Photocurable resin composition for laser drawing, three-dimensional object, and method for producing three-dimensional object

Abstract

To provide a photocurable resin composition for laser drawing that allows high-precision production of fine three-dimensional objects by focusing a laser beam within the resin composition.SOLUTION: A photocurable resin composition for laser drawing comprises a photocurable compound containing a (meth)acryloyl group, a photopolymerization initiator, and an aromatic isocyanate having two or more functional groups.SELECTED DRAWING: None

Description

[Technical Field]

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

[0002] In recent years, there has been a demand for miniaturization of various electronic devices, and there is a demand for obtaining fine three-dimensional objects on the order of microns or nanometers. As a method for producing such fine three-dimensional objects, a method has been proposed in which a laser is focused inside a photocurable resin composition and only the resin composition near the focus of the laser is cured (for example, Patent Document 1). Patent Document 1 describes that microfabrication below the diffraction limit of light is performed by using a femtosecond pulse laser or the like and utilizing two-photon absorption of the resin composition. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Laid-Open No. 2003-1599 Summary of the Invention [Problem to be solved by the invention]

[0004] However, the resin composition used for the above-mentioned modeling is usually a liquid composition with fluidity. When such a resin composition is irradiated with a laser and a volume change occurs due to curing, the surrounding resin composition flows into the volume-decreased portion, causing the resin composition to flow. As a result, the position of the previously formed cured product is easily shifted, and the surrounding resin composition is easily irradiated with the laser during laser irradiation, making it difficult to obtain a three-dimensional object with the desired accuracy.

[0005] The present invention has been made in view of the above-mentioned problems. It is an object of the present invention to provide a photocurable resin composition for laser drawing that can be used to accurately produce a fine three-dimensional object by focusing a laser beam inside the composition. Another object of the present invention is to provide a three-dimensional object obtained from the photocurable resin composition for laser drawing, and a method for producing a three-dimensional object using the same. [Means for solving the problem]

[0006] The present invention provides the following photocurable resin composition for laser writing. [1] A photocurable resin composition for laser writing, comprising a photocurable compound containing a (meth)acryloyl group, a photopolymerization initiator, and a difunctional or higher aromatic isocyanate. [2] The photocurable resin composition for laser writing according to [1], wherein the aromatic isocyanate is diphenylmethane diisocyanate. [3] The photocurable resin composition for laser writing according to [1] or [2], wherein the refractive index of the cured product for light with a wavelength of 589 nm at 25°C is 1.60 or more and the Abbe number of the cured product for light with a wavelength of 589 nm at 25°C is 25 or less. [4] The photocurable resin composition for laser writing according to any one of [1] to [3], wherein the photocurable compound contains a fluorene-containing (meth)acrylate having two or more (meth)acryloyl groups and a fluorene structure in the molecule. [5] The photocurable resin composition for laser writing according to [4], wherein the amount of the fluorene-containing (meth)acrylate is 30% by mass or more and 70% by mass or less based on the total amount of the photocurable compounds. [6] A photocurable resin composition for laser writing according to any one of [1] to [5], wherein the photocurable compound contains a sulfur-containing (meth)acrylate containing two or more (meth)acryloyl groups and a sulfur atom in the molecule. [7] The photocurable resin composition for laser writing according to [6], wherein the sulfur-containing (meth)acrylate is a (meth)acrylic acid thioester compound represented by the following general formula (1): [ka] (In general formula (1), X represents an alkylene group having 1 to 4 carbon atoms, which may be bonded to a group represented by the following general formula (2), and in which any methylene group may be substituted with a carbonyl group; n represents an integer of 5 or more; R 1 and R 2 each independently represents a hydrogen atom or a methyl group. [ka] (In general formula (2), R 3 represents a hydrogen atom or a methyl group, Z represents an alkylene group having 1 to 4 carbon atoms, and p represents an integer of 1 or more.

[0007] The present invention provides the following three-dimensional object and method for manufacturing the three-dimensional object. [8] A three-dimensional object comprising a cured product of the photocurable resin composition for laser writing according to any one of [1] to [7] above. [9] A method for producing a three-dimensional object, comprising the steps of: forming a layer containing the photocurable resin composition for laser drawing according to any one of [1] to [7] above on a laser-transparent substrate; provisionally curing the layer containing the photocurable resin composition for laser drawing in air; and irradiating a laser through the substrate into the provisionally cured photocurable resin composition for laser drawing.

[10] The method for manufacturing a three-dimensional object according to [9], wherein the laser is a femtosecond pulse laser. [Effects of the Invention]

[0008] According to the photocurable resin composition for laser writing of the present invention, it is possible to produce a fine three-dimensional object with high precision by concentrating a laser beam inside the composition. DETAILED DESCRIPTION OF THE INVENTION

[0009] The photocurable resin composition for laser drawing, the three-dimensional object, and the method for manufacturing the three-dimensional object of the present invention will be described below using specific embodiments as examples, although the photocurable resin composition for laser drawing, the three-dimensional object, and the method for manufacturing the three-dimensional object of the present invention are not limited to these embodiments.

[0010] 1. Photocurable resin composition for laser drawing The photocurable resin composition for laser writing of the present invention (hereinafter also simply referred to as "resin composition") can be used in a method for manufacturing a three-dimensional object in which a laser is focused inside the resin composition and only the resin composition near the focal point of the laser is cured. However, the use of the resin composition of the present invention is not limited to this method, and the resin composition can also be used in other methods for manufacturing three-dimensional objects.

[0011] As mentioned above, conventional resin compositions for three-dimensional modeling have a problem in that they tend to flow during laser scanning, preventing the precision of the resulting three-dimensionally modeled object from being sufficiently improved. In contrast, the resin composition of the present invention contains a photocurable compound, a photopolymerization initiator, and a bifunctional or higher aromatic isocyanate. When the resin composition is left standing in the air, the aromatic isocyanate reacts with moisture in the air to form a crosslinked structure within the resin composition. This makes the resin composition less likely to flow, and even if a portion of the resin composition is cured by laser irradiation, the other portions are less likely to flow. Therefore, misalignment and an increase in the processing line width are less likely to occur during laser scanning, making it possible to produce three-dimensionally modeled objects with extremely high precision.

[0012] The resin composition of the present invention only needs to contain a photocurable compound, a photopolymerization initiator, and an aromatic isocyanate, and may further contain other components as necessary. Each component will be described in detail below.

