JP4863288B2 - Photo-curable resin composition for optical three-dimensional modeling and three-dimensional modeling - Google Patents

Description

  The present invention relates to a photocurable resin composition for optical three-dimensional modeling.

  An optical three-dimensional modeling method for forming a three-dimensional modeled object in which the cured resin layer is integrally laminated by repeating the step of selectively irradiating light to a photocurable resin composition to form a cured resin layer Is known (patent documents 1 to 4). To explain a typical example of this optical three-dimensional modeling method, a predetermined pattern is formed by selectively irradiating light such as an ultraviolet laser onto the liquid surface of the photocurable resin composition contained in a container. A cured resin layer is formed. Next, a single layer of the photocurable resin composition is supplied onto the cured resin layer, and the liquid surface is selectively irradiated with light to thereby form a layer on the previously formed cured resin layer. A new cured resin layer is integrally laminated so as to be continuous. Then, by repeating the above process a predetermined number of times while changing or not changing the pattern irradiated with light, a three-dimensional modeled object in which a plurality of cured resin layers are integrally laminated is formed. This optical three-dimensional modeling method has an advantage that even if the target three-dimensional model has a complicated shape, it can be obtained easily and in a short time. Therefore, the optical three-dimensional modeling method is extremely useful in the trial production process in the development of new products such as automobiles and home appliance industries, and is becoming an indispensable means for shortening the development period and reducing costs.

Conventionally, as a photocurable resin composition for optical three-dimensional modeling used in the optical three-dimensional modeling method, the following resin compositions [a] to [c] have been proposed.
[I] Resin compositions containing radically polymerizable organic compounds such as urethane (meth) acrylate, oligoester (meth) acrylate, epoxy (meth) acrylate, thiol and ene compounds, and photosensitive polyimide (Patent Documents 5 to 7) .
[B] A resin composition containing a cationically polymerizable compound such as an epoxy compound, a cyclic ether compound, a cyclic lactone compound, a cyclic acetal compound, a cyclic thioether compound, a spiro orthoester compound, or a vinyl ether compound (Patent Document 8).
[C] A resin composition containing a radical polymerizable organic compound and a cationic polymerizable compound (Patent Documents 9 to 14).

The three-dimensional model obtained by such a three-dimensional modeling method has been widely used as a model for studying a design and a shape confirmation model for a prototype of a machine part. However, as a recent market trend, there is a tendency to strongly demand physical properties equivalent to general-purpose resins such as thermoplastic resins used for mounting materials. This is because the three-dimensionally shaped product obtained from the radiation curable resin is used not only for shape confirmation but also for the same evaluation test as the mounting material such as assembly test, drop test, heat resistance test, durability test, etc. It aims at cost reduction. In order to apply to such an evaluation test, the cured resin must have the same characteristics as the mounting material.
In particular, when the mounting material is an engineering plastic such as ABS resin, the three-dimensional structure used as a prototype of the plastic part is subjected to fine processing faithful to the design drawing with high accuracy, and ABS resin. It is required to have properties such as excellent mechanical properties (for example, excellent rigidity, impact resistance, and toughness) similar to or equivalent to engineering plastics such as

However, in the techniques of Patent Documents 5 to 14, it is difficult to obtain a composition excellent in all of rigidity, impact resistance, toughness and the like in addition to high modeling accuracy.
Here, for the purpose of improving the mechanical properties of the three-dimensional structure, a technique for blending particles made of an elastomer or the like is known (Patent Document 15). However, there is still room for improvement in the balance of physical properties such as rigidity, impact resistance, and toughness for use in prototypes of plastic parts manufactured with engineering plastics such as ABS resin.

JP 60-247515 A JP-A-62-35966 JP 62-101408 A See JP-A-5-24119 JP-A-1-204915 JP-A-2-208305 Japanese Patent Laid-Open No. 3-160013 JP-A-1-213304 JP-A-2-28261 Japanese Patent Laid-Open No. 2-75618 JP-A-6-228413 Japanese Patent Laid-Open No. 11-310626 JP 11-228610 A JP-A-11-240939 JP 2003-192877 A

  Then, an object of this invention is to provide the photocurable resin composition for optical three-dimensional model | molding which gives the hardened | cured material (three-dimensional model | molded item) excellent in all of rigidity, impact resistance, toughness, etc.

As a result of intensive studies to solve the above-mentioned problems, the present inventor has a specific blend of a plurality of components composed of a specific cationic polymerizable compound having two or more bisphenol structures and one or more hydroxyl groups in the molecule. It has been found that a cured product having the above physical properties can be obtained according to the photocurable resin composition contained in a proportion, and the present invention has been completed.

（式（１）中、Ｒ^１は、−Ｃ（ＣＨ_３）_２−、−ＣＨ_２−、−ＳＯ_２−のいずれかであり、ｋは、１〜４の整数であり、ｎは、１〜１０の整数である。）
［２］ 前記（Ｂ）成分が、オキセタン構造を有する化合物を含有する上記［１］に記載の光学的立体造形用光硬化性樹脂組成物。
［３］ 前記（Ｂ）成分が、ビスフェノール構造を有する化合物を含有する上記［１］又は［２］に記載の光学的立体造形用光硬化性樹脂組成物。
［４］ さらに（Ｆ）平均粒子径１０〜７００ｎｍのエラストマー粒子を含有する上記［１］〜［３］のいずれか１つに記載の光学的立体造形用光硬化性樹脂組成物。
［５］ 上記［１］〜［４］のいずれか１つに記載の光学的立体造形用光硬化性樹脂組成物の硬化物からなる立体造形物。 That is, the present invention provides the following [1] to [ 5 ].
[ 1 ] When the total amount of the composition is 100% by mass,
(A) 3-40% by mass of a cationically polymerizable compound having two or more bisphenol structures and one or more hydroxyl groups,
(B) Cationic polymerizable compound other than component (A) 20 to 85% by mass,
(C) Cationic photopolymerization initiator 0.1 to 10% by mass,
(D) Radical polymerizable compound 3-45 mass%, and
(E) 0.01-10% by mass of a radical photopolymerization initiator,
A photocurable resin composition for optical three-dimensional modeling containing
The said (A) component is an epoxy compound represented by following General formula (1), The photocurable resin composition for optical three-dimensional modeling characterized by the above-mentioned .

(In formula (1), R ¹ is any ^one of —C (CH ₃ ) ₂ —, —CH ₂ —, and —SO ₂ —, k is an integer of 1 to 4, and n is 1 It is an integer of -10.)
[ 2 ] The photocurable resin composition for optical three-dimensional modeling according to the above [1] , wherein the component (B) contains a compound having an oxetane structure.
[ 3 ] The photocurable resin composition for optical three-dimensional modeling according to the above [1] or [2] , wherein the component (B) contains a compound having a bisphenol structure.
[ 4 ] The photocurable resin composition for optical three-dimensional modeling according to any one of [1] to [ 3 ], further including (F) elastomer particles having an average particle diameter of 10 to 700 nm.
[ 5 ] A three-dimensional structure made of a cured product of the photocurable resin composition for optical three-dimensional structure described in any one of [1] to [ 4 ].

The composition of this invention can give the hardened | cured material (three-dimensional molded item) excellent in the mechanical characteristic. Specifically, a cured product obtained by photocuring the resin composition of the present invention has high rigidity (high Young's modulus, flexural modulus, etc.), excellent impact resistance (high Izod impact value, etc.), and excellent And toughness (for example, a large number of times of bending until the film is broken when the film is bent multiple times).
Since the composition of the present invention can give a cured product having mechanical properties close to or equivalent to engineering plastics such as ABS resin, prototypes of plastic parts manufactured with these engineering plastics are produced and evaluated. It is suitably used as a material for the purpose.

