscosity or impart functions. The filler is not particularly limited as long as the filler does not deteriorate the mechanical properties of the cured product. The types of fillers include metal salts, metal oxides, polymer fine particles, rubber particles, inorganic fibers, organic fibers and carbon. Examples of metal oxides include, but are not limited to, silicon oxide, titanium oxide and aluminum oxide. Examples of polymer fine particles include, but are not limited to, acrylic fine particles, polystyrene fine particles and nylon particles. Examples of rubber particles include, but are not limited to, butadiene rubber particles, styrene-butadiene rubber copolymer particles, acrylonitrile-butadiene copolymer rubber particles, or saturated rubber particles obtained by hydrogenating or partially hydrogenating such diene rubbers, crosslinked butadiene rubber particles, isoprene rubber particles, chloroprene rubber particles, natural rubber particles, silicone rubber particles, ethylene / propylene / diene monomer terpolymer rubber particles, acrylic rubber particles and acrylic / silicone composite rubber particles. Examples of organic fibers include, but are not limited to, nylon fibers and cellulose nanofibers. The content thereof may be within a range that does not impair the mechanical properties of the photocurable resin composition, and is preferably 0.01% by mass or more and 30% by mass or less based on the total amount of the photocurable resin composition.

[0083] <Method for preparing photocurable resin composition>

[0084] The preparation method of the photocurable resin composition is not particularly limited, and the simplest method thereof is to weigh all materials and then heat and stir them. However, if there is a concern about polymerization by heating, a polymerization inhibitor may be appropriately added. If uniform mixing is difficult only by heating, the photocurable resin composition may be prepared by dissolving all materials in a solvent such as acetone and then distilling out the solvent. In addition, stirring may be performed with a dispersing machine such as an ultrasonic homogenizer, a ball mill or a disc mill.

[0085] <Product Forming Method>

[0086] In the step of curing the photocurable resin composition, the shape of the cured product and the curing method are not particularly limited. Examples of the curing method include a method of coating the photocurable resin composition on a substrate and then irradiating it with light; a method of injecting the photocurable resin composition into a mold and then irradiating it with light; and an optical three-dimensional forming process (stereolithography) involving layer-by-layer growth of a thin film of a cured product.

[0087] The method for applying the photocurable resin composition to the substrate is not particularly limited. For example, the photocurable resin composition can be applied to the substrate to the desired film thickness to form a coating film using a contact transfer coating device such as a roller coater, a reverse coater, a rod coater or a slit coater, or a non-contact coating device such as a spin coater (spin coating device) or a curtain flow coater. Stereolithography using the photocurable resin composition of the present invention can be performed using any previously known stereolithography process and equipment. The method preferably includes a method in which a process of photocuring the photocurable resin composition to a predetermined thickness to form a cured layer is repeated multiple times to cause layer-by-layer growth. Typical examples of preferred stereolithography processes include the following method: a process comprising supplying a photocurable resin composition with a predetermined thickness and a process of curing the photocurable resin composition with a predetermined thickness based on slice data generated according to three-dimensional shape data of the production target object (three-dimensional model) is repeated multiple times.

[0088] Stereolithography processes are roughly divided into two types: free liquid surface method and regulated liquid surface method.

[0089] Figure 1 The figure shows a configuration example of a forming device 100 using a free liquid surface method. The forming device 100 has a tank 11 containing a liquid photocurable resin composition 10. A forming table 12 is provided inside the tank 11, and the forming table 12 can be driven in a vertical direction by a drive shaft 13. Active energy rays 15 emitted from a light source 14 for curing the photocurable resin composition 10 are changed in irradiation position by a galvanometer mirror 16 and scanned on the surface of the tank 11. Figure 1 In FIG. 1 , the scanning range is shown by a thick dashed line. The galvanometer mirror 16 is controlled by a controller 18 according to the slice data.

[0090] The thickness d of the photocurable resin composition 10 cured by the active energy ray 15 is a value determined based on the setting when the slice data is generated, and affects the accuracy of the obtained product (reproducibility of the three-dimensional shape data of the formed product). The controller 18 controls the driving amount of the driving shaft 13 to achieve the thickness d.

[0091] First, the controller 18 controls the drive shaft 13 based on its setting, and supplies the photocurable resin composition to the forming table 12 with a thickness of d. Based on the slice data, the liquid photocurable resin composition on the forming table 12 is irradiated with active energy rays 15 to obtain a cured layer with a desired pattern, thereby forming a cured layer. Then, the forming table 12 moves in the direction of the hollow arrow, and the uncured photocurable resin composition is supplied to the surface of the cured layer with a thickness of d. Then, based on the slice data, the uncured photocurable resin composition is irradiated with active energy rays 15 to form a cured product integrated with the previously formed cured layer. This process of curing the photocurable resin composition in a layered form can be repeated to obtain the desired three-dimensional formed object 17.