[0013] (photocurable compound) The photocurable compound of the present invention may be a compound having an ethylenically unsaturated bond group and capable of being cured by the active species generated from the photopolymerizable compound described below. The ethylenically unsaturated bond group refers to a group containing an ethylenically unsaturated double bond. Examples of the ethylenically unsaturated bond group include a (meth)acryloyl group, a vinyl group, and an allyl group. The type of photocurable compound is appropriately selected depending on the application of the resin composition and the type and performance of the desired three-dimensional object. The resin composition may contain only one photocurable compound, or two or more types. Among the above ethylenically unsaturated bond groups, a compound containing a (meth)acryloyl group is preferred in terms of reactivity, availability, and the like. Below, an example will be described in which the photocurable compound has a (meth)acryloyl group. However, the photocurable compound is not limited to these. In this specification, the term "(meth)acryloyl" refers to either methacryloyl, acryloyl, or a mixture thereof. The term "(meth)acrylate" refers to any of methacrylate, acrylate, and mixtures thereof, and the term "(meth)acrylic" refers to any of methacrylic, acrylic, and mixtures thereof.

[0014] Here, the number of (meth)acryloyl groups contained in the photocurable compound is preferably 2 or more, more preferably 2 or more and 5 or less, from the viewpoint of the curability of the resin composition and the strength of the resulting three-dimensionally shaped object. However, the resin composition may partially contain a photocurable material having only one (meth)acryloyl group.

[0015] Examples of preferred photocurable compounds in the present invention include fluorene-containing (meth)acrylates, which have two or more (meth)acryloyl groups and a fluorene structure in the molecule. When the photocurable compound contains the fluorene-containing (meth)acrylate, the refractive index of the cured product of the resin composition tends to increase. Cured products with high refractive indexes are very useful as optical materials, semiconductor materials, and sensor materials, and can be used in a variety of optical products.

[0016] Specific examples of the fluorene-containing (meth)acrylate include compounds represented by the following general formula (A): The resin composition may contain only one type of the fluorene-containing (meth)acrylate, or may contain two or more types.

[0017] [ka]

[0018] In the above general formula (A), Z 1 and Z 2 each independently represents an aromatic ring or an alkylene group, which may be substituted with an alkyl group or an alkoxy group. The aromatic ring is preferably a benzene ring or a naphthalene ring, and more preferably a benzene ring. The alkylene group preferably has 1 to 4 carbon atoms, and more preferably 1 to 3 carbon atoms.

[0019] R 1 and R 3 each independently represents an alkylene group having from 1 to 10 carbon atoms, preferably from 1 to 4 carbon atoms, more preferably from 1 to 3 carbon atoms, still more preferably 2 or 3, and particularly preferably 2 (ethylene group). x and y each independently represent an integer of 0 or greater, preferably from 0 to 2 carbon atoms, more preferably 0 or 1.

[0020] R 2 and R 4 each independently represents a hydrogen atom or a methyl group, and is preferably a hydrogen atom.

[0021] Z 3 and Z 4 each independently represents an aromatic ring or an alkyl group which may be substituted with an alkyl group or an alkoxy group. 3 and Z 4 are each independently preferably an aromatic ring, more preferably a benzene ring or a naphthalene ring, and even more preferably a naphthalene ring.

[0022] R 5 and R 6 each independently represents an alkyl group. The alkyl group preferably has 1 or more and 4 or less carbon atoms. The alkyl group is more preferably a methyl group or an ethyl group, and particularly preferably a methyl group. t, u, v, and w each represent an integer of 0 or more, and are values ​​that satisfy t + v ≦ 4 and u + w ≦ 4. t and u each independently are preferably 0 or more and 2 or less, more preferably 0 or 1. On the other hand, v and w each independently are preferably 0 or more and 2 or less, more preferably 0 or 1, and even more preferably 0.