The photocurable resin composition for optical three-dimensional model | molding of this invention contains (A)-(E) component and the other component added as needed.
Hereinafter, each component will be described in detail.
[(A) component]
The component (A) used in the composition of the present invention is a specific cationic polymerizable compound having two or more bisphenol structures and one or more hydroxyl groups. By using the component (A) at a specific blending ratio, the physical property balance such as rigidity, impact resistance and toughness can be improved with respect to the mechanical properties of the cured product of the composition.
Here, the bisphenol structure refers to a divalent group derived from bisphenol A, bisphenol F or bisphenol S, and is preferably a divalent group derived from bisphenol A. The number of bisphenol structure contained in the molecule of the component (A), 2 to 11, preferably 2 to 5, more preferably 2 to 4. When the number of bisphenol structures exceeds 11, the viscosity of the composition becomes excessive, which is not preferable. On the other hand, if the number of bisphenol structures is less than 2, it is difficult to improve the physical property balance of the mechanical properties of the cured product. By having two or more bisphenol structures in the molecule, the interaction of aromatic rings is expected in the cured product, and the physical property balance of the mechanical properties of the cured product (three-dimensional model) is improved.

  Furthermore, the component (A) needs to have a hydroxyl group. By having a hydroxyl group, interaction due to hydrogen bonding is expected in the cured product, and the physical property balance of the mechanical properties of the three-dimensional structure is improved. The number of hydroxyl groups contained in the component (A) is not particularly limited as long as it is 1 or more.

（式中、Ｒ^１は、−Ｃ（ＣＨ_３）_２−、−ＣＨ_２−、−ＳＯ_２−のいずれかであり、ｋは、１〜４の整数であり、ｎは、１〜１０の整数である。） Component (A) is a compound represented by the following general formula (1).

(In the formula, R ¹ is any ^one of —C (CH ₃ ) ₂ —, —CH ₂ —, —SO ₂ —, k is an integer of 1 to 4, and n is 1 to 10) (It is an integer.)

In the general formula (1), R ¹ is any ^one of —C (CH ₃ ) ₂ —, —CH ₂ —, and —SO ₂ —, and preferably —C (CH ₃ ) ₂ —. k is an integer of 1 to 4, preferably 1 or 2. n is an integer of 1 to 10, preferably an integer of 2 to 5, more preferably an integer of 2 to 4.
As a commercial item of the compound represented by the general formula (1), Epicote 834, 1001, 1002, 1003, 1004, 1055, 1003F, 1004F, 1005F (manufactured by Japan Epoxy Resin Co., Ltd.) and the like can be mentioned.
The epoxy equivalent of (A) component is 230-1500 g / eq, for example, Preferably it is 230-900 g / eq, More preferably, it is 230-500 g / eq.

  In the composition of the present invention, the blending ratio of the component (A) is 3 to 40% by mass, preferably 5 to 30% by mass, more preferably 5 to 25% by mass, with the total amount of the composition being 100% by mass. When the blending ratio of the component (A) is less than 3% by mass or exceeds 40% by mass, the improvement in the physical property balance of the mechanical properties of the three-dimensional model becomes insufficient, which is not preferable.

[Component (B)]
The component (B) used in the composition of the present invention is a cationically polymerizable compound other than the component (A). Component (B) is an organic compound that undergoes a polymerization reaction or a crosslinking reaction when irradiated with light in the presence of a cationic photopolymerization initiator. For example, an epoxy compound, an oxetane compound, an oxolane compound, a cyclic acetal compound, a cyclic lactone compound And a thiirane compound, a thietane compound, a vinyl ether compound, a spiro orthoester compound which is a reaction product of an epoxy compound and a lactone, an ethylenically unsaturated compound, a cyclic ether compound, a cyclic thioether compound, and a vinyl compound.

  Examples of the epoxy compound that can be used as the component (B) include bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, brominated bisphenol A diglycidyl ether, brominated bisphenol F diglycidyl ether, Brominated bisphenol S diglycidyl ether, epoxy novolac resin, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol S diglycidyl ether, 3,4-epoxycyclohexylmethyl-3 ′, 4′- Epoxycyclohexanecarboxylate, ε-caprolactone modified 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, Methyl caprolactone-modified 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, β-methyl-δ-valerolactone-modified 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, 2- (3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane-meta-dioxane, bis (3,4-epoxycyclohexylmethyl) adipate, vinylcyclohexene oxide, 4-vinylepoxycyclohexane, Bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, 3,4-epoxy-6-methylcyclohexyl-3 ′, 4′-epoxy-6′-methylcyclohexanecarboxylate, methylenebis (3,4 Poxycyclohexane), dicyclopentadiene diepoxide, di (3,4-epoxycyclohexylmethyl) ether of ethylene glycol, ethylene bis (3,4-epoxycyclohexanecarboxylate), dioctyl epoxyhexahydrophthalate, epoxyhexahydrophthalic acid Di-2-ethylhexyl, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ethers One or more alkylene oxalates in aliphatic polyhydric alcohols such as ethylene glycol, propylene glycol and glycerin Polyglycidyl ethers of polyether polyols obtained by adding an id; diglycidyl esters of aliphatic long-chain dibasic acids; monoglycidyl ethers of higher aliphatic alcohols; phenol, cresol, butylphenol or alkylene oxides on these Examples include monoglycidyl ethers of polyether alcohol obtained by addition; glycidyl esters of higher fatty acids; epoxidized soybean oil; butyl epoxy stearate; octyl epoxy stearate; epoxidized linseed oil; it can.

  Examples of other cationically polymerizable compounds that can be used as the component (B) include trimethylene oxide, 3,3-dimethyloxetane, 3,3-dichloromethyloxetane, 3-ethyl-3-hydroxymethyloxetane, 3- Oxetanes such as ethyl-3-phenoxymethyloxetane and bis (3-ethyl-3-methyloxy) butane; oxolanes such as tetrahydrofuran and 2,3-dimethyltetrahydrofuran; trioxane, 1,3-dioxolane, 1,3, Cyclic acetals such as 6-trioxane cyclooctane; cyclic lactones such as γ-propiolactone and ε-caprolactone; thiiranes such as ethylene sulfide, 1,2-propylene sulfide and thioepichlorohydrin; Thietanes such as dimethylthietan Vinyl ethers such as ethylene glycol divinyl ether, triethylene glycol divinyl ether and trimethylolpropane trivinyl ether; spiro orthoesters obtained by reaction of an epoxy compound with a lactone; ethylenically unsaturated compounds such as vinylcyclohexane, isobutylene and polybutadiene; Class: Derivatives of each of the above compounds can be exemplified.

Of these cationically polymerizable compounds, an epoxy compound and an oxetane compound are preferable from the viewpoint of the physical property balance of the mechanical properties of the cured product formed of the composition of the present invention.
Among epoxy compounds, an epoxy compound having two or more alicyclic epoxy groups in one molecule and an epoxy compound having a bisphenol structure are particularly preferable.
In the component (B), when the content of the epoxy compound having two or more alicyclic epoxy groups in one molecule and the oxetane compound content is 50% by mass or more, the cationic polymerization reaction rate (curing rate) of the resulting resin composition ), Suppression of temporal deformation of the three-dimensional object, and the like can be achieved.

  Specifically, among the cationically polymerizable compounds, 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, bis (3,4-epoxycyclohexylmethyl) adipate, bisphenol A diglycidyl ether, Bisphenol F diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, 3-ethyl-3-hydroxymethyloxetane and the like are preferable.