[0092] When the surface of the photocurable resin composition is irradiated with active energy light to form a cured layer having a predetermined shape pattern, the resin can be cured in a point-drawing or line-drawing manner using energy light focused in a dot-shaped or line-shaped form. Alternatively, the resin can be cured by irradiating active energy light in a planar manner through a planar drawing mask formed by arranging a plurality of micro shutters such as liquid crystal shutters and digital micromirror shutters.

[0093] Similar to the forming by the free liquid surface method, the forming by the regulating liquid surface method is also preferred. The forming apparatus using the regulating liquid surface method is configured so that Figure 1 The forming table 12 of the forming device 100 is arranged to make the formed object 17 rise above the liquid surface, and a light irradiation unit is arranged below the groove 11. A typical forming example by adjusting the liquid level method is as follows. First, the supporting surface of the supporting table set for free lifting is at a predetermined distance from the bottom surface of the groove containing the photocurable resin composition, and the photocurable resin composition is supplied between the supporting surface of the supporting table and the bottom surface of the groove. Then, according to the slice data through the laser light source or the projector, the photocurable resin composition between the supporting surface of the supporting table and the bottom surface of the groove is selectively irradiated with light from the bottom surface side of the groove containing the photocurable resin composition. The photocurable resin composition between the supporting surface of the supporting table and the bottom surface of the groove is cured by light irradiation to form a solid cured layer. Afterwards, the cured layer is peeled off from the bottom surface of the groove by raising the supporting table.

[0094] Subsequently, the height of the support table is adjusted so that the distance between the solidified layer formed on the support table and the bottom surface of the groove is a predetermined distance. Thereafter, similarly to the above, a photocurable resin composition is supplied between the bottom surface of the groove and the solidified layer and light is irradiated according to the slice data to form a new solidified layer between the bottom surface of the groove and the solidified layer. This process can be repeated multiple times to obtain a molded product 17 in which a plurality of solidified layers are grown integrally.

[0095] The molded article 17 thus obtained can be taken out from the tank 11, and any unreacted photocurable resin composition remaining on the surface of the molded article can be removed and then post-treated as necessary to obtain a desired product.

[0096] Examples of post-processing include washing, post-curing, cutting, polishing, and assembly.

[0097] Examples of detergents that can be used for washing include alcoholic organic solvents represented by isopropyl alcohol or ethanol. Other examples of detergents that can be used include ketone organic solvents represented by acetone, ethyl acetate or methyl ethyl ketone and aliphatic organic solvents represented by terpenes.

[0098] After washing, post-curing can be performed by light irradiation, heat irradiation, or both as needed. Post-curing can cure any unreacted photocurable resin composition remaining on the surface and inside of the molded object, suppress the stickiness of the surface of the three-dimensional molded object, and in addition, improve the initial strength of the three-dimensional molded object.

[0099] Examples of active energy rays may include ultraviolet rays, electron beams, X-rays, radioactive rays and high frequency waves. Among them, ultraviolet rays with a wavelength of 300nm to 430nm are preferably used due to their high versatility. As the light source of this ultraviolet light, ultraviolet lasers (such as semiconductor pumped solid lasers, Ar lasers or He-Cd lasers), high pressure mercury lamps, ultrahigh pressure mercury lamps, mercury lamps, xenon lamps, halogen lamps, metal halide lamps, ultraviolet LEDs (light emitting diodes) or fluorescent lamps, etc. can be used. In particular, due to the excellent light focusing, the energy level can be increased to reduce the forming time and high forming accuracy can be provided, so ultraviolet lasers are preferably used.

[0100] <Purpose>

[0101] The photocurable resin composition of the present invention can be suitable for additive manufacturing (AM) processes, and in particular stereolithography processes. In addition, the cured product and formed product obtained by the 3D printer of the present invention can be widely used in the field of optical three-dimensional forming. The application field is not subject to any limitation, but typical examples thereof include prototype models, design models, working models, basic models for producing molds, direct molds for prototype molds, service parts and housings of industrial products (including products such as electrical and electronic equipment, office automation equipment, cameras or computers); and components of industrial products. The photocurable resin composition of the present invention can be particularly used for the production of industrial products or components such as those requiring flame retardancy and impact resistance.

[0102] [Example]

[0103] <<Examples 1 to 19 and Comparative Examples 1 to 5>>

[0104] <Component>

[0105] The components used in Examples and Comparative Examples are shown in Table 1, respectively.

