JP4925900B2 - Optical three-dimensional resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin composition for optically three-dimensional forming, which allows the smooth production, with high productivity, of a three-dimensional form having high heat resistance and toughness with a short optically forming time. <P>SOLUTION: The resin composition for optically three-dimensional forming comprises, based on the total mass thereof, 1 mass% or more and less than 10 mass% of an epoxy compound (I) of general formula (I) (wherein, R<SP>1</SP>is an a-valent organic group, and b is an integer of 1-30, provided that a is an integer of 1-6 and that the average of b's is in the range of 1-30) as a cationically polymerizable organic compound, 0.01-10 mass% of a photocationic polymerization initiator and 1 mass% or more and less than 10 mass% of elastomer particles. <P>COPYRIGHT: (C)2009,JPO&amp;INPIT

Description

  The present invention relates to a resin composition for optical three-dimensional modeling. More specifically, the present invention is an optical three-dimensional object that is capable of producing a three-dimensional structure excellent in heat resistance and toughness and also in other mechanical properties smoothly with high modeling accuracy and dimensional accuracy with high productivity. The present invention relates to a molding resin composition.

In recent years, a method for three-dimensional optical modeling of a liquid photocurable resin composition based on data input to a three-dimensional CAD has achieved good dimensional accuracy without producing a mold or the like. Have been widely adopted.
As a typical example of the optical three-dimensional modeling method, a spot-shaped ultraviolet laser beam controlled by a computer is selectively irradiated so that a desired pattern can be obtained on the liquid surface of the liquid photocurable resin placed in a container. Then, a predetermined thickness is cured, and then a liquid resin for one layer is supplied onto the cured layer, and similarly, it is irradiated and cured with an ultraviolet laser beam in the same manner as described above to repeat a lamination operation to obtain a continuous cured layer. The method of finally obtaining a three-dimensional molded item can be mentioned. With this optical three-dimensional modeling method, it is possible to easily obtain a model having a considerably complicated shape in a relatively short time.

Conventionally, as the resin composition for optical three-dimensional modeling, an acrylate-based photocurable resin composition, an epoxy-based photocurable resin composition, or the like is used. Among these, the epoxy-based photocurable resin composition has been widely used in recent years because it can produce a molded article having excellent dimensional accuracy.
With the progress of the optical three-dimensional modeling technology, the applications of the optical three-dimensional model are also expanding, and high heat resistance is required depending on the applications and the like. For example, high heat resistance is required for an optical three-dimensional structure used for an engine portion.

  For the purpose of obtaining a three-dimensional model with improved heat resistance, a resin composition for optical three-dimensional modeling containing diglycidyl ether of bisphenol A has been proposed (Patent Document 1). However, this resin composition for optical three-dimensional modeling has a high viscosity of the composition and is inferior in handleability during optical modeling. Moreover, since diglycidyl ether of bisphenol A is a chemical substance that may cause harm to human health and ecosystems, its use is restricted by the Chemical Substance Release and Transfer Notification System (PRTR).

3D modeling with improved heat resistance, containing a cationically polymerizable organic compound having one or more cyclohexyleneoxy groups substituted with 1,2-epoxyethyl groups in a proportion of 10 wt% or more or 25 wt% or more A resin composition for optical three-dimensional modeling for obtaining a product is known (Patent Documents 2 and 3). However, the three-dimensional object obtained by using these optical three-dimensional resin compositions has improved heat resistance but has no toughness and is brittle and has an external force such as impact, bending, compression, and screw pushing. When it receives, it is easily damaged and inferior in durability.
In addition, as a resin composition for optical three-dimensional modeling that can form a three-dimensional model with relatively excellent heat resistance, di (meth) having a cyclohexane ring in the molecule, such as cyclohexanedimethanol di (meth) acrylate, etc. Although the resin composition for optical three-dimensional modeling containing an acrylate is known, the heat-resistant temperature of the three-dimensional model obtained by optical modeling of the resin composition for optical three-dimensional modeling is about 60 ° C., The heat resistance is still insufficient.

On the other hand, in order to impart toughness to a modeled article, it has been proposed that the epoxy resin composition contains a polyether compound, crosslinked rubber particles, or the like (Patent Documents 4 and 5). However, in these materials, the toughness is improved by the addition of the polyether compound and the crosslinked rubber particles, but the heat resistance of the resulting molded article is lowered.
In a molded article obtained from a resin composition for optical three-dimensional modeling, heat resistance and toughness are generally in a trade-off relationship, and improving heat resistance decreases toughness, while increasing toughness decreases heat resistance. In fact, a resin composition for optical three-dimensional modeling that can form a three-dimensional molded article having both good heat resistance and good toughness has not been obtained yet.
From such a point, optical three-dimensional modeling that forms a three-dimensional model that is excellent in both heat resistance and toughness is required.

  Furthermore, for the resin composition for optical three-dimensional modeling, in addition to the requirements for heat resistance and toughness for the three-dimensional model to be obtained, it has low viscosity and good handling at the time of molding, and has excellent storage stability. High curing sensitivity by active energy rays, modeling is possible in a short time, shrinkage during photocuring is small, warpage is small, dimensional accuracy, modeling accuracy, appearance is excellent, strength, etc. It is demanded that a three-dimensionally shaped object having excellent mechanical properties can be produced smoothly.

JP-A-8-20728 Japanese Patent No. 3824286 JP-A-11-228804 JP-A-11-240939 Japanese Patent Laid-Open No. 11-310626 Paul F. Jacobs, “Rapid Prototyping & Manufacturing, Fundamentals of Stereo-Lithography”, “Society of Manufacturing Engineers”, 1992, p. 28-39.

The objective of this invention is providing the resin composition for optical three-dimensional model | molding which can manufacture smoothly the three-dimensional model | molding thing which is excellent in heat resistance and toughness by optical modeling.
Furthermore, the objective of this invention is providing the resin composition for optical three-dimensional model | molding which can manufacture the optical three-dimensional model | molding thing excellent in heat resistance and toughness smoothly with sufficient productivity in a short optical modeling time. .
And in addition to the above-mentioned properties, the object of the present invention is low in viscosity and excellent in handleability during optical modeling, excellent in stability over time during storage, small in shrinkage during curing, dimensional accuracy, modeling An object of the present invention is to provide a photocurable resin composition capable of producing a three-dimensional molded article that is excellent in accuracy and appearance and also excellent in mechanical properties with high productivity.

  In order to solve the above-mentioned problems, the present inventors have intensively studied. As a result, the present inventors have added 1% by mass or more of a compound having a cyclohexyleneoxy group substituted with a 1,2-epoxyethyl group as a cationically polymerizable organic compound in the resin composition for optical three-dimensional modeling. A resin composition for optical three-dimensional modeling that can form a three-dimensional model having excellent characteristics of both heat resistance and toughness when it is contained in a proportion of less than mass% and elastomer particles are contained in a proportion of 1 to 20 mass%. It was found that can be obtained.

  Furthermore, the inventors of the present invention provide a resin composition for optical three-dimensional modeling containing a compound having a cyclohexyleneoxy group substituted with a 1,2-epoxyethyl group and an elastomer particle in the specific ratio, As part of the polymerizable organic compound, an aliphatic or alicyclic epoxy compound having 3 or more glycidyl groups) and an aliphatic or alicyclic group having 2 or more glycidyl groups and 1 or more hydroxyl groups Further blending one or more of a mixture of epoxy compounds, diglycidyl ether of hydrogenated bisphenol and 3,4-epoxycyclohexyl-3 ′, 4′-epoxycyclohexanecarboxylate in specific amounts, Preferred from the viewpoints of improving heat resistance, improving photocuring speed, dimensional stability over time, etc. If the oxetane compound is further added in a specific amount as a part of the thione-polymerizable organic compound, even if the resin composition for optical three-dimensional modeling is stored in an uncured state for a long time, it absorbs less moisture and moisture and is long. It was found that high curing sensitivity (active energy ray sensitivity) can be maintained over time.