  As commercially available products of cationically polymerizable compounds that can be suitably used as the component (B), UVR-6100, UVR-6105, UVR-6110, UVR-6128, UVR-6200, UVR-6216 (manufactured by Union Carbide), Celoxide 2021, Celoxide 2021P, Celoxide 2081, Celoxide 2083, Celoxide 2085, Celoxide 2000, Celoxide 3000, Glycidol, AOEX24, Cyclomer A200, Cyclomer M100, Epolide GT-300, Epolide GT-301, Epolide GT-302, Epolide GT-302 -400, Epolide 401, Epolide 403 (above, manufactured by Daicel Chemical Industries), Epicoat 828, Epicoat 812, Epicoat 1031, Epicoat 8 2, Epicoat CT508, Epicoat 834, 1001, 1002, 1003, 1004, 1055, 1003F, 1004F, 1005F (above, manufactured by Japan Epoxy Resin Co., Ltd.), KRM-2100, KRM-2110, KRM-2199, KRM-2400, KRM -2410, KRM-2408, KRM-2490, KRM-2200, KRM-2720, KRM-2750 (above, manufactured by Asahi Denka Kogyo Co., Ltd.), Rapi-Cure DVE-3, CHVE, PEPC (above, made by ISP), VECTOMER 2010, 2020, 4010, 4020 (above, manufactured by Allied Signal) can be exemplified. Said cationically polymerizable compound can comprise (B) component individually by 1 type or in combination of 2 or more types.

In the composition of the present invention, the blending ratio of the component (B) is 20 to 85% by mass, preferably 25 to 70% by mass, more preferably 30 to 60% by mass, with the total amount of the composition being 100% by mass.
When the blending ratio of the component (B) is less than 20% by mass, the physical property balance of the mechanical properties of the three-dimensional model is deteriorated (particularly, the rigidity is reduced), which is not preferable. On the other hand, when the blending ratio of the component (B) exceeds 85% by mass, the blending ratio of the other components to be blended, particularly the component (A), is small, and the physical property balance of the mechanical properties of the three-dimensional model is deteriorated. Is not preferable.

[Component (C)]
(C) component used for the composition of this invention is a cationic photoinitiator. The cationic photopolymerization initiator is a compound that can release a substance that initiates cationic polymerization of the component (A) and the component (B) by receiving energy rays such as light. Here, energy rays such as light means visible light, ultraviolet light, infrared light, X-rays, α rays, β rays, γ rays, and the like. A particularly preferred compound (C) is an onium salt having a structure represented by the following general formula (2).
_{^{[R 2 a R 3 b R}} 4 c R 5 d W] + m [MX n + m] -m (2)
(Wherein the cation is an onium ion, W is S, Se, Te, P, As, Sb, Bi, O, I, Br, Cl or ^{-N = N, R 2, R} 3, R 4 And R ⁵ are the same or different organic groups, a, b, c and d are each an integer of 0 to 3, and (a + b + c + d) is equal to the valence of W + m, M is a halide complex [MX _{n + m} ], For example, B, P, As, Sb, Fe, Sn, Bi, Al, Ca, In, Ti, Zn, Sc, V, Cr, Mn, Co, etc. X is a halogen atom such as F, Cl, Br, etc., m is the net charge of the halide complex ion, and n is the valence of M.)

The onium salt represented by the general formula (2) is a compound that releases a Lewis acid by receiving light. Specific examples of the anion [MX _{n + m} ] in the general formula (2) include tetrafluoroborate (BF ₄ ⁻ ), hexafluorophosphate (PF ₆ ⁻ ), hexafluoroantimonate (SbF ₆ ⁻ ), hexafluoroarsenate. (AsF ₆ ⁻ ), hexachloroantimonate (SbCl ₆ ⁻ ) and the like.

Moreover, the onium salt which has an anion represented with general formula [MXn (OH) _< ^- >] can be used. Further, perchlorate ion (ClO ₄ ⁻ ), trifluoromethane sulfonate ion (CF ₃ SO ₃ ⁻ ), fluorosulfonate ion (FSO ₃ ⁻ ), toluene sulfonate ion, trinitrobenzene sulfonate anion, trinitrotoluene sulfonate Onium salts having other anions such as anions can also be used.

  Among such onium salts, aromatic onium salts are particularly effective as the component (C). Of these, aromatic halonium salts described in JP-A-50-151996, JP-A-50-158680, JP-A-50-151997, JP-A-52-30899, JP-A-56. Group VIA aromatic onium salts described in JP-A-55420, JP-A-55-125105, etc., Group VA aromatic onium salts described in JP-A-50-158698, etc., JP-A-56-8428 Oxosulfoxonium salts described in JP-A-56-149402 and JP-A-57-192429, aromatic diazonium salts described in JP-A-49-17040, US Pat. , 139,655 specification, and the like. Moreover, an iron / allene complex, an aluminum complex / photolytic silicon compound-based initiator, and the like can also be mentioned.

  Commercially available cationic photopolymerization initiators that can be suitably used as the component (C) include UVI-6950, UVI-6970, UVI-6974, UVI-6990 (manufactured by Union Carbide), Adekaoptomer SP- 150, SP-151, SP-170, SP-172 (above, manufactured by Asahi Denka Kogyo Co., Ltd.), Irgacure 261 (above, manufactured by Ciba Specialty Chemicals Co., Ltd.), CI-2481, CI-2624, CI-2639, CI-2064 (Nippon Soda Co., Ltd.), CD-1010, CD-1011, CD-1012 (Sartomer Co., Ltd.), DTS-102, DTS-103, NAT-103, NDS-103, TPS-103, MDS- 103, MPI-103, BBI-103 (manufactured by Midori Chemical Co., Ltd.), PCI-061T PCI-062T, PCI-020T, PCI-022T (or more, manufactured by Nippon Kayaku Co., Ltd.), and the like. Among these, UVI-6970, UVI-6974, Adekaoptomer SP-170, SP-172, CD-1012, and MPI-103 express high photocuring sensitivity in the resin composition containing them. It is particularly preferable because Said cationic photoinitiator can comprise (C) component individually by 1 type or in combination of 2 or more types.

  In the composition of the present invention, the blending ratio of the component (C) is 0.1 to 10% by mass, preferably 0.5 to 10% by mass, more preferably 1 to 10% by mass, with the total amount of the composition being 100% by mass. %. When the blending ratio of the component (C) is less than 0.1% by mass, the photocurability of the obtained resin composition is lowered, and it becomes difficult to form a three-dimensional modeled object having sufficient mechanical strength. On the other hand, when the blending ratio of the component (C) exceeds 10% by mass, when the resulting resin composition is subjected to an optical three-dimensional modeling method, appropriate light transmittance cannot be obtained, and the curing depth is controlled. Becomes difficult, and there is a tendency that the modeling accuracy of the three-dimensional model to be obtained decreases.

[(D) component]
(D) component used for the photocurable resin composition for optical three-dimensional model | molding of this invention is a radically polymerizable compound. The radical polymerizable compound is a compound having an ethylenically unsaturated bond (C = C) in the molecule, a monofunctional monomer having one ethylenically unsaturated bond in one molecule, and 2 in one molecule. Mention may be made of polyfunctional monomers having one or more ethylenically unsaturated bonds.

