JP5334389B2 - Photo-curable resin composition for optical three-dimensional modeling and three-dimensional modeling - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photocurable resin composition capable of yielding a three-dimensional article having a high rigidity (Young's modulus, flexural modulus) and a high toughness (bending resistance, impact resistance). <P>SOLUTION: The photocurable resin composition comprises (A) a cationically polymerizable compound having two or more bisphenol structures and one or more hydroxyl groups, (B) a cationically polymerizable compound other than the component (A), (C) a cationic photoinitiator, (D) a radically polymerizable compound, (E) a radical photoinitiator, and (F) multilayer polymer particles having a core and a shell layer, provided that the shell layer contains functional group-modified rubber polymer particles having at least one reactive functional group chosen from the group consisting of an epoxy group, a hydroxyl group, a (meth)acryloyl group and an oxetanyl group. The composition 1 is used as a material for preparing cured layers 6 and 7 in a photofabrication method to yield the three-dimensional article. <P>COPYRIGHT: (C)2009,JPO&amp;INPIT

Description

  The present invention relates to a photocurable resin composition for optical three-dimensional modeling, and a three-dimensional modeled product made of the composition.

  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, resin compositions such as the following [a] to [c] have been disclosed as photocurable resin compositions for optical three-dimensional modeling used in the optical three-dimensional modeling method.
[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 high mechanical properties that are close to or equivalent to the original engineering plastics.

However, the techniques of Patent Documents 5 to 7 (the composition of [A] above) have a problem that curing shrinkage is large and it is difficult to obtain high modeling accuracy. Moreover, although the technique of the patent document 8 (composition of said [b]) can obtain high modeling precision, it exists in the tendency to give a brittle hardened | cured material with low toughness, and there exists a problem that a cure rate is inferior. In the techniques of Patent Documents 9 to 14 (composition of [C] above), there is a problem that some mechanical properties, particularly toughness, are inferior compared to general-purpose resins.
Here, for the purpose of improving the mechanical strength of the three-dimensional structure, a technique for blending particles made of an elastomer or the like is known (Patent Document 15). However, mechanical properties, particularly toughness, are still insufficient for use in prototypes of plastic parts manufactured with engineering plastics such as ABS resin. Also, a large amount of elastomer particles is used for the purpose of improving toughness. When it mix | blends, a Young's modulus etc. will fall and there exists a problem that the molded article which has high rigidity cannot be obtained.

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

  Therefore, the present invention provides an optical solid that gives a cured product (three-dimensional model) having high toughness (for example, bending resistance, impact resistance, etc.) and high rigidity (Young's modulus, flexural modulus, etc.) after curing. It aims at providing the photocurable resin composition for modeling, and the three-dimensional molded item which consists of this composition.

  As a result of intensive studies to solve the above problems, the present inventor has developed a specific cationic polymerizable compound, another cationic polymerizable compound, a cationic photopolymerization initiator, a radical polymerizable compound, a radical photopolymerization initiator, And a photocurable resin composition containing functional group-modified rubber-like polymer particles, it was found that a cured product having the above physical properties can be obtained, 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］ 上記（Ｆ）成分である多層構造重合体粒子中、官能基の含量が１０００〜２５００ｇ／ｅｑである上記［１］に記載の光学的立体造形用光硬化性樹脂組成物。
［３］ 上記（Ｆ）成分である多層構造重合体粒子が、１０〜７００ｎｍの平均粒子径を有する上記［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］ 上記（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］〜［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（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］〜［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。
［６］ 上記［１］〜［５］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 [6].
[1] (A) a cationic polymerizable compound having two or more bisphenol structures and one or more hydroxyl groups, (B) a cationic polymerizable compound other than the component (A), (C) a cationic photopolymerization initiator, D) a radically polymerizable compound, (E) a radical photopolymerization initiator, and (F) a multilayer structure polymer particle comprising a core and a shell layer, wherein the shell layer comprises an epoxy group, a hydroxyl group, (meth) A photocurable resin composition for optical three-dimensional modeling, comprising functional group-modified rubber-like polymer particles having at least one reactive functional group selected from the group consisting of an acryloyl group and an oxetanyl group, wherein the light The total amount of the curable resin composition is 100% by mass, the compounding ratio of the component (A) is 3 to 40% by mass, the compounding ratio of the component (B) is 20 to 85% by mass, and the compounding of the component (C). The ratio is 0. 1 to 10% by weight, the blending ratio of the component (D) is 3 to 45% by weight, the blending ratio of the component (E) is 0.01 to 10% by weight, and the blending ratio of the component (F) is 1 to 1%. 35% by mass, and the component (A) is an epoxy compound having an epoxy equivalent of 230 to 1500 g / eq represented by the following general formula (1) . Resin composition.