[0023] Specific examples of the fluorene-containing (meth)acrylate represented by the general formula (A) include 9,9-bis(4-(meth)acryloyloxyphenyl)fluorene, 9,9-bis(4-(2-(meth)acryloyloxyethoxy)phenyl)fluorene, 9,9-bis(4-(3-(meth)acryloyloxypropoxy)phenyl)fluorene, 9,9-bis(4-(2-(meth)acryloyloxypropoxy)phenyl)fluorene, 9,9-bis(4-(meth)acryloyloxy-3-methylphenyl)fluorene, 9,9-bis[4-(2- (meth)acryloyloxyethoxy)-3-methylphenyl]fluorene, 9,9-bis[4-(3-(meth)acryloyloxypropoxy)-3-methylphenyl]fluorene, 9,9-bis[4-(2-(meth)acryloyloxypropoxy)-3-methylphenyl]fluorene, 9,9-bis(4-(meth)acryloyloxy-3-ethylphenyl)fluorene, 9,9-bis[4-(2-(meth)acryloyloxyethoxy)-3-ethylphenyl]fluorene, 9,9-bis[4-(3-(meth)acryloyloxypropoxy )-3-ethylphenyl]fluorene, 9,9-bis[4-(2-(meth)acryloyloxypropoxy)-3-ethylphenyl]fluorene, 9,9-bis(2-(meth)acryloyloxyethyl)-1,8-diphenylfluorene, 9,9-bis(3-(meth)acryloyloxypropyl)-1,8-diphenylfluorene, 9,9-bis(2-(meth)acryloyloxypropyl)-1,8-diphenylfluorene, 9,9-bis(2-(meth)acryloyloxyethyl)-2,7-diphenylfluorene, 9,9-bis(3-(meth)acryloyloxypropyl)-1,8-diphenylfluorene 9,9-bis(2-(meth)acryloyloxypropyl)-2,7-diphenylfluorene, 9,9-bis(2-(meth)acryloyloxypropyl)-2,7-diphenylfluorene, 9,9-bis(2-(meth)acryloyloxyethyl)-3,6-diphenylfluorene, 9,9-bis(3-(meth)acryloyloxypropyl)-3,6-diphenylfluorene, 9,9-bis(2-(meth)acryloyloxypropyl)-3,6-diphenylfluorene, 9,9-bis(2-(meth)acryloyloxyethyl)-4,5-diphenylfluorene, 9,9-bis(3-(meth)acryloyloxypropyl)-4,5-diphenylfluorene, 9,9-bis(2-(meth)acryloyloxypropyl)-4,5-diphenylfluorene, 9,9-bis(2-(meth)acryloyloxyethyl)-1,8-bis(naphth-1-yl)fluorene, 9,9-bis(3-(meth)acryloyloxypropyl)-1,8-bis(naphth-1-yl)fluorene, 9,9-bis(2-(meth)acryloyloxypropyl)-1,8-bis(naphth-1-yl)fluorene, 9,9-bis(2-(meth)acryloyloxypropyl)-1,8-bis(naphth-1-yl)fluorene, )acryloyloxyethyl)-2,7-bis(naphth-1-yl)fluorene, 9,9-bis(3-(meth)acryloyloxypropyl)-2,7-bis(naphth-1-yl)fluorene, 9,9-bis(2-(meth)acryloyloxypropyl)-2,7-bis(naphth-1-yl)fluorene, 9,9-bis(2-(meth)acryloyloxyethyl)-3,6-bis(naphth-1-yl)fluorene, 9,9-bis(3-(meth)acryloyloxypropyl)-3,6-bis(naphth-1-yl)fluorene, 9,9-bis(2- (meth)acryloyloxypropyl)-3,6-bis(naphth-1-yl)fluorene, 9,9-bis(2-(meth)acryloyloxyethyl)-4,5-bis(naphth-1-yl)fluorene, 9,9-bis(3-(meth)acryloyloxypropyl)-4,5-bis(naphth-1-yl)fluorene, 9,9-bis(2-(meth)acryloyloxypropyl)-4,5-bis(naphth-1-yl)fluorene, 9,9-bis(2-(meth)acryloyloxyethyl)-1,8-bis(naphth-2-yl)fluorene, 9,9-bis (3-(meth)acryloyloxypropyl)-1,8-bis(naphth-2-yl)fluorene, 9,9-bis(2-(meth)acryloyloxypropyl)-1,8-bis(naphth-2-yl)fluorene, 9,9-bis(2-(meth)acryloyloxyethyl)-2,7-bis(naphth-2-yl)fluorene, 9,9-bis(3-(meth)acryloyloxypropyl)-2,7-bis(naphth-2-yl)fluorene, 9,9-bis(2-(meth)acryloyloxypropyl)-2,7-bis(naphth-2-yl)fluorene, 9,Examples include 9-bis(2-(meth)acryloyloxyethyl)-3,6-bis(naphth-2-yl)fluorene, 9,9-bis(3-(meth)acryloyloxypropyl)-3,6-bis(naphth-2-yl)fluorene, 9,9-bis(2-(meth)acryloyloxypropyl)-3,6-bis(naphth-2-yl)fluorene, 9,9-bis(2-(meth)acryloyloxyethyl)-4,5-bis(naphth-2-yl)fluorene, 9,9-bis(3-(meth)acryloyloxypropyl)-4,5-bis(naphth-2-yl)fluorene, and 9,9-bis(2-(meth)acryloyloxypropyl)-4,5-bis(naphth-2-yl)fluorene.

[0024] Among the above, examples of preferred compounds include 9,9-bis(4-(meth)acryloyloxyphenyl)fluorene, 9,9-bis(4-(2-(meth)acryloyloxyethoxy)phenyl)fluorene, 9,9-bis(4-(3-(meth)acryloyloxypropoxy)phenyl)fluorene, 9,9-bis(4-(2-(meth)acryloyloxypropoxy)phenyl)fluorene, 9,9-bis(2-(meth)acryloyloxyethyl)-2,7-diphenylfluorene, and 9,9-bis(3-(meth)acryloyloxypropyl) -2,7-diphenylfluorene, 9,9-bis(2-(meth)acryloyloxypropyl)-2,7-diphenylfluorene, 9,9-bis(2-(meth)acryloyloxyethyl)-3,6-diphenylfluorene, 9,9-bis(3-(meth)acryloyloxypropyl)-3,6-diphenylfluorene, 9,9-bis(2-(meth)acryloyloxypropyl)-3,6-diphenylfluorene, 9,9-bis(2-(meth)acryloyloxyethyl)-2,7-bis(naphth-1-yl)fluorene, 9,9-bis(3-( 9,9-bis(2-(meth)acryloyloxypropyl)-2,7-bis(naphth-1-yl)fluorene, 9,9-bis(2-(meth)acryloyloxypropyl)-2,7-bis(naphth-1-yl)fluorene, 9,9-bis(2-(meth)acryloyloxyethyl)-3,6-bis(naphth-1-yl)fluorene, 9,9-bis(3-(meth)acryloyloxypropyl)-3,6-bis(naphth-1-yl)fluorene, 9,9-bis(2-(meth)acryloyloxypropyl)-3,6-bis(naphth-1-yl)fluorene, 9,9-bis( 2-(meth)acryloyloxyethyl)-2,7-bis(naphth-2-yl)fluorene, 9,9-bis(3-(meth)acryloyloxypropyl)-2,7-bis(naphth-2-yl)fluorene, 9,9-bis(2-(meth)acryloyloxypropyl)-2,7-bis(naphth-2-yl)fluorene, 9,9-bis(2-(meth)acryloyloxyethyl)-3,6-bis(naphth-2-yl)fluorene, 9,9-bis(3-(meth)acryloyloxypropyl)-3,6-bis(naphth-2-yl)fluorene, and 9,9-bis(2-(meth)acryloyloxypropyl)-3,6-bis(naphth-2-yl)fluorene is included.

[0025] Examples of more preferred compounds include 9,9-bis(4-(2-(meth)acryloyloxyethoxy)phenyl)fluorene, 9,9-bis(4-(3-(meth)acryloyloxypropoxy)phenyl)fluorene, 9,9-bis(4-(2-(meth)acryloyloxypropoxy)phenyl)fluorene, 9,9-bis(2-(meth)acryloyloxyethyl)-2,7-bis(naphth-1-yl)fluorene, fluorene, 9,9-bis(3-(meth)acryloyloxypropyl)-2,7-bis(naphth-1-yl)fluorene, 9,9-bis(2-(meth)acryloyloxypropyl)-2,7-bis(naphth-1-yl)fluorene, 9,9-bis(2-(meth)acryloyloxyethyl)-3,6-bis(naphth-1-yl)fluorene, 9,9-bis(3-(meth)acryloyloxypropyl)-3,6-bis(naphth-1-yl)fluorene (Naphth-1-yl)fluorene, 9,9-bis(2-(meth)acryloyloxypropyl)-3,6-bis(naphth-1-yl)fluorene, 9,9-bis(2-(meth)acryloyloxyethyl)-2,7-bis(naphth-2-yl)fluorene, 9,9-bis(3-(meth)acryloyloxypropyl)-2,7-bis(naphth-2-yl)fluorene, 9,9-bis(2-(meth)acryloyloxypropyl)- 9,9-bis(2-(meth)acryloyloxypropyl)-2,7-bis(naphth-2-yl)fluorene, 9,9-bis(2-(meth)acryloyloxyethyl)-3,6-bis(naphth-2-yl)fluorene, 9,9-bis(3-(meth)acryloyloxypropyl)-3,6-bis(naphth-2-yl)fluorene, and 9,9-bis(2-(meth)acryloyloxypropyl)-3,6-bis(naphth-2-yl)fluorene.