[0106] [Table 1]

[0107]

[0108] <Production of photocurable resin composition>

[0109] The components were prepared and mixed uniformly in the formulation ratio shown in Table 2. The formulation ratio (composition) shown in Table 2 is expressed as a mass percentage based on the total amount of the photocurable resin composition.

[0110] <Production of Cured Material for Test Pieces>

[0111] The prepared photocurable resin composition was used to prepare a cured product by the following method. A 3D printer (product name "Foto 8.9", manufactured by Flashforge) was used to grow the photocurable resin composition layer by layer in the width direction of the test piece with a thickness of 100 μm and an irradiation time of 10 seconds per layer as a primary cure to prepare a cured product. The cured product was washed with an organic solvent and subjected to a secondary curing treatment of 1 hour with a secondary curing device (product name "Formcure", manufactured by Formlabs). In addition, the product was placed in a heating oven at 100 ° C and subjected to a heat treatment of 1 hour to obtain a cured product for the test piece.

[0112] <Evaluation of flame retardancy>

[0113] Using each prepared test piece (length: 125 mm, width: 13 mm, thickness: 1.5 mm or 3 mm), V-0, V-1 and V-2 were determined based on the UL94-20 mm vertical flammability test according to the afterflame time or afterglow time of the sample after flame contact, and the presence or absence of burning or falling objects. Grade A is better than Grade B and Grade B is better than Grade C.

[0114] A: V-1 or V-0 when the test piece thickness is 1.5 mm.

[0115] B: V-1 or V-0 when the test piece thickness is 3 mm.

[0116] C: Burning, no level.

[0117] <Evaluation of impact resistance>

[0118] Each test piece (length: 80mm, width: 10mm, thickness: 4mm) was used to form a 45° notch with a depth of 2mm in its center according to JIS K 7111 with a notch forming machine (product name "Notching Tool A-4", manufactured by Toyo Seiki Seisaku-sho, Ltd.). Afterwards, the sample was broken from the back of the notch with an energy of 2J using an impact tester (product name "IMPACT TESTER IT", manufactured by Toyo Seiki Seisaku-sho, Ltd.). The energy required for the fracture was calculated based on the angle at which the hammer that had been swung to 150° swung upward after the test piece broke, and the Charpy impact strength was used as an indicator of impact resistance. Impact resistance was evaluated according to the following benchmarks. Grade A is better than Grade B and Grade B is better than Grade C.

[0119] A: Charpy impact strength is 3kJ / m 2 above.

[0120] B: Charpy impact strength is 1kJ / m 2 Above and less than 3kJ / m 2 .

[0121] C: Charpy impact strength is less than 1kJ / m 2 .

[0122] <Evaluation of heat resistance>

[0123] The deflection temperature under load was measured using each of the prepared test pieces (length: 80 mm, width: 10 mm, thickness: 4 mm) with an HDT tester (manufactured by Toyo Seiki Seisaku-sho, Ltd.) according to JIS 7191-1A method and JIS 7111-1. The deflection temperature under load was evaluated according to the following criteria. Grade A was better than Grade B and Grade B was better than Grade C.

[0124] A: The deflection temperature under load is 70° C. or higher.

[0125] B: The deflection temperature under load is 50°C or more and less than 70°C.

[0126] C: The deflection temperature under load is less than 50°C.

[0127] <Overall Evaluation>

[0128] A: A was obtained in all the evaluations of flame retardancy, impact resistance, and heat resistance.

[0129] B: A or B was obtained in the evaluation of flame retardancy, impact resistance, and heat resistance, and B was obtained in one or more of the evaluations.

[0130] C: A or B was obtained in the evaluation of flame retardancy and impact resistance, and C was obtained in the evaluation of heat resistance.

[0131] D: C was obtained in one or more of the evaluations of flame retardancy and impact resistance.

[0132]

[0133] Table 2 shows that the flame retardancy of the cured products of Examples 1 to 19 is high when compared to the cured products of Comparative Example 1 not containing component (D), Comparative Example 2 containing condensed phosphate ester (F-1) instead of component (D), Comparative Example 3 containing polyphosphate melamine (F-2) instead of component (D), and Comparative Example 4 not containing component (B). Table 2 also shows that the heat resistance of the cured products of Examples 1 to 18 containing component (C) is high when compared to the cured product of Example 19 not containing component (C). In Comparative Example 5 not containing component (A), due to the high viscosity of the photocurable resin composition, the molding is poor when formed with a 3D printer, and thus the cured product required for the evaluation formed by the 3D printer cannot be obtained. In Example 19 not containing component (C), due to the low elastic modulus of the primary cured product composition, the molding is poor when formed with a 3D printer, and thus the cured product required for the evaluation formed by the 3D printer cannot be obtained. However, for Comparative Example 5 and Example 19, a test piece prepared by casting by injecting the resin composition into a mold having a cavity of the same shape as that of the test piece formed by the 3D printer may be evaluated.