(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 content of the functional group is 1000 to 2500 g / eq in the multilayer structure polymer particle as the component (F).
[ 3 ] The photocurable resin composition for optical three-dimensional modeling according to the above [1] or [2] , wherein the multilayer structure polymer particles as the component (F) have an average particle diameter of 10 to 700 nm.
[4] The photocurable resin composition for optical three-dimensional modeling according to any one of [1] to [3], wherein the component (B) includes a compound having an oxetane structure.
[5] The photocurable resin composition for optical three-dimensional modeling according to any one of [1] to [4], wherein the component (B) includes a compound having a bisphenol structure.
[6] A three-dimensional molded article made of a cured product of the photocurable resin composition for optical three-dimensional modeling according to any one of [1] to [5].

Since the photocurable resin composition of the present invention contains a specific cationic polymerizable compound and functional group-modified polymer particles, the bending resistance is maintained while maintaining good rigidity (Young's modulus, bending elastic modulus, etc.). Further, it is possible to give a three-dimensional molded article (cured product) having excellent toughness with greatly improved impact resistance (film impact value, Izod impact value, etc.).
Since the photocurable resin composition of the present invention can give a cured product having mechanical properties close to engineering plastics such as ABS resin, it is suitable as a material for forming prototypes of parts made of engineering plastics. Used for.

The photocurable resin composition for optical three-dimensional model | molding of this invention contains (A)-(F) component and the other component added as needed.
Hereinafter, each component will be described in detail.
[(A) component]
The component (A) used in the photocurable resin composition for optical three-dimensional modeling of the present invention is a cationically polymerizable compound having two or more bisphenol structures and one or more hydroxyl groups, which will be described later. Is an epoxy compound having an epoxy equivalent of 230 to 1500 g / eq . By blending the component (A), a three-dimensional structure (cured material) having improved mechanical properties, that is, excellent bending resistance and impact resistance, and high rigidity can be obtained.
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 structures contained in the component (A) molecule needs to be 2 or more, preferably 2 to 11, more preferably 2 to 6, and particularly preferably 2 to 5. When the number of bisphenol structures exceeds 11, the viscosity of the composition becomes excessive, which is not preferable. On the other hand, when the number of bisphenol structures is less than 2, it is not preferable because the mechanical strength of the cured product cannot be improved. By having two or more bisphenol structures in the molecule, the interaction of aromatic rings is expected in the cured product, and the mechanical properties of the three-dimensional structure are improved.

  Furthermore, the component (A) needs to have a hydroxyl group. By having a hydroxyl group, interaction by hydrogen bonding is expected in the cured product, and the mechanical properties of the three-dimensional structure are 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。） It is the component (A), a compound represented by the following general formula (1) is used.

(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.
(A) an epoxy equivalent of the component, 230~1500g / eq, preferably 230~900g / eq, more preferably 230~500g / eq.

In the photocurable resin composition for optical three-dimensional modeling of the present invention, the blending ratio of the component (A) is 3 to 40% by mass , preferably 5 to 30% by mass , with the total amount of the composition being 100% by mass. Especially preferably, it is 5-25 mass%. When the blending ratio of the component (A) is less than 3% by mass, it is not preferable because the mechanical properties of the three-dimensional model cannot be improved. On the other hand, when the blending ratio of the component (A) exceeds 40% by mass, the rigidity is not preferable.