[0026] The fluorene-containing (meth)acrylate may be a commercially available product or may be synthesized. Examples of commercially available products include A-BPEF (manufactured by Shin-Nakamura Scientific Industrial Co., Ltd.) and OGSOL EA-0200 or EA-0300 (both manufactured by Osaka Gas Chemicals Co., Ltd.).

[0027] On the other hand, it can be synthesized by (meth)acryloyl esterification of commercially available fluorene derivative diols (e.g., bisphenoxyethanolfluorene, bisphenolfluorene, etc.) using (meth)acrylic anhydride, (meth)acryloyl chloride, etc. Furthermore, 9,9-bis(2-(meth)acryloyloxyethyl)-2,7-bis(naphth-2-yl)fluorene (DNEOA) can also be synthesized by the following synthesis scheme. [ka]

[0028] When the resin composition is used to manufacture optical components, semiconductor materials, or sensor materials, the amount of the fluorene-containing (meth)acrylate is preferably 10% by mass or more and 90% by mass or less, more preferably 20% by mass or more and 80% by mass or less, and even more preferably 30% by mass or more and 60% by mass or less, based on the total amount of the photocurable compound. When the amount of the fluorene-containing (meth)acrylate is within this range, the refractive index of the resulting cured product tends to be high and the Abbe number tends to be low. Furthermore, the transparency and heat resistance of the cured product tend to be good.

[0029] Other examples of compounds preferred as photocurable compounds include sulfur-containing (meth)acrylates that contain two or more (meth)acryloyl groups and a sulfur atom in the molecule. The resin composition may contain only one type of sulfur-containing (meth)acrylate, or two or more types. When the photocurable compound contains a sulfur-containing (meth)acrylate, the refractive index of the cured product of the resin composition tends to be further increased, and the Abbe number tends to be further increased.

[0030] Examples of the sulfur-containing (meth)acrylate include a (meth)acrylic acid thioester compound represented by the following general formula (1): The resin composition may contain only one type of (meth)acrylic acid thioester compound, or may contain two or more types of (meth)acrylic acid thioester compounds. [ka]

[0031] In the above general formula (1), R 1 and R 2 each independently represents a hydrogen atom or a methyl group. n represents an integer of 5 or greater. n is preferably 6 or greater, and more preferably 7 or greater. n is preferably 20 or less, more preferably 15 or less, even more preferably 12 or less, and particularly preferably 10 or less.

[0032] X represents an alkylene group having 1 to 4 carbon atoms, which may be bonded to a group represented by the following general formula (2), and in which any methylene group may be substituted with a carbonyl group. The alkylene group preferably has 2 to 4 carbon atoms, and more preferably 2 or 3 carbon atoms. The methylene group constituting the alkylene group may not be substituted with a carbonyl group. On the other hand, when a methylene group is substituted with a carbonyl group, the number of carbonyl groups is preferably 1 to 4, more preferably 1 to 3, and even more preferably 1 or 2.

[0033] [ka] In general formula (2), R 3 represents a hydrogen atom or a methyl group. Z represents an alkylene group having 1 to 4 carbon atoms, preferably 1 to 3 carbon atoms, more preferably 1 or 2, and even more preferably 1 (methylene group). p represents an integer of 1 or more, preferably 1 to 4 carbon atoms, more preferably 1 to 3 carbon atoms, and even more preferably 1 or 2. When p is 2 or more, each Z may be the same or different. The number of groups represented by general formula (2) bonded to the alkylene group may be 0, but is preferably 1 to 4, more preferably 1 to 3, even more preferably 1 or 2, and particularly preferably 2. When multiple groups represented by general formula (2) are bonded to the alkylene group, the structures of the respective substituents may be the same or different.

[0034] Specific examples of the (meth)acrylic acid thioester compound include a compound represented by the following general formula (3) and a compound represented by the following general formula (4). [ka] In the above general formula (3) and general formula (4), X 11 ~X 14 each independently represents an alkylene group having 1 to 4 carbon atoms, which may be bonded to a group represented by the above general formula (2). The number of carbon atoms in the alkylene group is preferably 1 to 3, more preferably 1 or 2, and particularly preferably 2. e, f, g, and h each independently represent an integer of 2 or more, preferably 2 to 6, more preferably 2 to 5, and even more preferably 2 or 3. R 11 ~R 14 each independently represents a methyl group or a hydrogen atom.

[0035] Specific examples of the compound represented by the above general formula (3) or (4) include compounds represented by the following formulae: [ka]

[0036] Here, the weight-average molecular weight of the (meth)acrylic acid thioester compound is preferably at least 1,000, more preferably at least 1,500. Also, it is preferably at most 100,000, more preferably at most 50,000, even more preferably at most 20,000, particularly preferably at most 10,000, and even more preferably at most 5,000. When the weight-average molecular weight of the (meth)acrylic acid thioester compound is within this range, the refractive index of the cured product of the resin composition is likely to be further increased, and the Abbe number is likely to be further decreased.

[0037] The (meth)acrylic acid thioester compound can be synthesized, for example, by the following method: A polythiol is prepared, and when all thiol groups contained in the polythiol are taken as 1 equivalent, 0.5 to 0.9 equivalents of thiol groups are converted into functional groups represented by the following general formula: [ka] In the above general formula, X 21 represents a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, and preferably represents a chlorine atom. 21 represents a hydrogen atom or a methyl group.