  Examples of the monofunctional monomer that can be suitably used as the component (D) include acrylamide, (meth) acryloylmorpholine, 7-amino-3,7-dimethyloctyl (meth) acrylate, isobutoxymethyl (meth) acrylamide, and isobornyl. Oxyethyl (meth) acrylate, isobornyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, ethyl diethylene glycol (meth) acrylate, t-octyl (meth) acrylamide, diacetone (meth) acrylamide, dimethylaminoethyl (meth) acrylate, Diethylaminoethyl (meth) acrylate, lauryl (meth) acrylate, dicyclopentadiene (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, dicyclope Tenenyl (meth) acrylate, N, N-dimethyl (meth) acrylamide tetrachlorophenyl (meth) acrylate, 2-tetrachlorophenoxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, tetrabromophenyl (meth) acrylate, 2 -Tetrabromophenoxyethyl (meth) acrylate, 2-trichlorophenoxyethyl (meth) acrylate, tribromophenyl (meth) acrylate, 2-tribromophenoxyethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2- Hydroxypropyl (meth) acrylate, vinylcaprolactam, N-vinylpyrrolidone, phenoxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, pentachloroph Nyl (meth) acrylate, pentabromophenyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, bornyl (meth) acrylate, methyltriethylene diglycol (meth) acrylate, and the following general formula The compounds represented by (3) to (5) can be exemplified.

（式（３）〜式（５）中、Ｒ^６はそれぞれ独立に水素原子またはメチル基を示し、Ｒ^７は炭素数２〜６、好ましくは２〜４のアルキレン基を示し、Ｒ^８は水素原子または炭素数１〜１２、好ましくは１〜９のアルキル基を示し、Ｒ^９は炭素数２〜８、好ましくは２〜５のアルキレン基を示す。ｒは０〜１２、好ましくは１〜８の整数であり、ｑは１〜８、好ましくは１〜４の整数である。）

(In the formulas (3) to (5), R ⁶ independently represents a hydrogen atom or a methyl group, R ⁷ represents an alkylene group having 2 to 6 carbon atoms, preferably 2 to 4 carbon atoms, and R ⁸ represents hydrogen. R ⁹ represents an atom or an alkyl group having 1 to 12 carbon atoms, preferably 1 to ⁹ carbon atoms, and R ⁹ represents an alkylene group having 2 to 8 carbon atoms, preferably 2 to 5. r is 0 to 12, preferably 1 to 8. And q is an integer of 1 to 8, preferably 1 to 4.)

  Of these monofunctional monomers, isobornyl (meth) acrylate, lauryl (meth) acrylate, and phenoxyethyl (meth) acrylate are particularly preferable. Examples of commercial products of these monofunctional monomers include Aronix M-101, M-102, M-111, M-113, M-117, M-152, TO-1210 (above, manufactured by Toagosei Co., Ltd.), KAYARAD. TC-110S, R-564, R-128H (manufactured by Nippon Kayaku Co., Ltd.), biscoat 192, biscoat 220, biscoat 2311HP, biscoat 2000, biscoat 2100, biscoat 2150, biscoat 8F, biscoat 17F (and above, Osaka Organic Chemical) (Made by an industrial company) etc. can be mentioned.

Examples of the polyfunctional monomer that can be suitably used as the component (D) include ethylene glycol di (meth) acrylate, dicyclopentenyl di (meth) acrylate, triethylene glycol di (meth) acrylate, and tetraethylene glycol di (meth) acrylate. , Tricyclodecanediyldimethylene di (meth) acrylate, tris (2-hydroxyethyl) isocyanurate di (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, caprolactone-modified tris (2-hydroxyethyl) ) Isocyanurate tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, ethylene oxide (hereinafter referred to as “EO”) modified trimethylolpropane tri (meth) acrylate Propylene oxide (hereinafter referred to as “PO”) modified trimethylolpropane tri (meth) acrylate, tripropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, both ends (meth) acrylic of bisphenol A diglycidyl ether Acid adduct, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, polyester di (meth) acrylate , Polyethylene glycol di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol tetra (meth) Chlorate, caprolactone modified dipentaerythritol hexa (meth) acrylate, caprolactone modified dipentaerythritol penta (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, EO modified bisphenol A di (meth) acrylate, PO modified bisphenol A di (meta) ) Acrylate, EO-modified hydrogenated bisphenol A di (meth) acrylate, PO-modified hydrogenated bisphenol A di (meth) acrylate, EO-modified bisphenol F di (meth) acrylate, phenol novolac polyglycidyl ether (meth) acrylate, bis ( (Meth) acryloxymethyl) hydroxymethyl isocyanurate, bis ((meth) acryloxyethyl) hydroxyethyl isocyanurate, tris ((meth) Examples include acryloxymethyl) isocyanurate, tris ((meth) acryloxyethyl) isocyanurate, caprolactone-modified tris ((meth) acryloxyethyl) isocyanurate, and the like.
Of these, isocyanurate compounds are preferably used.

  Commercially available products of these polyfunctional monomers include, for example, SA1002 (above, manufactured by Mitsubishi Chemical Corporation), biscoat 195, biscoat 230, biscoat 260, biscoat 215, biscoat 310, biscoat 214HP, biscoat 295, biscoat 300, biscoat 360, Viscoat GPT, Biscoat 400, Biscoat 700, Biscoat 540, Biscoat 3000, Viscoat 3700 (above, manufactured by Osaka Organic Chemical Industry Co., Ltd.), Kayarad R-526, HDDA, NPGDA, TPGDA, MANDA, R-551, R-712, R -604, R-684, PET-30, GPO-303, TMPTA, THE-330, DPHA, DPHA-2H, DPHA-2C, DPHA-2I, D-310, D-330, DPCA-20, D CA-30, DPCA-60, DPCA-120, DN-0075, DN-2475, T-1420, T-2020, T-2040, TPA-320, TPA-330, RP-1040, RP-2040, R- 011, R-300, R-205 (manufactured by Nippon Kayaku Co., Ltd.), Aronix M-210, M-220, M-233, M-240, M-215, M-305, M-309, M- 310, M-315, M-325, M-400, M-6200, M-6400 (above, manufactured by Toagosei Co., Ltd.), light acrylate BP-4EA, BP-4PA, BP-2EA, BP-2PA, DCP- A (above, Kyoeisha Chemical Co., Ltd.), New Frontier BPE-4, BR-42M, GX-8345 (above, Daiichi Kogyo Seiyaku Co., Ltd.), ASF-400 (above, Nippon Steel Chemical Co., Ltd.) ), Lipoxy SP-1506, SP-1507, SP-1509, VR-77, SP-4010, SP-4060 (above, Showa Polymer Co., Ltd.), NK ester A-BPE-4 (above, Shin-Nakamura Chemical) (Made by an industrial company) etc. can be mentioned.

The above monofunctional monomer and polyfunctional monomer are each used alone or in combination of two or more, or at least one monofunctional monomer and at least one polyfunctional monomer are combined to constitute component (D). However, in the component (D), a polyfunctional monomer having three or more functional groups, that is, three or more ethylenically unsaturated bonds in one molecule is 60% by mass with the total component (D) being 100% by mass. It is preferable to contain in the ratio of% or more. A more preferable content ratio of the trifunctional or higher polyfunctional monomer is 70% by mass or more, particularly preferably 80% by mass or more, and most preferably 100% by mass. When the content ratio of the trifunctional or higher polyfunctional monomer is less than 60% by mass, the photocurable property of the obtained resin composition is lowered, and the three-dimensional modeled object to be modeled is likely to be deformed over time. .
The trifunctional or higher polyfunctional monomer is selected from the tri (meth) acrylate compounds, tetra (meth) acrylate compounds, penta (meth) acrylate compounds, hexa (meth) acrylate compounds and the like exemplified above. Can do.

  In the composition of the present invention, the blending ratio of the component (D) is 3 to 45% by mass, preferably 5 to 35% by mass, more preferably 7 to 25% by mass, particularly preferably 100% by mass. Is 10 to 20% by mass. When the blending ratio of the component (D) is less than 3% by mass, the photocurability of the composition is lowered, and it becomes difficult to form a three-dimensional structure having sufficient mechanical strength. On the other hand, when the blending ratio of the component (D) exceeds 45% by mass, the composition tends to shrink by photocuring, and the resulting three-dimensional structure tends to decrease heat resistance, moisture resistance, and the like. .