[Component (B)]
The component (B) used in the photocurable resin composition of the present invention is a cationically polymerizable compound other than the component (A).
The component (B) is an organic compound that causes a polymerization reaction or a crosslinking reaction when irradiated with light in the presence of a cationic photopolymerization initiator. Examples of the component (B) include epoxy compounds, oxetane compounds, oxolane compounds, cyclic acetal compounds, cyclic lactone compounds, thiirane compounds, thietane compounds, vinyl ether compounds, spiro orthoester compounds that are reaction products of epoxy compounds and lactones. , Ethylenically unsaturated compounds, cyclic ether compounds, cyclic thioether compounds, vinyl compounds, and the like.

  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.

Among these cationically polymerizable compounds, epoxy compounds and oxetane compounds are preferable, and among epoxy compounds, epoxy compounds having two or more alicyclic epoxy groups in one molecule and epoxy compounds having a bisphenol structure are preferable. . When the component (B) contains an oxetane compound, the mechanical properties of the three-dimensional structure can be further improved. Moreover, when the (B) component contains the epoxy compound which has a bisphenol structure, the rigidity of a three-dimensional molded item can be improved. Furthermore, when the content of the epoxy compound having two or more alicyclic epoxy groups in one molecule in the component (B) is 35% by mass or more, the cation polymerization reaction rate (curing rate) of the resulting resin composition Improvement, 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, Epicort CT508 (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, made 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 photocurable resin composition for optical three-dimensional modeling of the present invention, the blending ratio of the component (B) is 20 to 85% by mass , preferably 25 to 70% by mass , where the total amount of the composition is 100% by mass . There is . When the blending ratio of the component (B) is less than 20% by mass, the rigidity of the three-dimensional model is not preferable. On the other hand, when the blending ratio of the component (B) exceeds 85% by mass, the ratio of the other components to be blended, particularly the ratio of the component (A) is decreased, and the mechanical properties of the three-dimensional structure cannot be improved. Absent.

[Component (C)]
(C) component used for the photocurable resin 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 components (A) and (B) by receiving energy rays such as light. Here, energy rays such as light mean 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 photocurable resin 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 , based on 100% by mass of the total composition. Preferably it is 1-10 mass%. If the blending ratio is less than 0.1% by mass, the photocurability of the obtained resin composition is lowered, and it is not preferable because a three-dimensional model having excellent mechanical properties cannot be formed. On the other hand, when the blending ratio exceeds 10% by mass, when the obtained resin composition is subjected to an optical three-dimensional modeling method, it is not possible to obtain appropriate light transmittance, and it becomes difficult to control the curing depth, Since there exists a tendency for the modeling precision of the obtained three-dimensional molded item to fall, it is not preferable.

[(D) component]
(D) component used for the photocurable resin composition 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) (Manufactured by Kogyo Co., Ltd.).

  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) Acrylate, 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. Among these, isocyanurate compounds are preferable, bis ((meth) acryloxyethyl) hydroxyethyl isocyanurate and tris ((meth) acryloxyethyl) isocyanurate are more preferable, and tris ((meth) acryloxyethyl) isocyanurate is further included. preferable.

  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) (Manufactured by Kogyo Co., Ltd.).

  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. Among these, tris ((meth) acryloxyethyl) isocyanurate, trimethylolpropane tri (meth) acrylate, EO-modified trimethylolpropane tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipenta Erythritol penta (meth) acrylate and ditrimethylolpropane tetra (meth) acrylate are particularly preferred.

Photocurable resin composition of the present invention, the blending ratio of the component (D) is 100% by mass of the total composition, 3 to 45 wt%, preferably from 5 to 35% by weight, particularly preferably from 7 to 25 mass %. When the blending ratio of the component (D) is less than 3% by mass, the photocurability of the obtained resin composition is lowered, and a three-dimensional molded article having excellent mechanical properties cannot be formed, which is not preferable. On the other hand, when the blending ratio of the component (D) exceeds 45% by mass, the resulting resin composition is easily shrunk by photocuring, and the resulting three-dimensional molded product has reduced heat resistance, moisture resistance, and the like. Since there is a tendency, it is not preferable.