  In the resin composition for optical three-dimensional modeling described above containing the compound having a cyclohexyleneoxy group substituted with a 1,2-epoxyethyl group and the elastomer particles in the specific ratio, Based on the total mass, it has been found that if a radical polymerizable organic compound and a photo radical polymerization initiator are further contained in specific amounts, modeling can be performed at high speed and with high accuracy. completed.

That is, the present invention
(1) A resin composition for optical three-dimensional modeling containing a cationically polymerizable organic compound, a photocationic polymerization initiator, and elastomer particles, and based on the total mass of the resin composition for optical three-dimensional modeling, cationic polymerizable As an organic compound, the following general formula (I);

（式中、Ｒ¹はａ価の有機基を示し、ａは１〜６の整数であり、ｂは１〜３０の整数であって且つａ個のｂの平均値が１〜３０の範囲内である。）
で表されるエポキシ化合物（Ｉ）を１質量％以上１０質量％未満の割合で含有し、光カチオン重合開始剤を０．１〜１０質量％の割合で含有し、且つエラストマー粒子を１〜２０質量％の割合で含有することを特徴とする光学的立体造形用樹脂組成物である。

(In the formula, R ¹ represents an a-valent organic group, a is an integer of 1 to 6, b is an integer of 1 to 30, and the average value of a b is in the range of 1 to 30. .)
The epoxy compound (I) represented by the formula is contained in a proportion of 1% by mass or more and less than 10% by mass, the photocationic polymerization initiator is contained in a proportion of 0.1 to 10% by mass, and the elastomer particles are contained in 1 to 20%. It is a resin composition for optical three-dimensional modeling characterized by containing in the ratio of the mass%.

And this invention,
(2) The above-mentioned (1) further containing other cationically polymerizable organic compound (II) other than epoxy compound (I) at a ratio of 1 to 85% by mass based on the total mass of the resin composition for optical three-dimensional modeling. ) Resin composition for optical three-dimensional modeling;
(3) As another cationically polymerizable organic compound (II), an aliphatic or alicyclic epoxy compound (II-A) having 3 or more glycidyl groups and / or 2 or more glycidyl groups and a hydroxyl group The aliphatic or alicyclic epoxy compound (II-B) having one or more of the total of the epoxy compound (II-A) and the epoxy compound (II-B) The resin composition for optical three-dimensional modeling according to (2), which is contained at a ratio of 5 to 30% by mass based on mass;
(4) As other cationically polymerizable organic compound (II), the following general formula (II-C);

（式中、Ｒ²は水素原子またはメチル基を示す。）
で表される水素添加ビスフェノールのジグリシジルエーテル（II−Ｃ）を、光学的立体造形用樹脂組成物の全質量に基づいて３〜３０質量％の割合で含有する前記(２)または(３)の光学的立体造形用樹脂組成物；および、
（５） 他のカチオン重合性有機化合物（II）として、３，４−エポキシシクロヘキシル−３’，４’−エポキシシクロヘキサンカルボキシレート（II−Ｄ）を、光学的立体造形用樹脂組成物の全質量に基づいて、１〜６０質量％の割合で含有する前記（２）〜（４）のいずれかの光学的立体造形用樹脂組成物；
である。

(In the formula, R ² represents a hydrogen atom or a methyl group.)
(2) or (3) containing diglycidyl ether (II-C) of hydrogenated bisphenol represented by the formula (3) to 30% by mass based on the total mass of the resin composition for optical three-dimensional modeling. A resin composition for optical three-dimensional modeling; and
(5) 3,4-epoxycyclohexyl-3 ′, 4′-epoxycyclohexanecarboxylate (II-D) as another cationically polymerizable organic compound (II), the total mass of the resin composition for optical three-dimensional modeling Based on the above, the resin composition for optical three-dimensional modeling according to any one of (2) to (4), which is contained at a ratio of 1 to 60% by mass;
It is.

Furthermore, the present invention provides
(6) The oxetane compound (II-E) as the other cationic polymerizable organic compound (II) based on the total mass of the resin composition for optical three-dimensional modeling in a proportion of 1 to 20% by mass The resin composition for optical three-dimensional modeling according to any one of (2) to (5);
(7) Based on the total mass of the resin composition for optical three-dimensional modeling, the radical polymerizable organic compound is further contained in an amount of 1 to 50% by mass and a radical photopolymerization initiator in a proportion of 0.01 to 10% by mass. A resin composition for optical three-dimensional modeling according to any one of (1) to (6); and
(8) Based on the total mass of the resin composition for optical three-dimensional modeling, the epoxy compound (I) represented by the general formula (I) is 1% by mass or more and less than 10% by mass, other than the epoxy compound (I) 1 to 85% by mass of the other cationically polymerizable organic compound (II), 0.1 to 10% by mass of the cationic photopolymerization initiator, 1 to 50% by mass of the radically polymerizable organic compound, and the radical photopolymerization initiator. The resin composition for optical three-dimensional modeling according to any one of (1) to (7), which contains 0.01 to 10% by mass and elastomer particles in a proportion of 1 to 20% by mass;
It is.

As a cationically polymerizable organic compound, the epoxy compound (I) is contained in a proportion of 1% by mass or more and less than 10% by mass and the elastomer particles are contained in a proportion of 1 to 20% by mass. By using the product, it has excellent heat resistance and excellent toughness, and is resistant to damage even when subjected to external forces such as impact, bending, compression, and screwing, and has dimensional accuracy, appearance, A three-dimensional structure that is excellent in mechanical properties and the like can be manufactured smoothly with high productivity in a short modeling time.
In addition to the epoxy compound (I) and elastomer particles, as part of the cationically polymerizable organic compound, an aliphatic or alicyclic epoxy compound having 3 or more glycidyl groups) and 2 or more glycidyl groups and hydroxyl One or two of a mixture of aliphatic or cycloaliphatic epoxy compounds having one or more groups, diglycidyl ether of hydrogenated bisphenol and 3,4-epoxycyclohexyl-3 ', 4'-epoxycyclohexanecarboxylate The resin composition for optical three-dimensional model | molding of this invention which further contains a seed | species or more by the specific quantity prescribed | regulated by this invention has a higher photocuring rate, and forms the three-dimensional model | molding thing excellent in heat resistance.

Furthermore, the optical three-dimensional modeling of the present invention further containing an oxetane compound in an amount specified in the present invention as a part of the cationically polymerizable organic compound is stored in an uncured state for a long time in combination with the above-described properties. Furthermore, it has an excellent characteristic that it absorbs less moisture and moisture and maintains high curing sensitivity (sensitivity to active energy rays) over a long period of time.
The optical three-dimensional structure of the present invention further contains a radical polymerizable organic compound and a photo radical polymerization initiator in a specific amount specified in the present invention together with the above cationic polymerizable organic compound, photo cationic polymerization initiator and elastomer particles. The resin composition for modeling has a low shrinkage and is excellent in heat resistance and toughness.

The present invention is described in detail below.
The resin composition for optical three-dimensional modeling of the present invention has the following general formula (I) as a part of a cationically polymerizable organic compound, preferably a part of a cationically polymerizable organic compound:

（式中、Ｒ¹はａ価の有機基を示し、ａは１〜６の整数であり、ｂは１〜３０の整数であって且つａ個のｂの平均値が１〜３０の範囲内である。）
で表されるエポキシ化合物（Ｉ）を含有する。

(In the formula, R ¹ represents an a-valent organic group, a is an integer of 1 to 6, b is an integer of 1 to 30, and the average value of a b is in the range of 1 to 30. .)
The epoxy compound (I) represented by these is contained.