[0038] A specific example is a method in which a polythiol compound is reacted with a halogenated alkylcarbonyl halide compound such as 3-chloropropionyl chloride to convert the thiol group in the polythiol compound into a functional group represented by the above structural formula. The compound obtained above is then subjected to a β-elimination reaction and an enethiol reaction by a known method to obtain a (meth)acrylic acid thioester compound.

[0039] The (meth)acrylic acid thioester compound can also be obtained, for example, by a synthesis method including a step of reacting a polythiol compound with a polythio(meth)acrylate compound by an enethiol reaction using a known method.

[0040] When the resin composition is used to manufacture optical components, semiconductor materials, or sensor materials, the amount of the (meth)acrylic acid thioester compound is preferably 10% by mass or more and 90% by mass or less, more preferably 20% by mass or more and 80% by mass or less, and even more preferably 30% by mass or more and 60% by mass or less, based on the total amount of the photocurable compounds. When the amount of the (meth)acrylic acid thioester compound is within this range, the refractive index of the resulting cured product is likely to be further increased, and the Abbe number is likely to be further reduced. Furthermore, the transparency and heat resistance of the resulting cured product are likely to be improved.

[0041] Here, the resin composition may contain, as a photocurable compound, (meth)acrylates other than the above-mentioned fluorene-containing (meth)acrylate and sulfur-containing (meth)acrylate (hereinafter also referred to as "other (meth)acrylates"). In addition, among the following examples, (C a-b) indicates that the number of carbon atoms in the alkylene group, alkyl group, alkoxy group, etc. is between a and b.

[0042] Other examples of (meth)acrylates include alkylene (C ) di(meth)acrylates such as ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, and 1,6-hexanediol di(meth)acrylate. 2-10 ) glycol di(meth)acrylates; polyalkylene (C) di(meth)acrylates such as diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, and polypropylene glycol di(meth)acrylate; 2-4 ) glycol di(meth)acrylate; bisphenol A di(meth)acrylates such as 2,2-bis(4-(meth)acryloyloxydiethoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxyethoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxypolyethoxyphenyl)propane; tricyclodecane dimethanol di(meth)acrylate; alkane polyol poly(meth)acrylates such as trimethylolpropane tri(meth)acrylate, glycerin tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate; alkane polyols (C) such as trimethylolpropane and glycerin 2-4 ) alkylene oxide adduct tri(meth)acrylate; tri(meth)acrylates having a triazine ring such as tris(2-hydroxyethyl)isocyanurate tri(meth)acrylate, 4,4'-bis(methacryloylthio)diphenyl sulfide, triallyl cyanurate, triallyl isocyanurate, triallyl trimellitate, and oligomers thereof.

[0043] As described above, the other (meth)acrylate (photocurable compound) may contain a monofunctional (meth)acrylate monomer. Examples of the monofunctional (meth)acrylate monomer include alkyl (C) (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, t-butyl (meth)acrylate, hexyl (meth)acrylate, octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, and stearyl (meth)acrylate. 1-24 ) (meth)acrylate; haloalkyl (C such as trifluoroethyl (meth)acrylate, tetrafluoropropyl (meth)acrylate, hexafluoroisopropyl (meth)acrylate, etc. 1-10 ) (meth)acrylate; cycloalkyl (meth)acrylates such as cyclohexyl (meth)acrylate; bridged cyclic (meth)acrylates such as dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentadienyl (meth)acrylate, bornyl (meth)acrylate, isobornyl (meth)acrylate, and tricyclodecanyl (meth)acrylate; aralkyl (meth)acrylates such as benzyl (meth)acrylate; hydroxyalkyl (C) such as hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, and hydroxybutyl (meth)acrylate 2-10 ) (meth)acrylate; phenoxyalkyl (C such as phenoxyethyl (meth)acrylate 1-10 ) (meth) acrylate; alkoxy (C such as methoxyethyl (meth) acrylate 1-10 )(Alkyl(C 1-10 ) (meth)acrylate; glycidyl (meth)acrylate; dimethylamino (meth)acrylate; (meth)acrylamide; tetrahydrofurfuryl (meth)acrylate, O-phenylphenoxyethyl acrylate, and the like.

[0044] Furthermore, the total amount of the photocurable compounds (the total amount of the above-mentioned fluorene-containing (meth)acrylate, sulfur-containing (meth)acrylate, and other (meth)acrylates) relative to the total amount of the resin composition is preferably 60% by mass or more and 99% by mass, more preferably 70% by mass or more and 98% by mass or less. When the total amount of the photocurable compounds is within this range, a cured product with high strength is likely to be obtained.

[0045] (Photopolymerization initiator) The photopolymerization initiator is not particularly limited as long as it is a compound that can be excited by laser irradiation and polymerize the photocurable compound. The resin composition may contain only one type of photopolymerization initiator, or may contain two or more types.

[0046] Examples of the photopolymerization initiator include diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, 2-benzyl-2-(dimethylamino)-4'-morpholinobutyrophenone, 1,2-octanedione 1-[4-(phenylthio)phenyl]-2-(o-benzoyloxime), ethanone-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-1-(o-acetyloxime), 1-hydroxycyclohexyl-phenyl ketone, and 2-hydroxy-2-methyl-1-phenylpropanone. The photopolymerization initiator may also be a commercially available product. Examples of commercially available products include TPO (trade name, manufactured by Tokyo Chemical Industry Co., Ltd.); Irgacure 819 (BAPO, trade name), Irgacure 369 (Omnirad 369, trade name), Irgacure OXE 01 (trade name), Irgacure OXE 02 (trade name), Irgacure OXE 03 (trade name), Irgacure OXE 04 (trade name), Irgacure 184 (Omnirad 184, trade name), and Omnirad 1173 (Darocur 1173, trade name) (all of which are manufactured by BASF); NCI-831 (trade name) and NCI-930 (trade names, both of which are manufactured by ADEKA). These can be used alone or in combination of two or more types.

[0047] Among the above, Omnirad369E and Irgacure184 are preferred from the viewpoint of ease of excitation by laser irradiation.

[0048] The absorption wavelength of the photopolymerization initiator is appropriately selected according to the wavelength of the irradiated laser. For example, the photopolymerization initiator preferably absorbs light with a wavelength of 200 nm or more and 400 nm or less, and more preferably absorbs light with a wavelength of 230 nm or more and 380 nm or less. When the photopolymerization initiator has an absorption wavelength in this range, the resin composition can be well cured by laser irradiation.