[(E) component]
The component (E) used in the photocurable resin composition of the present invention is a radical photopolymerization initiator. The component (E) (radical photopolymerization initiator) is a compound that is decomposed by receiving energy rays such as light and initiates the radical polymerization reaction of the component (D) by the generated radicals.

  Specific examples of the radical photopolymerization initiator that can be used as the component (E) include, for example, acetophenone, acetophenone benzyl ketal, anthraquinone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropane-1 -One, 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 (2,6-dimethoxybenzoyl) -2,4,4-tri-methylpentylphosphine oxide, benzyldimethyl ketal, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropane 1-one, fluorenone, fluorene, benzaldehyde, benzoin ethyl ether, benzoin propyl ether, benzophenone, Michler's ketone, 3-methylacetophenone, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone (BTTB) And combinations of BTTB and xanthene, thioxanthene, 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 photocurable resin composition for optical three-dimensional modeling 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 , with the total amount of the composition being 100% by mass. %. When the blending ratio is less than 0.01% by mass, the radical polymerization reaction rate (curing rate) of the resulting resin composition tends to be low, and it takes time for modeling or the resolution tends to decrease. It is not preferable. On the other hand, when the blending ratio exceeds 10% by mass, an excessive amount of the polymerization initiator may adversely affect the moisture resistance and heat resistance of the three-dimensional structure, or may deteriorate the curing characteristics of the resin composition. Absent.

  The photo-curable resin composition for optical three-dimensional modeling 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 component (F) used in the photocurable resin composition for optical three-dimensional modeling of the present invention is a functional group-modified rubbery polymer particle.
(F) Preferred examples of functional group-modified rubber-like polymer particles include a core made of a specific rubber-like polymer, and a specific monomer graft-polymerized to the rubber-like polymer constituting the core. Examples thereof include elastomer particles having a core / shell structure composed of a layer (shell layer) covering a part or the whole of the surface of the core.
As the monomer constituting the shell layer in the elastomer particle having such a core / shell structure, at least one monomer having a functional group is used.
In the present invention, by including the (F) functional group-modified rubber-like polymer particles, compared with the case of using the rubber-like polymer particles not modified with the functional group, the three-dimensional shaped object which is a cured product of the composition Stiffness (Young's modulus, flexural modulus, etc.) and toughness (bending resistance, impact resistance, etc.) can be greatly improved.

  As the rubber-like polymer for forming the core, at least one monomer selected from a conjugated diene monomer and a (meth) acrylic acid ester monomer is 50 to 100% by mass, and these A diene / (meth) acrylic rubbery polymer obtained by (co) polymerizing a monomer component containing 0 to 50% by mass of another monomer copolymerizable with the monomer is preferred. Further, as the rubber-like polymer, the diene / (meth) acrylic rubber-like polymer and other rubber-like polymers (for example, polysiloxane rubber-like polymer) can be used in combination.

Examples of the conjugated diene monomer include butadiene, isoprene, chloroprene, and the like. Among them, butadiene is preferable because the properties of the resulting polymer as rubber are excellent.
Examples of the (meth) acrylic acid ester monomer include butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, and the like, but the properties of the resulting polymer as rubber From the point that is excellent, butyl (meth) acrylate and 2-ethylhexyl (meth) acrylate are preferable.
These monomers can be used alone or in combination of two or more.
Examples of other monomers copolymerizable with these monomers include vinyl monomers such as aromatic vinyl monomers and vinyl cyanide monomers. As the aromatic vinyl monomer, for example, styrene, α-methylstyrene, vinyl naphthalene and the like can be used. As the vinyl cyanide monomer, for example, (meth) acrylonitrile, substituted acrylonitrile and the like are used. Is possible. These can be used alone or in combination of two or more.