In the above general formula (I), R ¹ is an a-valent (1-6 valent) organic group. R ¹ is generally a 1-6 valent organic residue after removal of the active hydrogen atom from an organic compound having 1-6 active hydrogen atoms in the molecule, and the organic group R ¹ is Examples of the organic compound (precursor compound) having 1 to 6 active hydrogen atoms in the molecule to be formed include saturated or unsaturated alcohols having 1 to 6 active hydrogen atoms [for example, methanol, ethanol, propanol , Butanol, pentanol, hexanol, octanol, 3-cyclohexenemethanol, benzyl alcohol, ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, polyethylene glycol, polypropylene glycol, glycerin, trimethylolpropane, 2,2-bis (Hydroxymethyl) -1-butanol, 2,2-bis (hydroxyethyl) -1-butanol, alkylene oxide addition alcohol of bisphenols, pentaerythritol, dipentaerythritol, diglycerine, allyl alcohol, cyclohexene methanol], phenols (phenol, cresol, pyrogallol, bisphenol A, bisphenol S, bisphenol F, etc.), saturated or unsaturated carboxylic acids (acetic acid, propionic acid, maleic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, zebacic acid, phthalic acid, terephthalic acid, Acrylic acid, methacrylic acid, etc.) and thiols (methyl mercaptan, ethyl mercaptan, propyl mercaptan, thiophenol, etc.).

In said general formula (I), b is an integer of 1-30, and the average value of a b is in the range of 1-30. Among them, b is an integer of 1 to 20, and the average value of a b in the epoxy compound (I) is in the range of 1 to 20 in terms of material availability, reactivity, and the like. To preferred.
The epoxy compound (I) used in the present invention is a known compound, for example, the formula: R ^1- (Hact) a (wherein Hact is an active hydrogen atom, and a is an integer of 1 to 6). After ring-opening polymerization of cyclohexene oxide having a vinyl group as a substituent with the above-described organic compounds (alcohols, organic acids, phenols, thiols, etc.) having 1 to 6 active hydrogen atoms represented as starting ends The polymer obtained thereby can be produced by oxidizing with a peracid or the like to change the vinyl group into an epoxy group.

The resin composition for optical three-dimensional modeling of the present invention may contain only one type of epoxy compound (I), or may contain two or more types of epoxy compound (I).
Among them, the resin composition for optical three-dimensional modeling of the present invention is a trivalent (a = 3) organic residue in which R ¹ is derived from trimethylolpropane, trimethylolethane or the like as the epoxy compound (I). An epoxy compound in which 3 b is an integer of 1 to 30 and the average value of 3 b is 1 to 30 is preferably used from the viewpoints of reactivity and availability. Such an epoxy compound (I) includes “Celoxide EHPE-3150” (manufactured by Daicel Chemical Industries), “EHPE-3150CE” (mixture of EHPE-3150 and other alicyclic epoxy compounds) (manufactured by Daicel Chemical Industries, Ltd.). ) And so on.

The resin composition for optical three-dimensional model | molding of this invention may contain epoxy compound (I) in the ratio of 1 mass% or more and less than 10 mass% based on the total mass of the resin composition for optical three-dimensional model | molding. It is necessary, it is preferable to contain in the ratio of 1-9 mass%, and it is more preferable to contain in the ratio of 2-8 mass%.
When the content of the epoxy compound (I) is less than 1% by mass based on the total mass of the resin composition for optical three-dimensional modeling, the heat resistance of the three-dimensional model obtained from the resin composition for optical three-dimensional modeling is If it becomes insufficient, on the other hand, if it exceeds 10% by mass, the heat resistance of the three-dimensional structure will improve, but the toughness will decrease and become brittle, and it will break if subjected to external forces such as impact, bending, compression, and screwing in. It becomes easy and the resin composition for optical three-dimensional model | molding which forms the three-dimensional model | molded article excellent in the characteristic of both heat resistance and toughness cannot be obtained.

As a photocationic polymerization initiator contained in the resin composition for optical three-dimensional modeling of the present invention, an epoxy compound (I) contained in the resin composition for optical three-dimensional modeling of the present invention, and other cationic polymerizable organic compounds. Any cationic polymerization initiator that can be polymerized under irradiation of active energy rays such as light can be used.
Among them, as the cationic photopolymerization initiator, an onium salt that releases a Lewis acid when irradiated with active energy rays such as light is preferably used. Examples of such onium salts include aromatic sulfonium salts of Group VIIa elements, aromatic onium salts of Group VIa elements, aromatic onium salts of Group Va elements, and the like. Specifically, for example, triarylsulfonium hexafluoroantimonate, triphenylphenacylphosphonium tetrafluoroborate, triphenylsulfonium hexafluoroantimonate, bis- [4- (diphenylsulfonio) phenyl] sulfide bisdihexa Fluoroantimonate, bis- [4- (di4′-hydroxyethoxyphenylsulfonio) phenyl] sulfide bisdihexafluoroantimonate, bis- [4- (diphenylsulfonio) phenyl] sulfide bisdihexafluorophos Fate, diphenyliodonium tetrafluoroborate and the like can be mentioned.
In the present invention, one or more of the above cationic photopolymerization initiators can be used, and an aromatic sulfonium salt is particularly preferably used.
The resin composition for optical three-dimensional modeling of the present invention contains a photosensitizer, for example, benzophenone, benzoin alkyl ether, thioxanthone, etc., if necessary, with a cationic photopolymerization initiator for the purpose of improving the reaction rate. You may do it.

  Content of a photocationic polymerization initiator is 0.1-10 mass% based on the total mass of the resin composition for optical three-dimensional modeling, 1-10 mass% is preferable, and 1-5 mass% is more preferable. . Moreover, when based on the total mass of the cationically polymerizable organic compound contained in the resin composition for optical three-dimensional modeling, the content of the photocationic polymerization initiator is 0.1 to 15% by mass, further 1 to It is preferable that it is 15 mass%, especially 2-10 mass%.

The resin composition for optical three-dimensional model | molding of this invention contains an elastomer particle with above-described epoxy compound (I) and a photocationic polymerization initiator.
Examples of the elastomer particles include elastomer particles composed of one or more of natural rubber, synthetic rubber, and thermoplastic elastomer, and multilayer elastomer particles (core / core) having a layer composed of the aforementioned elastomer in the center, middle and / or outside. Any of shell type elastomer particles) may be used.
Specific examples of the elastomer particles include natural rubber, polybutadiene rubber, polyisoprene rubber, styrene / butadiene copolymer rubber, styrene / isoprene copolymer rubber, butadiene / acrylonitrile copolymer rubber, ethylene / propylene copolymer rubber, Ethylene / α-olefin copolymer rubber, ethylene / α-olefin / polyene copolymer rubber, acrylic rubber, butadiene / (meth) acrylate copolymer rubber, styrene / butadiene block copolymer rubber, styrene / Examples thereof include particles made of isoprene copolymer rubber, chloroprene rubber, butyl rubber, urethane rubber, polyester thermoplastic elastomer, polyamide thermoplastic elastomer, and the like.
In addition, as a specific example of the multilayer elastomer particles (core / shell type elastomer particles), one or more of the above-described elastomers (rubbers), or a partially cross-linked one is used as the inside (core). The outside is a (meth) acrylic acid ester polymer such as methyl methacrylate, a (meth) acrylic acid ester and glycidyl (meth) acrylate copolymer such as methyl methacrylate, or an epoxy resin such as bisphenol A diglycidyl ether. Examples thereof include coated core-shell type elastomer particles.
In the present invention, one or more of the above-described elastomer particles can be used.
Among them, in the present invention, the above-mentioned core / shell type elastomer particles, in which the elastomer (rubber) is a core (inner layer) and the outside is coated with another resin, are used as the elastomer particles. It is preferably used because it has a high affinity with objects and provides a high toughness improving effect in a small amount.
Examples of commercially available core / shell type elastomer particles as described above include, for example, “Reginas Bond RKB” (manufactured by Reginas Kasei Co., Ltd.), “Techno MBS-61” (manufactured by Technopolymer Co., Ltd.), and “Techno MBS-”. 69 "(manufactured by Techno Polymer Co., Ltd.).