[0134] As described above, a formed product having high flame retardancy and excellent impact resistance and heat resistance can be obtained.

[0135] The present invention is not limited to the above-described embodiments, and various modifications and variations can be made without departing from the spirit and scope of the present invention. Therefore, the following claims are attached to disclose the scope of the present invention.

[0136] This application claims priority based on Japanese Patent Application No. 2022-172965 filed on October 28, 2022, the entire contents of which are incorporated herein by reference.

[0137] 10 Curable resin composition

[0138] 11 slots

[0139] 12 units

[0140] 13 Drive shaft

[0141] 14 Light Source

[0142] 15 Active Energy Ray

[0143] 16 Galvanometer mirror

[0144] 17 Forming

[0145] 18 Controller

[0146] 100 Forming equipment

Claims

1. A photocurable resin composition comprising: Component (A): a free radical cyclization polymerizable compound; Component (B): a polyfunctional free radical polymerizable compound having a polyalkylene glycol ether skeleton and / or a diisocyanate skeleton; Component (D): ammonium polyphosphate; and Component (E): a free radical polymerization initiator.

2. The photocurable resin composition according to claim 1, Features Component (A) is a 1,6-diene compound and has an ether bond in its structure.

3. The photocurable resin composition according to claim 1 or 2, Features Component (A) is a monofunctional 2-(allyloxymethyl)acrylic acid or an ester thereof and has a structure represented by the following general formula (1): [Formula 1] Wherein R is a hydrogen atom or a hydrocarbon group.

4. The photocurable resin composition according to claim 3, Features R is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms.

5. The photocurable resin composition according to any one of claims 1 to 4, Features Component (B) is a polyfunctional urethane (meth)acrylate having a diisocyanate skeleton.

6. The photocurable resin composition according to any one of claims 1 to 5, Features Component (B) is a polyester-based urethane (meth)acrylate having at least an isophorone diisocyanate skeleton, a 1,4-butanediol skeleton and / or a neopentyl glycol skeleton.

7. The photocurable resin composition according to any one of claims 1 to 6, Features The content of the component (B) is 10% by mass or more and 40% by mass or less based on the total amount of the photocurable resin composition.

8. The photocurable resin composition according to any one of claims 1 to 7, Features The content of the component (D) is 10% by mass or more and 30% by mass or less based on the total amount of the photocurable resin composition.

9. The photocurable resin composition according to any one of claims 1 to 8, Features The content of the component (A) is 10% by mass or more and 45% by mass or less based on the total amount of the photocurable resin composition.

10. The photocurable resin composition according to any one of claims 1 to 9, Features Contains component (C): a polyfunctional free-radically polymerizable compound different from component (B).

11. The photocurable resin composition according to any one of claims 1 to 10, Features The content of the component (C) is 5% by mass or more and 50% by mass or less based on the total amount of the photocurable resin composition.

12. The photocurable resin composition according to claim 10 or 11, Features Component (C) has a (meth)acryloyl group.

13. The photocurable resin composition according to any one of claims 10 to 12, Features Component (C) is a polyfunctional radical polymerizable compound having no polyalkylene glycol ether skeleton and / or diisocyanate skeleton.

14. The photocurable resin composition according to any one of claims 10 to 13, Features Component (C) is a polyfunctional radical polymerizable compound having neither a polyalkylene glycol ether skeleton nor a diisocyanate skeleton.

15. The photocurable resin composition according to any one of claims 10 to 14, Features A compound having an isocyanurate ring is contained as component (C). 16 . A cured product obtained by curing the photocurable resin composition according to claim 1 . 17 . A method for producing an article, comprising repeating a plurality of times a step of photocuring the photocurable resin composition according to claim 1 to form a cured layer at a predetermined thickness.

18. A method for producing a product according to claim 17, Features include: A step of supplying the photocurable resin composition at a predetermined thickness, and a step of irradiating the photocurable resin composition with light energy based on slice data of a three-dimensional model to cure the photocurable resin composition.

19. The method for producing the product according to claim 17, Features The method further comprises a step of washing or post-curing the formed article, wherein the formed article is obtained by repeating a step of supplying the photocurable resin composition at a predetermined thickness and a step of irradiating the photocurable resin composition with light energy to cure the photocurable resin composition a plurality of times.

20. A product obtained by using the cured product according to claim 16, Features The product is an electrical or electronic device, an office automation device, a camera or a computer.

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