  The ratio of the conjugated diene monomer and the (meth) acrylic acid ester monomer used is preferably 100% by mass based on the total amount of monomer components constituting the diene / (meth) acrylic rubbery polymer. It is 50-100 mass%, More preferably, it is 60-100 mass%. If the ratio is less than 50% by mass, a three-dimensional model having excellent toughness may not be obtained. In addition, the proportion of the other copolymerizable monomer that is an optional component is preferably 0 to 100% by weight, based on the total amount of monomer components constituting the diene / (meth) acrylic rubber-like polymer. It is 50 mass%, More preferably, it is 0-40 mass%.

  In addition, as a monomer component constituting the diene / (meth) acrylic rubber-like polymer, a polyfunctional monomer may be included in order to adjust the degree of crosslinking. Examples of the polyfunctional monomer include divinylbenzene, butanediol di (meth) acrylate, triallyl (iso) cyanurate, allyl (meth) acrylate, diallyl itaconate, diallyl phthalate, and the like. The use ratio of these polyfunctional monomers is 10% by mass or less, preferably 5% by mass or less, based on 100% by mass of the total amount of monomer components constituting the diene / (meth) acrylic rubbery polymer. is there. If the use ratio exceeds 10% by mass, the toughness of the three-dimensional structure tends to be inferior.

  The rubbery polymer constituting the core includes polybutadiene, polyisoprene, and styrene / butadiene copolymer among diene / (meth) acrylic rubbery polymers obtained by (co) polymerizing the above monomer components. A rubbery polymer made of styrene / isoprene copolymer or butadiene / (meth) acrylic acid ester copolymer is preferred, and a rubbery polymer made of polybutadiene is more preferred.

The polysiloxane rubbery polymer used in combination with the diene / (meth) acrylic rubbery polymer is composed of alkyl or aryl disubstituted silyloxy units such as dimethylsilyloxy, methylphenylsilyloxy, diphenylsilyloxy and the like. A polysiloxane rubber-like polymer can be used. In addition, polysiloxane rubber-like polymer is preliminarily introduced with a cross-linked structure during polymerization by partially using a polyfunctional alkoxysilane compound or by radical reaction of a silane compound having a vinyl reactive group. It is more preferable to keep it.
In the rubbery polymer, the blending ratio of the diene / (meth) acrylic rubbery polymer is 70 to 100% by mass, preferably 80 to 100% by mass.

The shell layer is formed by graft polymerization of a specific monomer to the rubbery polymer. The specific monomer includes at least one monomer having a functional group, and preferably includes a monomer having a functional group and a monomer having no functional group.
The monomer having a functional group constituting the shell layer is preferably a monomer having at least one functional group selected from the group consisting of an epoxy group, a hydroxyl group, a (meth) acryloyl group, and an oxetanyl group. A monomer having an epoxy group is more preferable. Specific examples of such monomers include (meth) acrylic acid esters having a functional group and vinyl ethers containing a functional group. For example, 2-hydroxyethyl (meth) acrylate, (meta ) 2-aminoethyl acrylate, glycidyl (meth) acrylate, glycidyl vinyl ether, allyl vinyl ether, (meth) acrylate having an alicyclic epoxy group, and the like. Among these, glycidyl (meth) acrylate and (meth) acrylate having an alicyclic epoxy group (commercial product names: Cyclomer M100, A400 (manufactured by Daicel)) are preferable. Examples of these commercially available products include Cyclomer M100 and A400 (manufactured by Daicel Corporation).

The monomer having no functional group constituting the shell layer is selected from (meth) acrylic acid esters, aromatic vinyl compounds, vinyl cyanide compounds, unsaturated acid derivatives, (meth) acrylamide derivatives, and maleimide derivatives. One or more monomers are preferred.
Examples of the (meth) acrylic acid ester include (meth) acrylic acid alkyl esters such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate. Can be mentioned. Examples of the aromatic vinyl compound include styrene, α-methylstyrene, alkyl-substituted styrene; halogen-substituted styrenes such as bromostyrene and chlorostyrene. Examples of the vinyl cyanide compound include (meth) acrylonitrile and substituted acrylonitrile. Examples of the unsaturated carboxylic acid derivative include (meth) acrylic acid, itaconic acid, crotonic acid, maleic anhydride and the like. Examples of the (meth) acrylamide derivative include (meth) acrylamide (including N-substituted product). Maleimide derivatives include maleic imides (including N-substituents). Of these, methyl (meth) acrylate is preferred.
The shell layer composed of such a monomer component has a copolymer of methyl (meth) acrylate and glycidyl (meth) acrylate, or has a methyl (meth) acrylate and an alicyclic epoxy group. A shell layer made of a copolymer with (meth) acrylate is preferred.