The elastomer particles used in the present invention preferably have an average particle size of 10 to 700 nm, particularly 20 to 500 nm, from the viewpoint of improving toughness.
Here, the average particle diameter of the elastomer particles in the present specification refers to a laser diffraction / scattering particle size obtained by collecting 1 g of elastomer particles and dispersing it in 100 ml of a medium (ultra pure water-hexametaphosphoric acid). The average particle diameter obtained by statistically processing what was measured under the condition of a temperature of 25 ° C. using a distribution measuring device (“LA-920” manufactured by Horiba, Ltd.).

The resin composition for optical three-dimensional model | molding of this invention needs to contain an elastomer particle in the ratio of 1-20 mass% based on the total mass of the resin composition for optical three-dimensional model | mold, 2- It is preferable to contain in the ratio of 20 mass%.
When the content of the elastomer particles is less than 1% by mass based on the total mass of the resin composition for optical three-dimensional modeling, the toughness of the three-dimensional model obtained from the resin composition for optical three-dimensional modeling becomes insufficient. It becomes fragile and easily damaged when subjected to external forces such as impact, bending, compression, and screwing. On the other hand, when it exceeds 20% by mass, the heat resistance of the three-dimensional structure decreases.

  The resin composition for optical three-dimensional modeling of the present invention is composed of the above-described epoxy compound (I) and other cationically polymerizable organics from the viewpoints of improvement in modeling accuracy, improvement in photocuring speed, stability over time, and the like. Compound (II) is preferably contained in a proportion of 1 to 85% by mass, more preferably in a proportion of 10 to 80% by mass, based on the total mass of the resin composition for optical three-dimensional modeling. More preferably, it is contained in a proportion of 20 to 70% by mass.

  As the other cationically polymerizable organic compound (II), any compound that undergoes a polymerization reaction and / or a crosslinking reaction when irradiated with active energy rays such as light in the presence of a photocationic polymerization initiator can be used. Representative examples include epoxy compounds, oxetane compounds and other cyclic ether compounds, cyclic acetal compounds, cyclic lactone compounds, cyclic thioether compounds, spiro orthoester compounds, vinyl ether compounds, and the like. The resin composition for use may contain one or more of the above cationic polymerizable organic compounds as the other cationic polymerizable organic compound, or may contain two or more.

Among them, in the resin composition for optical three-dimensional modeling of the present invention, an epoxy compound and / or an oxetane compound is preferably used as the other cationic polymerizable organic compound (II). A polyepoxy compound having one or more epoxy groups is more preferably used.
In particular, the resin composition for optical three-dimensional modeling of the present invention includes an aliphatic or alicyclic epoxy compound (II-A) having three or more glycidyl groups as other cationically polymerizable organic compound (II) and / or Alternatively, an aliphatic or alicyclic epoxy compound (II-B) having two or more glycidyl groups and one or more hydroxyl groups is added to the total of the epoxy compound (II-A) and the epoxy compound (II-B). And it is preferable from the point of balance of heat resistance and toughness to contain in the ratio of 5-30 mass% based on the total mass of the resin composition for optical three-dimensional model | molding, especially 5-20 mass%.
Moreover, the content ratio of the epoxy compound (II-A) and the epoxy compound (II-B) in the resin composition for optical three-dimensional modeling is a mass ratio, and (II-A) :( II-B) = 4: 1. ~ 3: 2 is preferable, and 3: 1 to 2: 1 is more preferable.

As the epoxy compound (II-A), any of aliphatic or alicyclic epoxy compounds having 3 or more glycidyl groups can be used. Specific examples include glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, Pentaerythritol tetraglycidyl ether, hexaglycidyl ether of dipentaerythritol, castor oil triglycidyl ether, ditrimethylolpropane tetraglycidyl ether, homopolymer synthesized by vinyl polymerization of glycidyl acrylate or glycidyl methacrylate, glycidyl acrylate or glycidyl methacrylate and other vinyl One of aliphatic polyhydric alcohols such as copolymers synthesized by vinyl polymerization with monomers, trimethylolpropane, glycerin, etc. Other birds of polyether polyol obtained by adding two or more kinds of alkylene oxide - can and the like, or more polyglycidyl ethers, can be used alone or in combination of two or more thereof.
In addition, as the epoxy compound (II-B), any of aliphatic or alicyclic epoxy compounds having two or more glycidyl groups and one or more hydroxyl groups can be used, and specific examples thereof include glycerin diglycidyl. Ether, trimethylolpropane diglycidyl ether, di- or tri-glycidyl ether of pentaerythritol, di-, tri-, tetra- or penta-glycidyl ether of dipentaerythritol, di-, tri-, tetra- of sorbitol , Penta-glycidyl ether, polyglycidyl ether having one or more residual hydroxyl groups of polyglycerin, and the like, and one or more of these can be used.

  As commercially available products of the epoxy compound (II-A) and the epoxy compound (II-B), “Decenal EX-321” (mixture of dimethylidyl ether and triglycidyl ether of trimethylolpropane) manufactured by Nagase ChemteX Corporation, “Deconal EX-411” (pentaerythritol tetraglycidyl ether), “Deconal EX-611, EX-611, EX-614, EX-614B or EX-622” (polyglycidyl ether having hydroxyl group of sorbitol), “Deconal EX -512 or EX-521 "[hydroxyglycerin residual polyglycidyl ether of polyglycerin (di- or tri-glycerin)," deconal EX-421 "(triglycidyl ether of diglycerin)," deconal EX-313 or E X-314 "(mixture of diglycidyl ether of glycidyl ether and triglycidyl ether)," GE-30 "(trimethylolpropane triglycidyl ether)," GE-31 "(manufactured by PI / R Japan Co., Ltd.) Trimethylolethane triglycidyl ether), “GE-35” (castor oil triglycidyl ether), “GE-36” triglycidyl ether of glycerin polypropylene oxide adduct), and the like. More than seeds can be used.

The resin composition for optical three-dimensional model | molding of this invention is an epoxy compound (I), an epoxy compound (II-A), and an epoxy compound (with the above-mentioned epoxy compound (I) as a cationically polymerizable organic compound (II) ( II-B) is different from epoxy compound (I), epoxy compound (II-A) and epoxy compound (II-B), and other aliphatic or alicyclic polymers having two or more epoxy groups in the molecule An epoxy compound can be contained.
Examples of such other aliphatic or alicyclic polyepoxy compounds include diglycidyl ethers of aliphatic dihydric alcohols or alkylene oxide adducts thereof, diglycidyl ethers of alicyclic dihydric alcohols, and aliphatic long chain 2 Examples thereof include diglycidyl esters of basic acids. Specific examples include 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, neopentylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, polybutylene glycol diglycidyl. Diglycidyl ether of dihydric alcohol such as ether, diglycidyl ester of aliphatic long chain dibasic acid, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F glycidyl ether, hydrogenated bisphenol Z glycidyl ether, 3,4-epoxycyclohexyl Methyl-3 ′, 4′-epoxycyclohexanecarboxylate, 2- (3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy) cycl Hexane-meta-dioxane, bis (3,4-epoxycyclohexylmethyl) adipate, vinylcyclohexene dioxide, 4-vinylepoxycyclohexane, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, 3,4-epoxy -6-methylcyclohexyl-3,4-epoxy-6-methylcyclohexanecarboxylate, methylenebis (3,4-epoxycyclohexane), dicyclopentadiene diepoxide, di (3,4-epoxycyclohexylmethyl) ether of ethylene glycol, Examples thereof include ethylenebis (3,4-epoxycyclohexanecarboxylate), epoxyhexahydrophthalate dioctyl, epoxyhexahydrophthalate di-2-ethylhexyl, and the like.
as,