[0049] The total amount of photopolymerization initiator in the resin composition may be 0.5% by mass or less, preferably 0.01% by mass to 0.3% by mass, more preferably 0.05% by mass to 0.3% by mass, and even more preferably 0.1% by mass to 0.2% by mass. When the amount of photopolymerization initiator is 0.01% by mass or more, the resin composition can be efficiently cured by laser irradiation. On the other hand, when the amount of photopolymerization initiator is excessively large, the amount of active species generated by the photopolymerization initiator upon laser irradiation may be excessively large, which may result in curing of the photocurable compound not only in the desired region but also in the surrounding region. In contrast, when the amount of photopolymerization initiator is 0.5% by mass or less relative to the amount of photocurable compound, a three-dimensional object can be produced with high precision.

[0050] (aromatic isocyanate) The aromatic isocyanate may be a compound having an aromatic ring and two or more isocyanate groups, and may be a compound capable of forming a crosslinked structure by reacting with moisture in the air. The number of isocyanate groups possessed by the aromatic isocyanate is not particularly limited as long as it is two or more, but is preferably two to five, and more preferably two to three. The resin composition may contain only one type of aromatic isocyanate, or may contain two or more types.

[0051] Examples of aromatic isocyanates include isocyanates such as toluene diisocyanate (TDI), xylene diisocyanate, nitrodiphenyl diisocyanate, diphenylpropane diisocyanate, dimethyldiphenylmethane diisocyanate, phenylene diisocyanate, naphthylene diisocyanate, dimethoxydiphenyl diisocyanate, nitrodiphenyl diisocyanate, diphenylpropane diisocyanate, dimethyldiphenylmethane diisocyanate, phenylene diisocyanate, naphthylene diisocyanate, and dimethoxydiphenyl diisocyanate; and polymeric, urethane-modified, urea-modified, allophanate-modified, biuret-modified, carbodiimide-modified, uretonimine-modified, uretdione-modified, and isocyanurate-modified products of these isocyanates.

[0052] Among these, diphenylmethane diisocyanate is preferred from the viewpoints of reactivity with moisture in the air and visible light transmittance of the cured product.

[0053] The total amount of aromatic isocyanate in the resin composition is preferably 5% by mass or more and 30% by mass or less, more preferably 10% by mass or more and 25% by mass or less, and even more preferably 10% by mass or more and 20% by mass or less, relative to the total amount of the photocurable compound. If the amount of aromatic isocyanate is 10% by mass or more, the resin composition can be moisture-cured (pre-cured) before laser irradiation, making it easier to reduce its fluidity. On the other hand, if the amount of aromatic isocyanate is 20% by mass or less, the amount of photocurable compound becomes relatively large, making it easier to obtain a three-dimensional object with high strength.

[0054] (Other ingredients) The resin composition may contain other components as needed in addition to the photocurable compound, photopolymerization initiator, and aromatic isocyanate. Examples of the other components include a silane coupling agent, an antioxidant, a light stabilizer, etc.

[0055] The total amount of other components is preferably 10% by mass or less, and more preferably 3% by mass or less, based on the total amount of the resin composition.

[0056] (Method for preparing resin composition and physical properties of resin composition) The method for preparing the resin composition is not particularly limited, and the resin composition can be prepared by mixing a photocurable compound, a photopolymerization initiator, an aromatic isocyanate, and other components as needed. The mixing is preferably carried out using a stirrer or a flask under dry air.

[0057] The viscosity of the resin composition before moisture curing, measured at 25°C with an E-type viscometer, is preferably 100 mPa·s or more and 20,000 mPa·s or less, and more preferably 200 mPa·s or more and 10,000 mPa·s or less. When the viscosity of the resin composition is within this range, the resin composition becomes easy to handle. The viscosity of the resin composition can be adjusted by the type and combination of photocurable compounds.

[0058] Furthermore, the resin composition was irradiated with light of 365 nm wavelength at 3000 mJ / cm 2 The refractive index of the cured product obtained by irradiation with light having a wavelength of 589 nm at 25°C is preferably 1.60 or more, more preferably 1.61 or more. In addition, the Abbe number of light having a wavelength of 589 nm at 25°C is preferably 25 or more, more preferably 27 or more. The refractive index and Abbe number of the cured product can be appropriately adjusted depending on the type of photocurable compound, etc. Increasing the amount of the above-mentioned fluorene-containing (meth)acrylate or (meth)acrylic acid thioester compound as the photocurable compound tends to increase the refractive index and also the Abbe number.

[0059] 2. Manufacturing method of three-dimensional object and three-dimensional object The resin composition described above is suitable for a method for producing a three-dimensional object by laser drawing. The three-dimensional object can be produced by carrying out the following steps: forming a layer containing a photocurable resin composition for laser drawing on a laser-transparent substrate (hereinafter also referred to as a "resin layer forming step"); provisionally curing the layer containing the photocurable resin composition for laser drawing in air (hereinafter also referred to as a "provisional curing step"); and irradiating the provisionally cured photocurable resin composition for laser drawing with a laser through the substrate (laser irradiation step). This method will be described below, but the method for producing a three-dimensional object using the resin composition described above is not limited to this method.

[0060] In the resin layer formation step, a layer of a resin composition is formed on a laser-transparent substrate. The method for forming the layer is not particularly limited, and may be, for example, a known coating method, such as spin coating or a dispenser method. The substrate used is not particularly limited as long as it is capable of transmitting the laser irradiated in the laser irradiation step and supporting a layer of the resin composition, and may be a glass substrate or the like. The shape of the substrate is not particularly limited, and may be a flat plate or may have a storage section for storing the resin composition.

[0061] In the pre-curing step, the layer of resin composition formed on the substrate is left standing for a certain period of time in an atmosphere containing moisture (humidity), causing the aromatic isocyanate to react with water and pre-cure the resin composition. The temperature of the atmosphere in which the resin composition is pre-cured is preferably 10°C or higher and 40°C or lower, and more preferably 20°C or higher and 30°C or lower. The humidity of the atmosphere is more preferably 50% Rh or higher and 99% Rh. The time for pre-curing is appropriately selected depending on the type of resin composition, the coating film thickness, etc., but is usually preferably 60 seconds to 72 hours, and more preferably 60 seconds to 24 hours.