The (F) functional group-modified rubber-like polymer particle comprising such a core and shell layer comprises a functional group, preferably an epoxy group, a hydroxyl group, a (meth) acryloyl group, and an oxetanyl group in the shell layer. It has at least one functional group selected from the group. Thereby, the three-dimensional molded item which has the outstanding toughness and has high rigidity can be obtained.
The functional group content in the functional group-modified rubbery polymer particles is preferably 1000 to 2500 g / eq, and more preferably 1200 to 2500 g / eq.
Moreover, the ratio (weight ratio) of the preferable core / shell layer of (F) functional group containing rubber-like polymer particle is 40 / 60-95 / 5, More preferably, it is 60 / 40-85 / 15. If the ratio of the core / shell layer deviates from 40/60 and the core ratio decreases, the toughness of the resulting three-dimensional structure may be inferior. On the other hand, when the ratio of the core / shell layer exceeds 95/5 and the ratio of the shell layer decreases, the polymer particles are difficult to disperse in the composition, and the expected physical properties may not be obtained.

  (F) The functional group-modified rubber-like polymer particles can be produced 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 size of the (F) functional group-modified rubber-like polymer particles thus obtained is 10 nm to 700 nm. If the average particle size of the particles is less than 10 nm, the impact resistance of the resulting three-dimensional product may be reduced, or the viscosity of the resin liquid may be increased, affecting the productivity and modeling accuracy of the three-dimensional product. Therefore, it is not preferable. On the other hand, if the average particle diameter of the particles exceeds 700 nm, a solid surface with a sufficiently smooth surface cannot be obtained, or the modeling accuracy is lowered.
In the present invention, the average particle size of the (F) functional group-modified rubber-like polymer particles is preferably 100 to 400 nm, more preferably 120 to 300 nm, and still more preferably 150 to 250 nm, from the viewpoint of improving impact resistance. is there.
According to the experiments of the present inventors, when unmodified rubber-like polymer particles are used, from the viewpoint of improving impact resistance (Izod impact value, etc.), the average particle of unmodified rubber-like polymer particles It has been confirmed that the diameter is optimal near 200 nm (150 to 250 nm). Also from this experimental result, it can be inferred that the optimum value of the average particle diameter of the (F) functional group-modified rubber-like polymer particles in the present invention is 150 to 250 nm.
Examples of commercially available functional / core-modified core / shell type elastomer particles include Kane Ace MX (manufactured by Kaneka Corporation).

Photocurable resin composition of the present invention, the mixing ratio of the component (F), 100 mass% of the composition total amount, from 1 to 35 wt%, preferably from 3 to 30% by weight, particularly preferably from 5 to 25 weight %. If the blending ratio is less than 1% by mass, the toughness of the three-dimensional structure tends to decrease, such being undesirable. On the other hand, if the blending ratio exceeds 35% by mass, the viscosity increases, bubbles are generated during modeling, and the modeling accuracy of the resulting three-dimensional object tends to decrease, such being undesirable.