  Among the above-described diepoxy compounds, the resin composition for optical three-dimensional modeling of the present invention is used together with the epoxy compound (I), or the epoxy compound (I), the epoxy compound (II-A), and the epoxy compound (II-). Along with B), as part of the cationically polymerizable organic compound (II), the following general formula (II-C);

（式中、Ｒ²は水素原子またはメチル基を示す。）
で表される水素添加ビスフェノールのジグリシジルエーテル（II−Ｃ）を、光学的立体造形用樹脂組成物の全質量に基づいて、３〜３０質量％、更には５〜２５質量％、特に５〜２０質量％の割合で含有することが、造形速度、造形精度、経時の寸法安定性の点から好ましい。
上記の一般式（II−Ｃ）において、２個のＲ²は水素原子またはメチル基のいずれであってもよいが、２個のＲ²ともにメチル基であることが、造形物の耐湿性、入手容易性などの点から好ましい。

(In the formula, R ² represents a hydrogen atom or a methyl group.)
The diglycidyl ether (II-C) of hydrogenated bisphenol represented by 3 to 30% by mass, further 5 to 25% by mass, particularly 5 to 5% by mass, based on the total mass of the resin composition for optical three-dimensional modeling. It is preferable to contain it in the ratio of 20 mass% from the point of modeling speed, modeling precision, and dimensional stability over time.
In the above general formula (II-C), two R ² may be either a hydrogen atom or a methyl group, but both R ² are methyl groups, It is preferable from the viewpoint of availability.

  Further, the resin composition for optical three-dimensional modeling of the present invention is used together with the above-described epoxy compound (I), or together with the epoxy compound (I) and the epoxy compound (II-A) and the epoxy compound (II-B), or epoxy. Along with the compound (I), the epoxy compound (II-A), the epoxy compound (II-B) and the epoxy compound (II-C), as part of the cationically polymerizable organic compound (II), 3,4-epoxycyclohexyl- 3 ′, 4′-epoxycyclohexanecarboxylate (II-D) is 1 to 60% by mass, further 5 to 55% by mass, especially 10 to 50% based on the total mass of the resin composition for optical three-dimensional modeling. It is preferable to contain in the ratio of the mass% from points, such as modeling speed and the mechanical characteristics of the three-dimensional molded item obtained.

  Moreover, the resin composition for optical three-dimensional modeling of this invention is an epoxy compound (I) with the above-mentioned epoxy compound (I), an epoxy compound (II-A), an epoxy compound (II-B), or an epoxy. Compound (I), or epoxy compound (II-A), epoxy compound (II-B), and epoxy compound (II-C), or epoxy compound (II-A), epoxy compound (II-B), epoxy compound Along with (II-C) and 3,4-epoxycyclohexyl-3 ′, 4′-epoxycyclohexanecarboxylate (II-D), as part of epoxy compound (II), oxetane compound (II-E) is optically converted. Based on the total mass of the resin composition for three-dimensional modeling, it may be contained in a proportion of 1 to 20% by mass, particularly 3 to 15% by mass, in an uncured state for a long period of time. In particular, it is preferable from the viewpoint of obtaining a resin composition for optical three-dimensional modeling that has less excellent absorption of moisture and moisture and maintains high curing sensitivity (active energy ray sensitivity) over a long period of time.

In this case, the oxetane compound (II-E) includes a monooxetane compound (II-E1) having one oxetane group in one molecule and a polyoxetane compound (II-E2) having two or more oxentane groups in one molecule. ) Or two or more of them can be used.
As the monooxetane compound (II-E1), any compound having one oxetane group in one molecule can be used, and in particular, one oxetane group and one alcoholic hydroxyl group in one molecule. The monooxetane monoalcohol compound having is preferably used.
Among such monooxetane monoalcohol compounds, the monooxetane monoalcohol compound (II-E1a) represented by the following general formula (II-E1a) and the following general formula (II-E1b) At least one of the monooxetane monoalcohol compounds (II-E1b) is more preferably used as the monooxetane compound (II-E1) from the viewpoints of availability, high reactivity, and low viscosity.

（式中、Ｒ³およびＲ⁴は炭素数１〜５のアルキル基、Ｒ⁵はエーテル結合を有していてもよい炭素数２〜１０のアルキレン基を示す。）

(In the formula, R ³ and R ⁴ represent an alkyl group having 1 to 5 carbon atoms, and R ⁵ represents an alkylene group having 2 to 10 carbon atoms which may have an ether bond.)

In the above general formula (II-E1a), examples of R ³ include methyl, ethyl, propyl, butyl, and pentyl.
Specific examples of monooxetane alcohol (II-E1a) include 3-hydroxymethyl-3-methyloxetane, 3-hydroxymethyl-3-ethyloxetane, 3-hydroxymethyl-3-propyloxetane, and 3-hydroxymethyl-3. -Normal butyl oxetane, 3-hydroxymethyl-3-propyl oxetane, etc. can be mentioned, These 1 type (s) or 2 or more types can be used. Among these, 3-hydroxymethyl-3-methyloxetane and 3-hydroxymethyl-3-ethyloxetane are more preferably used from the viewpoints of easy availability and reactivity.

In the above general formula (II-E1b), examples of R ⁴ include methyl, ethyl, propyl, butyl, and pentyl.
In the general formula (II-E1b), R ⁵ may be either a chain alkylene group or a branched alkylene group as long as it is an alkylene group having 2 to 10 carbon atoms, or an alkylene group ( It may be a C2-C10 chain or branched alkylene group having an ether bond (ether oxygen atom) in the middle of the (alkylene chain). Specific examples of R ⁵ include ethylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, heptamethylene group, and 3-oxypentylene group. Among these, R ⁵ is preferably a trimethylene group, a tetramethylene group, a pentamethylene group or a heptamethylene group from the viewpoints of ease of synthesis and easy handling of the compound which is liquid at room temperature.

  In addition, as the polyoxetane compound (II-E2), any of a compound having two oxetane groups, a compound having three or more oxetane groups, and a compound having four or more oxetane groups can be used. The dioxetane compound which has one piece is used preferably, among these, the following general formula (II-E2a);

（式中、２個のＲ⁶は互いに同じかまたは異なる炭素数１〜５のアルキル基、Ｒ⁷は芳香環を有しているかまたは有していない２価の有機基、ｍは０または１を示す。）
で表されるジオキセタン化合物（II−Ｅ２ａ）が、入手性、反応性、低吸湿性、硬化物の力学的特性などの点から好ましく用いられる。
上記の一般式（II−Ｅ２ａ）において、Ｒ⁶例としては、メチル、エチル、プロピル、ブチル、ペンチルを挙げることができる。また、Ｒ⁷例としては、炭素数１〜１２の直鎖状または分岐状のアルキレン基（例えばエチレン基、プロピレン基、ブチレン基、ネオペンチレン基、ｎ−ペンタメチレン基、ｎ−ヘキサメチレン基など）、式：−ＣＨ₂−Ｐｈ−ＣＨ₂−または−ＣＨ₂−Ｐｈ−Ｐｈ−ＣＨ₂−で表される２価の基、水素添加ビスフェノールＡ残基、水素添加ビスフェノールＦ残基、水素添加ビスフェノールＺ残基、シクロヘキサンジメタノール残基、トリシクロデカンジメタノール残基などを挙げることができる。

(In the formula, two R ⁶ are the same or different alkyl groups having 1 to 5 carbon atoms, R ⁷ is a divalent organic group having or not having an aromatic ring, and m is 0 or 1) Is shown.)
The dioxetane compound (II-E2a) represented by the formula is preferably used in terms of availability, reactivity, low hygroscopicity, mechanical properties of the cured product, and the like.
In the above general formula (II-E2a), examples of R ⁶ include methyl, ethyl, propyl, butyl, and pentyl. Examples of R ⁷ include linear or branched alkylene groups having 1 to 12 carbon atoms (for example, ethylene group, propylene group, butylene group, neopentylene group, n-pentamethylene group, n-hexamethylene group, etc.) A divalent group represented by the formula: —CH ₂ —Ph—CH ₂ — or —CH ₂ —Ph—Ph—CH ₂ —, a hydrogenated bisphenol A residue, a hydrogenated bisphenol F residue, and a hydrogenated bisphenol. Z residue, cyclohexane dimethanol residue, tricyclodecane dimethanol residue and the like can be mentioned.