[0062] In the laser irradiation process, a laser is focused at a specific position on the pre-cured resin composition (pre-cured layer) to cure the resin composition into a desired shape. In this process, laser irradiation may be performed with the substrate positioned so that it faces upward in the direction of gravity and the pre-cured layer faces downward in the direction of gravity, or with the substrate positioned so that it faces downward in the direction of gravity and the pre-cured layer faces upward in the direction of gravity. Laser irradiation may also be performed with the substrate or pre-cured layer positioned in a different orientation, but in either case, laser irradiation is performed from the substrate side. Furthermore, it is preferable to place immersion oil between the objective lens for focusing the laser and the substrate.

[0063] Here, the laser irradiated onto the resin composition is preferably a pulsed laser from the viewpoint of performing fine processing, and a femtosecond pulsed laser is particularly preferred because it is capable of performing extremely fine processing. The wavelength of the laser irradiated onto the resin composition is preferably 300 nm or more and 700 nm or less, and more preferably 500 nm or more and 600 nm or less.

[0064] The configuration of the laser irradiation device may be the same as that of a known laser irradiation device, as long as it can focus the laser at a desired position within the temporarily cured layer. For example, the device may include a laser light source that emits a laser, an objective lens for focusing the laser from the laser light source, and an optical system for adjusting the focus of the laser. The laser light source preferably includes a nonlinear optical element capable of generating a second harmonic. The nonlinear element allows the laser light source to irradiate the temporarily cured layer with a second harmonic, thereby enabling two-photon excitation of the photopolymerization initiator, etc. Manufacturing a three-dimensional object using such two-photon excitation enables microfabrication below the laser diffraction limit.

[0065] After the laser irradiation step, a removal step may be performed as needed to remove the resin composition from areas other than those cured by the laser irradiation. Examples of a method for removing the resin composition include a method using a solvent such as xylene.

[0066] The type and shape of the three-dimensional object formed by this method are appropriately selected depending on the intended use of the three-dimensional object. As described above, the three-dimensional object can have a refractive index of 1.60 or more for light with a wavelength of 589 nm, and can also have an Abbe number of 25 or more. Such three-dimensional objects with high refractive indexes and Abbe numbers are very useful as materials for various optical components, semiconductor components, sensors, and the like, and can be used in a variety of applications, including optical products, semiconductor products, sensors, and the like. [Example]

[0067] The present invention will be described below with reference to examples, which should not be construed as limiting the scope of the present invention.

[0068] 1. Material Preparation The following compounds were used in the following examples and comparative examples.

[0069] (photocurable compound) OPPEOA (O-phenylphenoxyethyl acrylate) A-BPEF (fluorene-containing diacrylate represented by the following structural formula, OGSOL EA-0200, manufactured by Osaka Gas Chemicals Co., Ltd.) [ka] A composition containing a tetrafunctional acrylic acid thioester compound represented by the following (1a), prepared in the synthesis example described below: [ka]

[0070] (Photopolymerization initiator) Omnirad 369E (manufactured by IGM Resins BV)

[0071] (aromatic isocyanate) Mixture of 2,4'-diphenylmethane diisocyanate and 4,4'-diphenylmethane diisocyanate

[0072] (Other isocyanates) Aliphatic isocyanate (Duranate TPA-100 (Asahi Kasei Corporation))

[0073] (Silane coupling agent) KBE-503 (Shin-Etsu Chemical Co., Ltd.)

[0074] <Synthesis example> A four-neck flask equipped with a stirrer, thermometer, nitrogen inlet line, and dropping funnel was charged with GST (trithiol, 100.0 g, 383.9 mmol), diluted with dichloromethane (100 mL), and stirring was initiated. Next, 3-chloropropionyl chloride (121.84 g, 959.7 mmol) was added dropwise while the reaction solution was cooled in an ice bath to maintain the internal temperature below 40°C.

[0075] After stirring the reaction mixture at room temperature for 48 hours, 100 mL of purified water was added and the organic phase was separated by a separation operation. The resulting organic phase was washed twice with 100 mL of saturated aqueous sodium bicarbonate solution to obtain a dichloromethane solution of a composition in which some of the thiol groups of GST had been converted to 3-chloropropionate (a group of compounds including the tri-, di-, and mono-substituted GSTs shown below). The peak area ratio of the tri-, di-, and mono-substituted GSTs determined by high-performance liquid chromatography (HPLC) was 56:38:6.

[0076] [ka]

[0077] To the above solution, 4-methoxyphenol (150 mg) was further added as a polymerization inhibitor and dissolved with stirring at room temperature. Next, triethylamine (116.5 g, 1152 mmol) was added dropwise while the reaction solution was cooled in an ice bath to maintain the internal temperature at 40°C or below. After stirring the reaction solution at room temperature for 1 hour, 1 M hydrochloric acid (300 mL) was added, and the organic phase was separated by a separation operation. The resulting organic phase was passed through silica gel (100 mL), and 4-methoxyphenol (150 mg) as a polymerization inhibitor was added. The mixture was then concentrated under reduced pressure to obtain a colorless, transparent composition (132.5 g) containing the tetrafunctional acrylic acid thioester compound represented by formula (1a) above. The molecular weight was measured by the following method (GPC), and the number average molecular weight (Mn) was 500 and the weight average molecular weight (Mw) was 1600.

[0078] ·Molecular weight measurement The number average molecular weight (Mn) and weight average molecular weight (Mw) of the composition containing the tetrafunctional acrylic acid thioester compound obtained in the above synthesis example were measured by gel permeation chromatography (GPC) according to the following procedure.

[0079] (1) Preparation of sample solution The composition was dissolved in tetrahydrofuran to a concentration of 1 g / 100 mL, and the solution was then filtered through a 1 μm pore size filter (manufactured by Membrane Solutions, product name: Syringe Filter PTFE013100) to remove insoluble components, thereby obtaining a sample solution.

[0080] (2) Molecular weight measurement Using a GPC measurement device (product name: Alliance, manufactured by WATERS), tetrahydrofuran (Fujifilm Wako Pure Chemical Industries, for high-performance liquid chromatography) was flowed as the eluent at a flow rate of 1.0 mL / min. Three analytical columns (gel permeation columns, manufactured by Agilent, product name: PLgel 5 μm Mixed-C) connected in series were stabilized in a constant temperature bath at 40 °C. 10 μL of the sample solution was injected into the column for measurement. A differential refractive index (RI) detector was used as the detector. The molecular weight of the sample was calculated based on a calibration curve prepared in advance. The calibration curve was prepared using several types of monodisperse polystyrene (manufactured by Agilent) with known molecular weights as standard samples.