[(G) component]
It is preferable that the photocurable resin composition for optical three-dimensional modeling of the present invention further contains a polyether polyol as the component (G). By blending the polyether polyol, the photocurability of the resin composition, the shape stability of the three-dimensional structure obtained by optical three-dimensional modeling (performance for suppressing deformation over time), and the physical property stability (of mechanical properties) (Suppressing performance of change over time) can be improved. 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 elastic modulus of the resulting three-dimensional structure tends to decrease. There is. 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 Kasei Co., Ltd.), TMP-3Glycol, PNT-4 Glycol, EDA-P-4, EDA-P-8 (above, manufactured by Nippon Emulsifier Co., Ltd.), 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 of the present invention, the blending ratio of the component (G) is preferably 5 to 35% by mass, more preferably 5 to 30% by mass, particularly preferably 5%, based on 100% by mass of the total composition. -25% by mass. If the blending ratio is 5% by mass or more, the effect of improving the photocurability of the obtained resin composition can be sufficiently obtained, and a three-dimensional modeled object having good shape stability and physical property stability can be surely obtained. Can be obtained. On the other hand, if the blending ratio is 35% by mass or less, the photocurability of the composition and the elastic modulus of the three-dimensional model can be made particularly good.

[Other ingredients]
In the photocurable resin composition for optical three-dimensional modeling 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 model | molding of this invention can be manufactured by mixing the said (A)-(F) component and the other component mix | blended as needed uniformly. The viscosity (25 ° C.) of the photocurable resin composition for optical three-dimensional modeling thus obtained is preferably 50 to 2,000 cps, more preferably 70 to 1,500 cps.

  The photocurable resin composition for optical three-dimensional modeling of the present invention obtained as described above is suitably used as a photocurable resin composition for optical three-dimensional modeling in the optical three-dimensional modeling method. That is, an optical solid that selectively irradiates light such as visible light, ultraviolet light, and infrared light to the photocurable resin composition for optical three-dimensional modeling of the present invention to supply energy necessary for curing. By the modeling method, a three-dimensional modeled object having a desired shape 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 typical 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 (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 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 high rigidity (Young's modulus, flexural modulus, etc.) and high toughness (bending resistance, impact resistance, etc.).
In addition, in order to improve the surface strength and heat resistance of a three-dimensional molded item, it is preferable to use a thermosetting or photocurable hard coat material after performing the cleaning 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.

[Example 1]
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. A test piece (cured product) was formed using the obtained liquid resin composition and evaluated by the following method. The results are shown in Table 2.
The test piece used was a solid creator SCS-300P (manufactured by Sony Manufacturing Systems) under the conditions of a laser power of 100 mW on the irradiated surface (liquid surface) and a scanning speed at which the curing depth in each composition was 300 μm. 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.

The details of each component described in Table 1 are as follows.
1) Epicoat 834, manufactured by Japan Epoxy Resin Co., Ltd.
2) Union Carbide, UVR-6110
3) Epicoat 828, manufactured by Japan Epoxy Resin Co., Ltd.
4) Epicoat 806, manufactured by Japan Epoxy Resin Co., Ltd.
5) Aron Oxetane OXT-101 manufactured by Toa Gosei Co., Ltd.
6) CPI-101A manufactured by San Apro
7) Aronix M-315, manufactured by Toa Gosei Co., Ltd.
8) Irgacure 184, manufactured by Ciba Specialty Chemicals
9) MX-153 (epoxy group-modified elastomer particles) manufactured by Kaneka Corporation
10) Sannix GP-400, manufactured by Sanyo Chemical

Evaluation method [film Young's modulus]
Based on JIS K7127, the Young's modulus of the test piece was measured using a tensile measurement tester AGS-50G manufactured by Shimadzu Corporation.
[Film bending resistance]
Using the MIT type bending tester, the number of bending until the test piece broke was measured. The initial load was measured at 200 g.
[Film impact value]
The film impact value was measured using a film impact tester manufactured by Yasuda Seiki Co., Ltd. A 12 mm diameter plastic sphere was used as the impact sphere.

[Comparative Example 1]
As an alternative to the component (F), the same procedure as in Example 1 was performed, except that unmodified elastomer particles (Reginus Kasei Co., Ltd .; RKB5610CP-60) were used. The results are shown in Table 2.
[Comparative Example 2]
(F) It carried out like Example 1 except having used unmodified elastomer particles (Resinus Kasei Co., Ltd. make, Resin Bond RKB (brand name)) as a component. The results are shown in Table 2.