Specific examples of the dioxetane compound (II-E2a) include a dioxetane compound represented by the following formula (II-E2a ₁ ) or formula (II-E2a ₂ ).

（式中、２個のＲ⁶は互いに同じかまたは異なる炭素数１〜５のアルキル基、Ｒ⁷は芳香環を有しているかまたは有していない２価の有機基を示す。）

(In the formula, two R ⁶ are the same or different alkyl groups having 1 to 5 carbon atoms, and R ⁷ is a divalent organic group having or not having an aromatic ring.)

Specific examples of the dioxetane compound represented by the above formula (II-E2a ₁ ) include bis (3-methyl-3-oxetanylmethyl) ether, bis (3-ethyl-3-oxetanylmethyl) ether, bis (3 -Propyl-3-oxetanylmethyl) ether, bis (3-butyl-3-oxetanylmethyl) ether, and the like.
Further, specific examples of the dioxetane compound represented by the above formula (II-E2a ₂ ) include, in the above formula (II-E2a ₂ ), two R ^{6 s} are both methyl, ethyl, propyl, butyl or pentyl groups. R ⁷ is ethylene group, propylene group, butylene group, neopentylene group, n-pentamethylene group, n-hexamethylene group, etc.), formula: —CH ₂ —Ph—CH ₂ — or —CH ₂ —Ph—Ph Dioxetane which is a divalent group represented by —CH ₂ —, a hydrogenated bisphenol A residue, a hydrogenated bisphenol F residue, a hydrogenated bisphenol Z residue, a cyclohexanedimethanol residue, or a tricyclodecanedimethanol residue A compound can be mentioned.

Among them, as the polyoxetane compound (II-E2a), bis (3-methyl-3-oxetanylmethyl) in which two R ^{6 s} are both a methyl group or an ethyl group in the above formula (II-E2a ₁ ). ) Ether and / or bis (3-ethyl-3-oxetanylmethyl) ether are preferably used from the viewpoints of availability, low hygroscopicity, mechanical properties of the cured product, and the like. -Oxetanylmethyl) ether is more preferably used.

Moreover, the resin composition for optical three-dimensional modeling of this invention contains an aromatic epoxy compound as needed other than the above-mentioned epoxy compound and oxetane compound as other cationically polymerizable organic compound (II). Can do. Examples of the aromatic epoxy compound include mono- or polyglycidyl ethers of monovalent or polyhydric phenols having at least one aromatic nucleus or alkylene oxide adducts thereof. Specific examples thereof include bisphenol A and bisphenol. Examples include glycidyl ether obtained by reaction of F or its alkylene oxide adduct with epichlorohydrin, epoxy novolac resin, phenol, cresol, butylphenol, or monoglycidyl ether of polyether alcohol obtained by adding alkylene oxide to these. Can do. When an aromatic epoxy compound is used, bisphenol A diglycidyl ether, ethylene oxide modified bisphenol A diglycidyl ether, propylene oxide modified bisphenol A diglycidyl ether, or the like is preferably used.
When the resin composition for optical three-dimensional shaping | molding contains an aromatic epoxy compound, the content is 30 mass% or less based on the total mass of the resin composition for optical three-dimensional modeling, Furthermore, it is 20 mass% or less. In particular, 1 to 10% by mass is preferable from the viewpoint that the viscosity of the resin composition for optical three-dimensional modeling does not become too high.

  The resin composition for optical three-dimensional modeling of the present invention is radically polymerizable together with the above-described epoxy compound (I) and elastomer particles, or together with epoxy compound (I), elastomer particles and other cationically polymerizable organic compounds (II). It is preferable to further contain an organic compound and a photo radical polymerization initiator from the viewpoints of an improvement in the curing reaction and modeling speed.

As the radical polymerizable organic compound in this case, any compound that undergoes a polymerization reaction and / or a crosslinking reaction when irradiated with active energy rays such as light in the presence of a radical photopolymerization initiator can be used. Examples include (meth) acrylate compounds and unsaturated polyester compounds, and one or more of these can be used.
Among them, as the radical polymerizable organic compound, a compound having at least one (meth) acryl group in one molecule is preferably used, and specific examples thereof include a reaction product of an epoxy compound and (meth) acrylic acid. And (meth) acrylic esters of alcohols, polyester (meth) acrylates, polyether (meth) acrylates, and the like.

  The reaction product of the above-described epoxy compound that can be used as a radical polymerizable organic compound and (meth) acrylic acid includes an aromatic epoxy compound, an alicyclic epoxy compound and / or an aliphatic epoxy compound, and (meth) acrylic acid. And an epoxy (meth) acrylate-based reaction product obtained by the reaction. Among them, an epoxy (meth) acrylate reaction product obtained by reaction of an aromatic epoxy compound and (meth) acrylic acid is preferably used. Specific examples include bisphenol compounds such as bisphenol A and bisphenol F or alkylene thereof. By reacting glycidyl ether obtained by reaction of an oxide adduct with an epoxidizing agent such as epichlorohydrin with (meth) acrylic acid, epoxy (meth) acrylate, epoxy novolac resin and (meth) acrylic acid are reacted. Examples thereof include an epoxy (meth) acrylate reaction product obtained.

In addition, (meth) acrylic acid esters of the above-mentioned alcohols that can be used as radically polymerizable organic compounds include aromatic alcohols, aliphatic alcohols, alicyclic alcohols having at least one hydroxyl group in the molecule and / or those (Meth) acrylate obtained by reaction with an alkylene oxide adduct of (meth) acrylic acid.
More specifically, for example, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, isooctyl (meth) Acrylate, tetrahydrofurfuryl (meth) acrylate, isobornyl (meth) acrylate, benzyl (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, diethylene glycol di (meth) ) Acrylate, triethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) a Relate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate and other dipentaerythritol poly (meth) acrylates, diols described above, triols, tetraols, hexaols And (meth) acrylates of alkylene oxide adducts of polyhydric alcohols, such as ethylene oxide-modified bisphenol A diacrylate and propylene oxide-modified bisphenol A diacrylate.
Among them, (meth) acrylates of alcohols include (meth) acrylates having two or more (meth) acrylic groups in one molecule obtained by reaction of polyhydric alcohol and (meth) acrylic acid, for example di- Pentaerythritol poly (meth) acrylate and the like are preferably used.
Of the (meth) acrylate compounds described above, an acrylate compound is preferably used in view of the polymerization rate rather than a methacrylate compound.

Furthermore, examples of the above-described polyester (meth) acrylate that can be used as the radical polymerizable organic compound include polyester (meth) acrylate obtained by a reaction between a hydroxyl group-containing polyester and (meth) acrylic acid.
Moreover, as above-mentioned polyether (meth) acrylate, the polyether acrylate obtained by reaction of a hydroxyl-containing polyether and acrylic acid can be mentioned.