[0081] <Preparation of Resin Compositions (Examples 1 to 6 and Comparative Examples 1 to 3)> A photocurable compound, a photopolymerization initiator, an aromatic isocyanate (or an aliphatic isocyanate), and a silane coupling agent were mixed according to the composition shown in Table 1. The composition in Table 1 is a mass ratio. Mixing was carried out by stirring using a stirrer while heating to an appropriate temperature such as 80°C.

[0082] <Evaluation> The moisture curability and resolution of the resin composition, as well as the refractive index and Abbe number of the resulting cured product, were measured by the methods described below.

[0083] (1) Moisture curing evaluation The resin compositions prepared in the examples and comparative examples were placed on glass and left in an environment of 23°C and 50%RH for one to three days at most, and then the glass was tilted to check for fluidity and evaluate moisture curability. The evaluation criteria were as follows: ○: No flow (hardening has progressed) ×: The glass flows when tilted (hardening has not progressed)

[0084] (2) Resolution A three-dimensional object was manufactured using a Yb:KGW femtosecond laser. One-shot exposure was performed under the conditions of a maximum average output of 10 W, a pulse width of 290 femtoseconds, a maximum pulse energy of 0.2 mJ, a repetition frequency of 1 MHz, and a central wavelength of 515 nm. The resolution of the three-dimensional object was evaluated by varying the irradiation power from 0.25 to 2%. The evaluation criteria were as follows: ◎: A three-dimensional object was fabricated with a resolution of less than 2 μm ○: A three-dimensional object was fabricated with a resolution of 2 μm or more and less than 20 μm. ×: A three-dimensional object was processed with a resolution of 20 μm or more.

[0085] (3) Refractive index A PET film (MelinexS) was placed on a glass plate (EAGLE-XG, Corning), a 100 μm-thick spacer was placed on the periphery, a resin composition was dripped onto the center, and the PET film and glass plate were placed in that order, sandwiching the spacer and the resin composition, and then fastened with clips. Then, light with a wavelength of 365 nm was applied at 3000 mJ / cm. 2 A cured film was produced by irradiating the film with light. The refractive index of the cured film was then measured using an Abbe refractometer (DR-M2, manufactured by Atago Co., Ltd.). RE-3520 (589 nm, D-line, manufactured by Atago Co., Ltd.) was used as an interference filter, and RE-1196 (monobromonaphthalene, manufactured by Atago Co., Ltd.) was used as an intermediate solution. The sample temperature was set to 25°C during the measurement. The evaluation criteria were as follows. Table 1 also shows actual measured values ​​in parentheses. ○: Refractive index was 1.61 or more △: The refractive index was 1.51 or more and less than 1.61 ×: Refractive index was less than 1.51

[0086] [Table 1]

[0087] As shown in Table 1 above, Comparative Example 1, which mainly contained a photocurable compound and a photopolymerization initiator but did not contain an aromatic isocyanate, exhibited low moisture curing properties. On the other hand, resin compositions containing a photocurable compound, a photopolymerization initiator, and an aliphatic isocyanate also exhibited low moisture curing performance (Comparative Examples 2 and 3). It is believed that the aliphatic isocyanate had low reactivity with water. Furthermore, the refractive index decreased as the amount of aliphatic isocyanate increased.

[0088] On the other hand, in Examples 1 to 6, which contained a photocurable compound, a photopolymerization initiator, and a difunctional or higher aromatic isocyanate, all of them were moisture-curable and had good resolution. In particular, when the ratio of the photopolymerization initiator to the total amount of the photocurable compound was reduced, the resolution was very good (Examples 4 and 5). [Industrial Applicability]

[0089] The photocurable resin composition for laser writing of the present invention enables precise production of fine three-dimensional objects by focusing a laser beam inside the composition, and is therefore applicable to a wide range of fields, and is particularly useful in, for example, the production of optical components.

Claims

1. a photocurable compound containing a (meth)acryloyl group; a photopolymerization initiator; a difunctional or higher aromatic isocyanate; containing Photocurable resin composition for laser drawing.

2. The aromatic isocyanate is diphenylmethane diisocyanate. The photocurable resin composition for laser writing according to claim 1 .

3. the refractive index of the cured product for light having a wavelength of 589 nm at 25°C is 1.60 or more, and the Abbe number for light having a wavelength of 589 nm at 25°C is 25 or less; The photocurable resin composition for laser writing according to claim 1 .

4. the photocurable compound contains a fluorene-containing (meth)acrylate having two or more (meth)acryloyl groups and a fluorene structure in the molecule; The photocurable resin composition for laser writing according to claim 1 .

5. the amount of the fluorene-containing (meth)acrylate is 30% by mass or more and 70% by mass or less with respect to the total amount of the photocurable compound; The photocurable resin composition for laser writing according to claim 4.

6. the photocurable compound contains a sulfur-containing (meth)acrylate containing two or more (meth)acryloyl groups and a sulfur atom in the molecule; 2. A photocurable resin composition for laser writing according to claim 1.

7. The sulfur-containing (meth)acrylate is a (meth)acrylic acid thioester compound represented by the following general formula (1): The photocurable resin composition for laser writing according to claim 6 . 【Chemical 1】 (In general formula (1), X represents an alkylene group having 1 to 4 carbon atoms, which may be bonded to a group represented by the following general formula (2) and in which any methylene group may be substituted with a carbonyl group: n represents an integer of 5 or more; R １ and R ２ each independently represents a hydrogen atom or a methyl group. 【Chemistry 2】 (In general formula (2), R ３ represents a hydrogen atom or a methyl group, Z represents an alkylene group having 1 to 4 carbon atoms; p represents an integer of 1 or more

8. A cured product of the photocurable resin composition for laser writing according to any one of claims 1 to 7, Three-dimensional sculpture.

9. forming a layer containing the photocurable resin composition for laser writing according to any one of claims 1 to 7 on a laser-transparent substrate; a step of provisionally curing the layer containing the photocurable resin composition for laser writing in air; irradiating a laser beam through the substrate into the pre-cured photocurable resin composition for laser writing; Including, A method for manufacturing a three-dimensional object.

10. The laser is a femtosecond pulse laser. The method for manufacturing a three-dimensional object according to claim 9 .

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