  Table 2 shows that in Example 1 using the functional group-modified elastomer particles, a cured product having high rigidity (Young's modulus) and high toughness (bending resistance, film impact value) is obtained. On the other hand, it can be seen that Comparative Examples 1 and 2 using unmodified elastomer particles are inferior in both rigidity and toughness (Comparative Example 2) or inferior in toughness (Comparative Example 1).

[Example 2]
A liquid resin composition was prepared in the same manner as in Example 1 except that the cleaning method for the component (F) was slightly changed. A test piece (cured product) was formed using the obtained liquid resin composition and evaluated by the following method. The results are shown in Table 3.

Evaluation method [flexural modulus]
This was performed in accordance with JIS K7171.
The test piece used was a solid creator SCS-300P (manufactured by Sony Manufacturing Systems) under the conditions of a laser power of 100 mW on the irradiated surface (liquid surface) and a scanning speed at which the curing depth in each composition was 300 μm. 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.

[Example 3]
After the test piece (cured product) was formed, it was evaluated in the same manner as in Example 2 except that the heat treatment was performed at 80 ° C. for 2 hours.
[Example 4]
The same procedure as in Example 2 was performed except that functional group-modified elastomer particles having an average particle diameter of 200 nm (manufactured by Kaneka Corporation; trade name: MX series) were used as an alternative to the component (F).
[Example 5]
After the test piece (cured product) was formed, it was evaluated in the same manner as in Example 4 except that heat treatment was performed at 80 ° C. for 2 hours.
[Example 6]
After the test piece (cured product) was formed, it was evaluated in the same manner as in Example 4 except that the heat treatment was performed at 120 ° C. for 2 hours.
The above results are shown in Table 3.

  From Table 3, it can be seen that in Examples 2 to 6 using the functional group-modified elastomer particles, a cured product having both high rigidity (bending strength) and high toughness (Izod impact value) is obtained. In particular, in Examples 4 to 6 using the functional group-modified elastomer particles having an average particle diameter of 200 nm, it is understood that a cured product having a greatly improved Izod impact value is obtained while maintaining good bending strength. .

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 (6)

(A) a cationic polymerizable compound having two or more bisphenol structures and one or more hydroxyl groups, (B) a cationic polymerizable compound other than the component (A), (C) a cationic photopolymerization initiator, and (D) a radical. A polymerizable compound, (E) a radical photopolymerization initiator, and (F) a multilayer structure polymer particle comprising a core and a shell layer, wherein the shell layer comprises an epoxy group, a hydroxyl group, a (meth) acryloyl group, And a photocurable resin composition for optical three-dimensional modeling containing functional group-modified rubber-like polymer particles having at least one reactive functional group selected from the group consisting of oxetanyl groups ,
The total amount of the photocurable resin composition is 100% by mass, the compounding ratio of the component (A) is 3 to 40% by mass, the compounding ratio of the component (B) is 20 to 85% by mass, and the component (C). The blending ratio of 0.1 to 10% by weight, the blending ratio of the component (D) is 3 to 45% by weight, the blending ratio of the component (E) is 0.01 to 10% by weight, and the component (F) Is 1 to 35% by mass,
The photocurable resin composition for optical three-dimensional modeling , wherein the component (A) is an epoxy compound having an epoxy equivalent of 230 to 1500 g / eq represented by the following general formula (1) .

(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 claim 1, wherein the content of the functional group is 1000 to 2500 g / eq in the multilayer structure polymer particle as the component (F). The photocurable resin composition for optical three-dimensional model | molding of Claim 1 or 2 with which the multilayer structure polymer particle which is the said (F) component has an average particle diameter of 10-700 nm.   The photocurable resin composition for optical three-dimensional modeling according to any one of claims 1 to 3, wherein the component (B) contains a compound having an oxetane structure.   The photocurable resin composition for optical three-dimensional modeling according to any one of claims 1 to 4, wherein the component (B) contains a compound having a bisphenol structure.   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 1-5.

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