  Among the radical polymerizable organic compounds described above, in the present invention, epoxy acrylate obtained by reacting bisphenol A diglycidyl ether and acrylic acid (for example, “VR-77” manufactured by Showa Polymer Co., Ltd.), isobornyl Acrylate, lauryl acrylate, isostearyl acrylate, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, ethylene oxide modified pentaerythritol tetraacrylate, ethylene oxide modified trimethylolpropane triacrylate are from the point of reactivity, mechanical properties of cured products, etc. Preferably used.

  In the resin composition for optical three-dimensional model | molding of this invention, content of a radically polymerizable organic compound is 1 based on the total mass of the resin composition for optical three-dimensional model | molding from points, such as reaction rate and mechanical property. -50 mass% is preferable, 5-40 mass% is more preferable, 10-30 mass% is still more preferable. If the content of the radically polymerizable organic compound is too small, the photocuring property is lowered, and the mechanical properties of the resulting three-dimensional structure are likely to be lowered. On the other hand, if the content is too large, the curing shrinkage rate of the three-dimensional structure is increased. And the modeling precision of the resin composition for optical three-dimensional modeling becomes low too much, and modeling tends to be difficult to be performed smoothly.

  Further, as the radical photopolymerization initiator to be contained together with the radical polymerizable organic compound, any polymerization initiator capable of initiating radical polymerization of the radical polymerizable organic compound when irradiated with active energy rays such as light can be used. Examples thereof include benzyl or its dialkyl acetal compound, phenyl ketone compound, acetophenone compound, benzoin or its alkyl ether compound, benzophenone compound, thioxanthone compound and the like.

Specifically, examples of benzyl or a dialkyl acetal compound thereof include benzyl dimethyl ketal and benzyl-β-methoxyethyl acetal.
Examples of the phenyl ketone compound include 1-hydroxy-cyclohexyl phenyl ketone.
Examples of the acetophenone compound include diethoxyacetophenone, 2-hydroxymethyl-1-phenylpropan-1-one, 4′-isopropyl-2-hydroxy-2-methyl-propiophenone, and 2-hydroxy-2. -Methyl-propiophenone, p-dimethylaminoacetophenone, p-tert-butyldichloroacetophenone, p-tert-butyltrichloroacetophenone, p-azidobenzalacetophenone and the like.

Examples of the benzoin compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin normal butyl ether, and benzoin isobutyl ether.
Further, examples of the benzophenone compound include benzophenone, methyl o-benzoylbenzoate, Michler's ketone, 4,4′-bisdiethylaminobenzophenone, 4,4′-dichlorobenzophenone, and the like.
Examples of the thioxanthone compound include thioxanthone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, and 2-isopropylthioxanthone.

The resin composition for optical three-dimensional model | molding of this invention can mix | blend and use 1 type, or 2 or more types of radical photopolymerization initiator according to desired performance.
Among them, in the present invention, 1-hydroxycyclohexyl phenyl ketone is preferably used as a radical photopolymerization initiator from the viewpoint that the hue of the resulting cured product is good (eg, the yellowness is small).

  The content of the radical photopolymerization initiator is preferably 0.01 to 10% by mass, more preferably 0.1 to 8% by mass, and 1 to 5% by mass based on the total mass of the resin composition for optical three-dimensional modeling. % Is more preferable. When based on the mass of the radical polymerizable organic compound, based on the total mass of the radical polymerizable organic compound, the radical photopolymerization initiator is 0.1 to 20% by mass, particularly 1 to 15% by mass. It is preferable to contain.

Speaking from the entire composition of the resin composition for optical three-dimensional modeling, the resin composition for optical three-dimensional modeling of the present invention is based on the total mass of the resin composition for optical three-dimensional modeling, and the above general formula (I) 1 to 85% by weight of the above-described other cationically polymerizable organic compound (II) other than the epoxy compound (I), 1 to 85% by weight of the epoxy compound (I) represented by the formula: 0.1 to 10% by mass, 1 to 50% by mass of a radical polymerizable organic compound, 0.01 to 10% by mass of a radical photopolymerization initiator, and 1 to 20% by mass of elastomer particles. preferable.
As long as the effects of the present invention are not impaired, the resin composition for optical three-dimensional modeling of the present invention, if necessary, colorants such as pigments and dyes, antifoaming agents, leveling agents, thickeners, flame retardants, oxidation agents An appropriate amount of one or two or more of an inhibitor, a filler (crosslinked polymer particles, silica, glass powder, ceramic powder, metal powder, etc.) and a modifying resin may be contained.

  The method for preparing the resin composition for optical three-dimensional modeling of the present invention is not particularly limited, and any method can be used as long as the above-described components can be mixed uniformly without causing photopolymerization of the resin composition for optical three-dimensional modeling. It may be prepared by the method.

Any of the conventionally known optical three-dimensional modeling methods and apparatuses can be used for optical three-dimensional modeling using the resin composition for optical three-dimensional modeling of the present invention. As a representative example of the optical three-dimensional modeling method that can be preferably adopted, the active energy ray is selectively irradiated so that a cured layer having a desired pattern can be obtained in the liquid resin composition for optical three-dimensional modeling of the present invention. Then, a cured layer is formed, and then the uncured liquid optical three-dimensional resin composition is supplied to the cured layer, and similarly, the cured layer continuous with the cured layer is irradiated by irradiating active energy rays. The method of finally obtaining the target three-dimensional molded item can be mentioned by repeating the lamination | stacking operation to form.
Examples of active energy rays at that time include ultraviolet rays, electron beams, X-rays, radiation, and high frequencies. Among them, ultraviolet rays having a wavelength of 300 to 400 nm are preferably used from an economical viewpoint, and as a light source at that time, an ultraviolet laser (for example, a semiconductor-excited solid laser, an Ar laser, a He—Cd laser), a high-pressure mercury lamp is used. Ultra high pressure mercury lamps, low pressure mercury lamps, xenon lamps, halogen lamps, metal halide lamps, ultraviolet LEDs (light emitting diodes), ultraviolet fluorescent lamps, and the like can be used.

  In forming each cured resin layer having a predetermined shape pattern by irradiating active energy rays onto a modeling surface made of a resin composition for optical three-dimensional modeling, the active energy is reduced to a point such as a laser beam. A planar drawing mask in which a hardened resin layer may be formed by a line drawing method using a line or a plurality of micro light shutters such as a liquid crystal shutter or a digital micromirror shutter (DMD). Alternatively, a modeling method may be employed in which a cured resin layer is formed by irradiating the modeling surface with active energy rays through the surface.

  The resin composition for optical three-dimensional modeling of the present invention can be widely used in the field of optical three-dimensional modeling, and is not limited at all, but as a typical application field, the appearance design is verified during the design. Such as a shape confirmation model for checking, a functional test model for checking the functionality of parts, a master model for producing molds, a master model for producing molds, a direct mold for prototype molds, etc. it can. In particular, the resin composition for optical three-dimensional modeling according to the present invention is effective for producing a shape confirmation model or a function test model of a precision part or the like. More specifically, for example, it can be effectively used for applications such as precision parts, electrical / electronic parts, furniture, building structures, automotive parts, various containers, castings, models, mother dies, processing, etc. .

EXAMPLES The present invention will be specifically described below with reference to examples and the like, but the present invention is not limited to the examples.
Moreover, in the following examples, the viscosity of the resin composition for optical three-dimensional modeling, the curing depth (Dp), the critical curing energy (Ec) and the work curing energy (E ₁₀ ), the shrinkage due to photocuring (volume shrinkage), As well as mechanical properties of three-dimensional objects obtained by stereolithography [tensile properties (tensile rupture strength, tensile rupture elongation, tensile elastic modulus), yield strength, bending properties (bending strength, bending elastic modulus)], thermal deformation Measurement or evaluation of temperature and self-tapping properties was performed as follows.