[(E) component]
(E) component used for the photocurable resin composition for optical three-dimensional model | molding of this invention is a radical photopolymerization initiator. The radical photopolymerization initiator is a compound that is decomposed by receiving energy rays such as light and initiates a radical polymerization reaction of the component (D) (radical polymerizable compound) by a generated radical.

  Specific examples of the component (E) (radical photopolymerization initiator) include, for example, acetophenone, acetophenone benzyl ketal, anthraquinone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, and carbazole. , Xanthone, 4-chlorobenzophenone, 4,4′-diaminobenzophenone, 1,1-dimethoxydeoxybenzoin, 3,3′-dimethyl-4-methoxybenzophenone, thioxanthone compound, 2-methyl-1- [4- ( Methylthio) phenyl] -2-morpholino-propan-2-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, triphenylamine, 2,4,6- Trimethylbenzoyldiphenylphosphine oxide, bis (2, -Dimethoxybenzoyl) -2,4,4-tri-methylpentylphosphine oxide, benzyldimethyl ketal, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, fluorenone, fluorene , Benzaldehyde, benzoin ethyl ether, benzoin propyl ether, benzophenone, Michler ketone, 3-methylacetophenone, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone (BTTB), and BTTB and xanthene, thio Examples thereof include combinations with xanthene, coumarin, ketocoumarin and other dye sensitizers. Of these, benzyldimethyl ketal, 1-hydroxycyclohexyl phenyl ketone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butane-1- On is particularly preferred. Said radical photoinitiator can comprise (E) component individually by 1 type or in combination of 2 or more types.

  In the composition of the present invention, the blending ratio of the component (E) is 0.01 to 10% by mass, preferably 0.1 to 8% by mass, where the total amount of the composition is 100% by mass. When the blending ratio of the component (E) is less than 0.01% by mass, the radical polymerization reaction rate (curing rate) of the composition tends to be low, and it takes time for modeling or the resolution tends to decrease. . On the other hand, when the blending ratio of the component (E) exceeds 10% by mass, an excessive amount of the polymerization initiator may deteriorate the curing characteristics of the composition or adversely affect the moisture resistance and heat resistance of the three-dimensional structure. .

  The composition of the present invention can further contain a photosensitizer (polymerization accelerator), a reactive diluent and the like. Photosensitizers include amine compounds such as triethanolamine, methyldiethanolamine, triethylamine, diethylamine; thioxanthone, thioxanthone derivatives, anthraquinone, anthraquinone derivatives, anthracene, anthracene derivatives, perylene, perylene derivatives, benzophenone, benzoin Examples of the reactive diluent include vinyl ethers, vinyl sulfides, vinyl urethanes, urethane acrylates, and vinyl ureas.

[(F) component]
The composition of the present invention preferably further contains elastomer particles having an average particle diameter of 10 to 700 nm as the component (F). By including the component (F), the toughness and impact resistance of the cured product can be improved.
As the component (F), polybutadiene, polyisoprene, butadiene / acrylonitrile copolymer, styrene / butadiene copolymer, styrene / isoprene copolymer, ethylene / propylene copolymer, ethylene / α-olefin copolymer, Elastomer particles based on ethylene / α-olefin / polyene copolymer, acrylic rubber, butadiene / (meth) acrylic acid ester copolymer, styrene / butadiene block copolymer, styrene / isoprene block copolymer, etc. Can be mentioned.

Moreover, the core / shell type particle | grains which coat | covered these elastomer particles with the methyl (meth) acrylate polymer, the methyl (meth) acrylate / glycidyl (meth) acrylate copolymer, etc. can be mentioned. The ratio of the core radius to the shell thickness is usually 1/2 to 1,000 / 1, preferably 1/1 to 200/1. For example, when the core radius is 350 nm and the shell thickness is 10 nm, the ratio is 35/1.
In the case of core / shell type particles, polybutadiene, polyisoprene, styrene / butadiene copolymer, styrene / isoprene copolymer, butadiene / (meth) acrylate copolymer, styrene / butadiene block copolymer, styrene / Elastomer particles formed by coating a partially crosslinked core of an isoprene block copolymer with a methyl (meth) acrylate polymer, a methyl (meth) acrylate / glycidyl methacrylate copolymer, or the like.

  Furthermore, the elastomer particles of the component (F) may have a crosslinked structure inside the particles, and can be crosslinked by means usually used. The crosslinking agent used in this case is divinylbenzene, ethylene glycol di (meth) acrylate, diallyl maleate, triallyl cyanurate, triallyl isocyanurate, diallyl phthalate, trimethylolpropane tri (meth) acrylate, (meth) Examples include allyl acrylate.

  These elastomer particles can be prepared by a commonly used method, and examples thereof include an emulsion polymerization method. Examples of the emulsion polymerization method include, for example, a method in which all monomer components are charged and polymerized at once, a method in which a part of the monomer component is polymerized, and then the remainder is added continuously or intermittently, the monomer component A method of continuously adding from the beginning of polymerization or a method using seed particles can be employed.

  The average particle diameter of the (F) elastomer particles thus obtained is 10 nm to 700 nm. If the average particle diameter of the elastomer particles is less than 10 nm, the impact resistance and fracture toughness of the resulting three-dimensional shaped product will decrease, or the viscosity of the resin liquid will increase, affecting the productivity and modeling accuracy of the three-dimensional shaped product. Since it may affect, it is not preferable. On the other hand, if the average particle diameter of the elastomer particles exceeds 700 nm, a three-dimensional object with a sufficiently smooth surface cannot be obtained, or the modeling accuracy decreases. Examples of commercially available core / shell type elastomer particles as described above include Resin Bond RKB (manufactured by Resin Chemicals), Techno MBS-61, MBS-69 (manufactured by Techno Polymer Co., Ltd.), and the like. be able to.

  In the photocurable resin composition for optical three-dimensional modeling of the present invention, the blending ratio of the component (F) is preferably 1 to 35% by mass, more preferably 3 to 30% by mass, with the total amount of the composition being 100% by mass. Especially preferably, it is 5-25 mass%. If the blending ratio of the component (F) is 1% by mass or more, improvement in toughness and impact resistance of the three-dimensional structure can be expected. On the other hand, when the blending ratio of the component (F) exceeds 35% by mass, the viscosity increases, and as a result, bubbles are generated during modeling or the modeling accuracy of the three-dimensional object tends to decrease, such being undesirable.

[(G) component]
The composition of the present invention preferably further contains a polyether polyol as the component (G). By blending with polyether polyol, improvement of photocurability of the composition, shape stability (inhibition of deformation over time) and stability of physical properties (inhibition of change in mechanical properties over time) An improvement effect can be obtained.
The polyether polyol used as the component (G) preferably has 3 or more hydroxyl groups in one molecule, more preferably 3 to 6 hydroxyl groups in one molecule. When a polyether polyol (polyether diol) having less than 3 hydroxyl groups in one molecule is used, the effect of improving the photocurability is not sufficient, and the rigidity (elastic modulus) of the resulting three-dimensional structure is not sufficient. There is a tendency to decrease. On the other hand, when more than 6 polyether polyols are used in one molecule, there is a tendency that the elongation of the resulting three-dimensional model is lowered and a problem is caused in moisture resistance.

  Examples of the component (G) include trivalent or higher polyhydric alcohols such as trimethylolpropane, glycerin, pentaerythritol, sorbitol, sucrose, and quadrol, ethylene oxide (hereinafter referred to as EO), propylene oxide (hereinafter referred to as PO). And polyether polyols obtained by modifying with cyclic ether compounds such as butylene oxide and tetrahydrofuran, specifically, EO-modified trimethylolpropane, PO-modified trimethylolpropane, tetrahydrofuran-modified trimethylol. Propane, EO-modified glycerin, PO-modified glycerin, tetrahydrofuran-modified glycerin, EO-modified pentaerythritol, PO-modified pentaerythritol, tetrahydrofuran-modified pentaerythritol Toll, EO-modified sorbitol, PO-modified sorbitol, EO-modified sucrose, PO-modified sucrose, EO-modified quadrole, etc. Among them, EO-modified trimethylolpropane, PO-modified trimethylolpropane, PO-modified glycerin, PO Modified sorbitol is preferred.

  (G) It is preferable that the molecular weight of the polyether polyol used as a component is 100-2,000, More preferably, it is 160-1,000. When a polyether polyol having a molecular weight of less than 100 is used as the component (G), it may be difficult to obtain a three-dimensional structure having shape stability and physical property stability depending on the resin composition obtained. On the other hand, when a polyether polyol having a molecular weight exceeding 2,000 is used as the component (G), the viscosity of the obtained resin composition becomes excessive, and the elastic modulus of the three-dimensional structure obtained by optical three-dimensional modeling may decrease. is there.

  Commercially available polyether polyols that can be used as the component (G) include Sannix TP-400, Sannix GP-600, Sannix GP-1000, Sannix SP-750, Sannix GP-250, Sannix GP- 400, Sanix GP-600 (above, manufactured by Sanyo Chemical Co., Ltd.), TMP-3Glycol, PNT-4 Glycol, EDA-P-4, EDA-P-8 (above, manufactured by Nippon Emulsifier Co.), G-300, G -400, G-700, T-400, EDP-450, SP-600, SC-800 (manufactured by Asahi Denka Kogyo Co., Ltd.). Said polyether polyol can comprise (G) component individually by 1 type or in combination of 2 or more types.

  In the photocurable resin composition for optical three-dimensional modeling of the present invention, the blending ratio of the component (G) is preferably 5 to 35% by mass, more preferably 5 to 30 with 100% by mass of the total composition. % By mass, particularly preferably 5 to 25% by mass. When the blending ratio of the component (G) is 5% by mass or more, the effect of improving the photocurability of the composition can be sufficiently achieved, and a three-dimensional modeled object having excellent shape stability and physical property stability is ensured. Can get to. On the other hand, when the blending ratio of the component (G) exceeds 35% by mass, the photocurability of the resin composition is lowered, and the rigidity (elastic modulus) of the resulting three-dimensional structure tends to be lowered.

[Others]
In the composition of the present invention, various additives can be blended as other optional components as long as the objects and effects of the present invention are not impaired. Such additives include epoxy resin, polyamide, polyamideimide, polyurethane, polybutadiene, polychloroprene, polyether, polyester, styrene-butadiene block copolymer, petroleum resin, xylene resin, ketone resin, cellulose resin, fluorine-based oligomer, Polymers or oligomers such as silicone oligomers and polysulfide oligomers; polymerization inhibitors such as phenothiazine and 2,6-di-t-butyl-4-methylphenol; polymerization initiation aids; leveling agents; wettability improvers; Plasticizer; UV absorber; Silane coupling agent; Inorganic filler; Pigment;
The photocurable resin composition for optical three-dimensional modeling of the present invention is obtained as a liquid by uniformly mixing the above components (A) to (E) and other components blended as necessary. Can do. The viscosity (25 ° C.) of the liquid composition of the present invention thus obtained is preferably 50 to 2,000 cps, more preferably 70 to 1,500 cps.

  The composition of the present invention obtained as described above is suitably used as a photocurable resin composition for optical three-dimensional modeling in an optical three-dimensional modeling method. That is, a three-dimensional object having a desired shape is obtained by an optical three-dimensional modeling method that selectively irradiates light such as visible light, ultraviolet light, and infrared light to the composition of the present invention and supplies energy necessary for curing. A model can be manufactured.

Next, the three-dimensional modeled object of the present invention will be described. The three-dimensional molded item of the present invention is composed of a laminate of the cured product of the above-described photocurable liquid composition.
Each layer of the laminate is obtained by irradiating the liquid surface of the photocurable liquid composition with light. The liquid level can be leveled with a recoater or the like. At this time, by selectively irradiating light, a cured product (cross-section cured layer) having a desired pattern cross section can be obtained.
The manufacturing method of the three-dimensional molded item of this invention irradiates light to a photocurable liquid composition, forms the hardened | cured material (cross-section hardened layer) of this composition, and on this hardened | cured material (cross-sectional hardened layer) The liquid composition is supplied again and irradiated with light to further form a cured product (cross-section cured layer) of the liquid composition. Thereafter, this is repeated to laminate a plurality of cured products (cross-section cured layer). Then, a three-dimensional structure formed by integrating them is obtained.

The means for selectively irradiating the photocurable liquid composition with light is not particularly limited, and various means can be employed. For example, (a) means for irradiating the composition while scanning a laser beam or convergent light obtained using a lens, a mirror, etc., (b) using a mask having a light transmission part of a predetermined pattern, Means for irradiating the composition with non-converged light through a mask; (c) using a light guide member formed by bundling a number of optical fibers; and composing light through the optical fiber corresponding to a predetermined pattern in the light guide member Means for irradiating an object, (d) means for repeatedly executing collective exposure for each predetermined area, and the like can be employed.
In the means using the mask of (b), a mask image composed of a light transmitting area and a light non-transmitting area is formed electro-optically as a mask according to a predetermined pattern according to the same principle as the liquid crystal display device. You can also use what you want.
Laser beam with a small spot diameter is used as a means for selectively irradiating light to the liquid composition when the target three-dimensional structure has fine portions or high dimensional accuracy is required. It is preferable to employ means for scanning.
In addition, when the liquid composition is accommodated in the container, the light irradiation surface (for example, the scanning plane of the convergent light) is either the liquid surface of the composition or the contact surface with the vessel wall of the translucent container. There may be. When the liquid surface of the liquid composition or the contact surface with the vessel wall is used as the light irradiation surface, the light can be irradiated directly from the outside of the container or through the vessel wall.

  As described above, the three-dimensional object of the present invention can be manufactured by an optical three-dimensional modeling method such as an optical layered modeling method. In the optical three-dimensional modeling method, usually, after curing a specific part of the liquid composition, the light irradiation position (irradiation surface) is moved continuously or stepwise from the uncured part to the uncured part. Thus, the cured portions are laminated to obtain a desired three-dimensional shape. Here, the irradiation position can be moved by various methods, for example, by moving any one of the light source, the composition container, and the already cured portion of the composition, or additionally supplying the composition to the container The method of doing etc. is mentioned.

A representative example of the optical three-dimensional modeling method of the present invention will be described with reference to FIGS. FIG. 1 is a diagram illustrating an example of an optical layered modeling method, and FIG. 2 is a diagram illustrating an example of a system of a micro stereo modeling method.
[Optical additive manufacturing method]
The size of the three-dimensional modeled object modeled by the optical layered modeling method is usually a scale of several mm to several m, typically several cm to several tens of cm.
In FIG. 1, as shown in FIG. 1 (a), a support stage 3 provided in a container 2 containing the photocurable liquid composition 1 so as to be movable up and down is slightly lowered from the liquid surface 4 of the composition 1 ( Settling), the composition 1 is supplied onto the support stage 3 to form a thin layer of the composition 1. Next, the thin layer is selectively irradiated with light 8 through the mask 5 to form a cured product (cured resin layer) 6 of the composition 1.
Next, as shown in FIG. 1 (b), the support stage 3 is lowered (sedimented) by a small amount, and the composition 1 is supplied onto the cured product 6 to form a thin layer of the composition. Form again. Next, the thin layer is selectively irradiated with light 8 through the mask 5, and a new cured product 7 is further formed on the cured product 6 so as to be laminated integrally therewith. . Then, by repeating this step a predetermined number of times while changing or not changing the pattern irradiated with light, a three-dimensional modeled object in which a plurality of cured products are integrally laminated is modeled.

  The three-dimensional structure obtained in this way is taken out from the storage container, removed from the unreacted composition remaining on the surface, and then washed as necessary. Here, as the cleaning agent, alcohol-based organic solvents typified by alcohols such as isopropyl alcohol and ethyl alcohol; ketone-based organic solvents typified by acetone, ethyl acetate, methyl ethyl ketone, etc .; aliphatics typified by terpenes Organic solvents; low viscosity thermosetting resins and photocurable resins.

[Micro stereolithography]
The size of the three-dimensional modeled object modeled by the micro stereolithography is usually a scale of several μm to several cm, typically several tens of μm to several mm.
The liquid composition of the present invention is suitably used as a material for a micro-stereolithography method capable of producing a three-dimensional model having a smaller size than when using an optical layered modeling method.
In the micro stereolithography method, light irradiation is not performed only on a portion that needs to be scanned and cured by light, but is performed by repeating collective exposure for each predetermined region (projection region). Such collective exposure is performed using, for example, a digital mirror device (DMD).

In FIG. 2, a photo-curing modeling apparatus (hereinafter also referred to as an optical modeling apparatus) 100 includes a light source 11, a digital mirror device (DMD) 12, a lens 13, a modeling table 14, a dispenser 15, a recoater 16, a control unit 17, and a storage. A portion 18 is provided.
The light source 11 is a means for generating a laser beam. As the light source 11, for example, a laser diode (LD) or an ultraviolet (UV) lamp that generates 405 nm laser light is used.
The digital mirror device (DMD) 12 is a device developed by Texas Instruments, and hundreds of thousands to millions of micromirrors moving independently on a CMOS semiconductor, for example, 480,000 to 1.31 million are spread. It has been. Such a micromirror can be tilted by about ± 10 degrees, for example, about ± 12 degrees about the diagonal line by an electrostatic field effect. The micromirror has a square shape in which the length of one side of the pitch of each micromirror is about 10 μm, for example, 13.68 μm. The interval between adjacent micromirrors is, for example, 1 μm. The entire DMD 2 has a square shape of 40.8 × 31.8 mm (of which the mirror portion has a square shape of 14.0 × 10.5 mm), and the length of one side is 13.68 μm. The micro mirrors 786 and 432 are provided.
The DMD 12 reflects the laser beam emitted from the light source 11 by the individual micromirrors, and forms only the laser beam reflected by the micromirrors controlled by the control unit 17 at a predetermined angle through the condenser lens 13. The liquid composition layer 19 on the table 14 is irradiated.

The lens 13 guides the laser beam reflected by the DMD 12 onto the liquid composition layer 19 to form a projection region. The lens 13 may be a condenser lens using a convex lens or a concave lens. When a concave lens is used, a projection area larger than the actual size of the DMD can be obtained. The lens 13 is a condensing lens, and condenses the incident light on the liquid composition layer 19 by reducing the incident light by about 15 times.
The modeling table 14 is a plate-like table for sequentially depositing and placing a cured layer obtained by curing the liquid composition layer 19. The modeling table 14 can be moved horizontally and vertically by a driving mechanism (not shown), that is, a moving mechanism. With this drive mechanism, stereolithography can be performed over a desired range.
The dispenser 15 is a means for containing the photocurable liquid composition 20 of the present invention and supplying a predetermined amount of the liquid composition 20 to a predetermined position on the modeling table.
The recoater 16 is means for uniformly applying the liquid composition 20 to form the liquid composition layer 19, and includes, for example, a blade mechanism and a moving mechanism.

The control unit 17 controls the light source 11, DMD 12, modeling table 14, dispenser 15, and recoater 16 according to control data including exposure data. The control unit 17 can typically be configured by installing a predetermined program in a computer. A typical computer configuration includes a central processing unit (CPU) and memory. The CPU and the memory are connected to an external storage device such as a hard disk device as an auxiliary storage device via a bus. This external storage device functions as the storage unit 18 of the control unit 17.
Storage medium driving devices such as a flexible disk device, a hard disk device, and a CD-ROM drive are connected to the bus via various controllers. A portable storage medium such as a flexible disk is inserted into a storage medium driving apparatus such as a flexible disk apparatus.
The storage medium can store a predetermined computer program for operating the system by giving instructions to the CPU in cooperation with the operating system.
The storage unit 18 stores control data including exposure data of cross-sectional groups obtained by slicing a three-dimensional model to be modeled into a plurality of layers.
The control unit 17 mainly controls the angle control of each micromirror in the DMD 12 and the movement of the modeling table 14 (that is, the position of the irradiation range of the laser beam with respect to the three-dimensional model) based on the exposure data stored in the storage unit 18. Execute the modeling of the three-dimensional model.

  The computer program is executed by being loaded into a memory. The computer program can be compressed or divided into a plurality of parts and stored in a storage medium. In addition, user interface hardware can be provided. Examples of the user interface hardware include a pointing device for inputting such as a mouse, a keyboard, or a display for presenting visual data to the user.

Next, the optical modeling operation of the optical modeling apparatus 100 will be described.
First, the liquid composition 20 is accommodated in the dispenser 15. The modeling table 14 is in the initial position. The dispenser 15 supplies the liquid composition 20 contained on the modeling table 14 by a predetermined amount. The recoater 16 forms the liquid composition layer 19 for one layer to be swept and stretched as the liquid composition 20 is stretched.
The laser beam emitted from the light source 11 enters the DMD 12. The DMD 12 is controlled by the control unit 17 in accordance with the exposure data stored in the storage unit 18, and adjusts the angle of a part of the micromirrors that are portions that irradiate the liquid composition layer 19 with the laser beam. As a result, the laser beam reflected by some of the micromirrors is applied to the liquid composition layer 19 via the condenser lens 13, while the laser beam reflected by the remaining micromirrors is applied to the liquid composition layer. 19 will not be irradiated.
The laser beam irradiation to the liquid composition layer 19 is performed for 0.4 seconds, for example. At this time, the projection area onto the liquid composition layer 19 is, for example, about 1.3 × 1.8 mm, and can be reduced to about 0.6 × 0.9 mm. The area of the projection region is desirably 100 mm ² or less.

By using a concave lens for the lens 13, the projection area can be enlarged to about 6 × 9 cm. If the projection area is enlarged beyond this size, the energy density of the laser beam applied to the projection area becomes low, and the liquid composition layer 19 may be insufficiently cured.
When forming a three-dimensional model larger than the size of the laser beam projection area, it is necessary to irradiate the entire modeling area by moving the irradiation position of the laser beam, for example, by horizontally moving the modeling table 14 using a moving mechanism. There is. Laser beam irradiation is performed one shot at each projection area. Control of laser beam irradiation to each projection area will be described in detail later.
In this way, by moving the projection area and performing irradiation of the laser beam with each projection area as a unit, that is, exposure, the liquid composition layer 19 is cured, and a first cured layer is formed. The The lamination pitch for one layer, that is, the thickness of the cured layer is, for example, 1 to 50 μm, preferably 2 to 10 μm, and more preferably 5 to 10 μm.

Then, the 2nd layer of the solid model of a desired shape is formed in the same process. Specifically, the liquid composition 20 supplied from the dispenser 15 is applied to the outer side of the cured layer formed as the first layer so as to be stretched beyond the three-dimensional model by the recoater 16. . Then, a second hardened layer is formed on the first hardened layer by irradiating with a laser beam.
Thereafter, the third and subsequent cured resin layers are sequentially deposited in the same manner. Then, when the deposition of the final layer is completed, the modeled object formed on the modeling table 14 is taken out. The molded object removes the photocurable resin liquid adhering to the surface by washing or other methods. The molded article can be further cured by being irradiated or heated with an ultraviolet lamp or the like as necessary.

  The three-dimensional structure obtained in this way is excellent in all of rigidity, impact resistance and toughness. Furthermore, in order to improve the surface strength and heat resistance of the three-dimensional structure, it is preferable to use a thermosetting or photo-curable hard coat material after the washing treatment. As such a hard coat material, an organic coat material made of an acrylic resin, an epoxy resin, a silicone resin or the like, or an inorganic hard coat can be used. These hard coat materials can be used alone or in combination of two or more. Can be used.

  EXAMPLES Next, although an Example is given and this invention is demonstrated further in detail, this invention is not limited to these Examples at all.

[Examples 1 to 5, Comparative Examples 1 to 4]
In accordance with the formulation shown in Table 1, each component was charged into a stirring vessel and stirred at 60 ° C. for 3 hours to produce a liquid resin composition. The physical properties of the obtained liquid resin composition were evaluated by the following methods. The results are also shown in Table 1.

Evaluation method [film Young's modulus]
(1) Preparation of test piece The liquid resin composition was applied in a glass plate shape to a thickness of 200 μm, and a cured film was obtained by irradiating 1 J / cm ² using a metal halide lamp. Then, it was left still for 24 hours in a constant temperature and humidity room with a temperature of 23 ° C. and a humidity of 50%.
(2) Measurement A test piece having a size of 8 cm × 0.6 cm was cut out from the cured film thus prepared. The Young's modulus of the test piece was measured according to JIS K7127 using a tensile measurement tester AGS-50G manufactured by Shimadzu Corporation. At this time, the tensile speed was 1 mm / min, and the distance between marked lines was 2.5 cm (the gripping distance on both ends was 2.75 cm).

[Film bending resistance]
(1) Preparation of test piece A cured film was prepared under the same conditions as the preparation of a test piece having a film Young's modulus.
(2) Measurement The cured film thus prepared was allowed to stand in a constant temperature and humidity chamber at a temperature of 23 ° C. and a humidity of 50% for 24 hours, and then a test piece having a size of 12 cm × 1.5 cm was cut out. Using the MIT type bending tester, the number of bending until the test piece broke was measured. The initial load was measured at 200 gf.

[Film impact value]
(1) Preparation of test piece A cured film was prepared under the same conditions as the preparation of a test piece having a film Young's modulus.
(2) Measurement The test piece prepared in this manner was allowed to stand in a constant temperature and humidity chamber at a temperature of 23 ° C. and a humidity of 50% for 24 hours, and then a test piece having a size of 10 cm × 10 cm was cut out. The film impact value was measured using a film impact tester manufactured by Yasuda Seiki Co., Ltd. The impact sphere was a 12 mm diameter plastic sphere.

[Bending elastic modulus]
This was performed in accordance with JIS K7171.
In addition, the test piece uses solid creator SCS-300P (manufactured by Sony Manufacturing Systems Co., Ltd.) under the conditions of a laser power of 100 mW on the irradiated surface (liquid surface) and a scanning speed with a curing depth of 300 μm in each composition. It was produced by repeating the step of selectively irradiating the resin composition with laser light to form a cured resin layer (thickness: 200 μm). The prepared test piece was allowed to stand for 24 hours in a constant temperature and humidity room at a temperature of 23 ° C. and a humidity of 50%, and then the measurement was performed.
[Izod impact value]
This was performed in accordance with JIS K7110.
The test piece was prepared under the same conditions as the preparation of the flexural modulus test piece, and the sample was allowed to stand in a constant temperature and humidity chamber at a temperature of 23 ° C. and a humidity of 50% for 24 hours, and then the measurement was performed.

The details of each component described in Table 1 are as follows.
1) Epicoat 834 (trade name) manufactured by Japan Epoxy Resin Co., Ltd.
2) Union Carbide, UVR-6110 (trade name)
3) Epicoat 828 (trade name) manufactured by Japan Epoxy Resin Co., Ltd.
4) Epicoat 806 (trade name) manufactured by Japan Epoxy Resin Co., Ltd.
5) Aron Oxetane OXT-101 (trade name) manufactured by Toa Gosei Co., Ltd.
6) CPI-101A (trade name) manufactured by San Apro
7) Aronix M-315 (trade name) manufactured by Toa Gosei Co., Ltd.
8) Irgacure 184 (trade name), manufactured by Ciba Specialty Chemicals
9) Resinous Kasei Co., Ltd., Resinous Bond RKB (trade name)
10) Sanyo Chemicals, Sannix GP-400 (trade name), molecular weight 396.5

From Table 1, the cured products (Examples 1 to 5) of the composition of the present invention have rigidity (high film Young's modulus, high flexural modulus), impact resistance (high film impact value, high Izod impact value), toughness. It turns out that it is excellent in all (film bending resistance). Specifically, the cured product (Examples 1 to 5) of the composition of the present invention has a film Young's modulus of 1,050 MPa or more, a film bending resistance of 130 times or more, and a film impact value of 40 J / cm or more. , Having a flexural modulus of 2,000 MPa or more and an Izod impact value of 4.2 kJ / m ² or more.
On the other hand, in Comparative Examples 1 to 4 in which the blending ratio of the component (A) is outside the scope of the present invention, the balance of the above characteristics is inferior. That is, in Comparative Example 1, each of the film bending resistance, the film impact value, and the Izod impact value is inferior. In Comparative Examples 2 to 4, the value of the flexural modulus is inferior.

It is a figure which shows an example of the optical lamination molding method. It is a figure which shows an example of the system of micro stereolithography.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Photocurable liquid composition 2 Container 3 Support stage 4 Liquid level of photocurable liquid composition 5 Mask 6,7 Hardened | cured material (hardened layer)
8 Light 11 Light source 12 Digital mirror device (DMD)
DESCRIPTION OF SYMBOLS 13 Condensing lens 14 Modeling table 15 Dispenser 16 Recoater 17 Control part 18 Memory | storage part 19 Liquid composition layer 20 Photocurable liquid composition 100 Photocurable modeling apparatus (optical modeling apparatus)

Claims (5)

The total amount of the composition is 100% by mass,
(A) 3-40% by mass of a cationically polymerizable compound having two or more bisphenol structures and one or more hydroxyl groups,
(B) Cationic polymerizable compound other than component (A) 20 to 85% by mass,
(C) Cationic photopolymerization initiator 0.1 to 10% by mass,
(D) Radical polymerizable compound 3-45 mass%, and
(E) 0.01-10% by mass of a radical photopolymerization initiator,
A photocurable resin composition for optical three-dimensional modeling containing
The said (A) component is an epoxy compound represented by following General formula (1), The photocurable resin composition for optical three-dimensional modeling characterized by the above-mentioned .

(In formula (1), R ¹ is any ^one of —C (CH ₃ ) ₂ —, —CH ₂ —, and —SO ₂ —, k is an integer of 1 to 4, and n is 1 It is an integer of -10.) The photocurable resin composition for optical three-dimensional modeling according to claim 1 , wherein the component (B) contains a compound having an oxetane structure. The photocurable resin composition for optical three-dimensional modeling according to claim 1 or 2 , wherein the component (B) contains a compound having a bisphenol structure. The photocurable resin composition for optical three-dimensional modeling according to any one of claims 1 to 3 , further comprising (F) elastomer particles having an average particle diameter of 10 to 700 nm. The three-dimensional molded item which consists of hardened | cured material of the photocurable resin composition for optical three-dimensional modeling of any one of Claims 1-4 .

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