(1) Viscosity of the resin composition for optical three-dimensional modeling:
After placing the resin composition for optical three-dimensional modeling in a thermostatic bath at 25 ° C. and adjusting the temperature of the resin composition for optical three-dimensional modeling to 25 ° C., a B-type viscometer (manufactured by Tokyo Keiki Co., Ltd.) is used. Measured.

(2) Curing depth (Dp), critical curing energy (Ec) and work curing energy (E ₁₀ ) of the resin composition for optical three-dimensional modeling:
Measurement was performed according to the theory described in Non-Patent Document 1. Specifically, a laser beam (ultraviolet light with a wavelength of 355 nm, a liquid surface laser intensity of 100 mW) of a semiconductor-excited solid laser is applied to a modeling surface (liquid surface) made of a resin composition for optical three-dimensional modeling, and the irradiation speed is 6 steps. A photocured film was formed by irradiating with a change (6 steps of irradiation energy amount). The produced photocured film was taken out from the resin composition liquid for optical three-dimensional modeling, the uncured resin was removed, and the thickness of the cured film corresponding to six levels of energy was measured with a vernier caliper. Plotting the photocured film thickness as the Y-axis and the irradiation energy amount as the X-axis (logarithmic axis), obtaining the cure depth [Dp (mm)] from the slope of the straight line obtained by plotting, and intercepting the X-axis Was the critical curing energy [Ec (mJ / cm ² )], and the exposure energy required to cure to a thickness of 0.25 mm was the work curing energy [(E ₁₀ / (mJ / cm ² )].

(3) Shrinkage rate:
Specific gravity (d ₀ ) of the resin composition for optical three-dimensional modeling (liquid) before photocuring and specific gravity (d ₁ ) of the photocured product obtained by photocuring (Examples 1 to 8 and Comparative Example 1) From the specific gravity (d ₁ ) (Examples 9 to 11) of the product obtained by heat-treating the photocured product at 60 ° C. for 1 hour, the shrinkage rate was determined by the following formula.

Shrinkage rate (%) = {(d ₁ −d ₀ ) / d ₁ } × 100

At that time, the specific gravity (d ₀ ) of the resin composition for optical three-dimensional modeling (liquid) before photocuring was measured at a temperature of 25 ° C. using a specific gravity bottle. Moreover, the specific gravity (d ₁ ) of the photocured product (molded product) obtained by photocuring is a temperature of 25 ° C., adopting a method of weighing in a liquid according to JIS Z8807, “Mr. It measured using "total SD-120L".

(4) Tensile properties of the three-dimensional structure (tensile breaking strength, tensile breaking elongation, tensile elastic modulus):
Use a three-dimensional model (a dumbbell-shaped test piece conforming to JIS K-7113) prepared in the following examples or comparative examples (Examples 1 to 8 and Comparative Examples 1 to 4) or use it at 60 ° C. Using the three-dimensional structure (Examples 9 to 11) after heat treatment for 1 hour, according to JIS K-7113, the tensile breaking strength (tensile strength), tensile breaking elongation (tensile elongation) and tensile elasticity of the test piece The rate was measured.

(5) Bending properties (bending strength, bending elastic modulus) of the three-dimensional structure:
Use the three-dimensional modeled object (bar-shaped test piece based on JIS K-7171) produced in the following examples or comparative examples (Examples 1 to 8 and Comparative Examples 1 to 4) or use it at 60 ° C. Using the three-dimensional structure (Examples 9 to 11) after heat treatment for 1 hour, the bending strength and the bending elastic modulus of the test piece were measured according to JIS K-7171.

(6) Thermal deformation temperature of the three-dimensional structure (load deflection temperature):
(I) High load deflection temperature:
Three-dimensional model manufactured in the following examples or comparative examples (bar-shaped test piece in accordance with JIS K-7171) [UV light (UV intensity 3 mW / cm ² ) at room temperature using a high-pressure mercury lamp after optical modeling at 20 Toyo Seiki Co., Ltd. using a three-dimensional model after irradiation for 1 minute (Examples 1 to 8 and Comparative Examples 1 to 4) or a three-dimensional model (Examples 9 to 11) after heat-treating it at 60 ° C. for 2 hours Using a “HDT tester 6M-2” manufactured by applying a load (high load) of 1.81 MPa to the test piece, and measuring the thermal deformation temperature of the test piece according to JIS K-7207 (Method A) Thus, it was used as an index of heat resistance. The higher the heat distortion temperature, the better the heat resistance.
(Ii) Low load deflection temperature:
Applying a load (low load) of 0.45 MPa to the three-dimensional modeled object (test piece) produced in the same manner as in (i) above, thermal deformation of the test piece according to JIS K-7207 (Method B) The temperature was measured and used as an index of heat resistance. The higher the heat distortion temperature, the better the heat resistance.

(7) Self-tapping property:
(I) Using the resin composition for optical three-dimensional modeling of the following examples or comparative examples, adopting the optical modeling method described in the examples or comparative examples, the three-dimensional model (test model) shown in FIG. ) A, specifically, a three-dimensional modeled object in which five cylinders 2 [outer diameter 8 mm, central through-hole diameter (inner diameter) 3.8 mm, height 25 mm] stand upright at equal intervals on the base 1 (test Model) A was manufactured.
In Examples 1-8 and Comparative Examples 1-4, the three-dimensional molded product (test model) A obtained by this is used as it is, and in Examples 9-11, the test model A obtained above is 60 ° C. The following test (ii) was carried out using the sample heat treated for 1 hour.
(Ii) A tapping screw (outside diameter of tapping screw = 4 mm) is applied to the through hole at the center of each cylinder in the non-heat-treated test model A or the heat-treated test model A obtained in (i). And a tap screw was made to enter the hole with a maximum torque of 1.5 MPa, and a self-tapping test was conducted.
And, when the tap screw can be completely inserted without causing damage in four or five of the five cylinders formed in the test model A (all of the five cylinders were not damaged or only one was damaged) Case) Good self-tapping (O), and two or three of the five cylinders formed in the test model A can be completely inserted into the tap screw without causing damage (out of the five cylinders) Self-tapping is slightly poor (△) when 2 or 3 are damaged), and self-tapping is poor when 4 or 5 of the 5 cylinders formed on test model A are damaged (X) was evaluated.

(8) Hygroscopic elongation:
(I) Using the resin composition for optical three-dimensional modeling of the following examples or comparative examples, adopting the optical modeling method described in the examples or comparative examples, the three-dimensional model (test model) shown in FIG. ) B, specifically, the length (length) × width (width) × thickness = 200 mm × 10 mm × 1 mm in the center in the width direction of the strip-shaped base 3, the thickness is 1 mm along the length direction, A three-dimensional modeled object (test model) B having a T-shaped cross section in which the vertical wall 4 having a height of 10 mm was formed was manufactured.
(Ii) In Examples 1 to 8 and Comparative Examples 1 to 4, the three-dimensional structure (test model) B obtained in (i) was left as it was for 2 weeks in a high humidity environment at a temperature of 25 ° C. and a humidity of 80%. In Examples 9 to 11, the test model B obtained above was heat-treated at 60 ° C. for 1 hour, and then left in an environment at a temperature of 25 ° C. and a humidity of 80% for 2 weeks. The rate was determined.

Hygroscopic elongation (%) = {(L ₁ −L ₀ ) / L ₀ } × 100

[In the above formula, L ₀ is the length (longitudinal dimension) (mm) of the three-dimensional structure (test model) immediately before being placed in a high humidity environment at a temperature of 25 ° C. and a humidity of 80% RH, and L ₁ is as described above. The length (longitudinal dimension) (mm) of the three-dimensional structure (test model) after being left to stand in a high humidity environment for 2 weeks is shown. ]

The types and abbreviations of the components used in the following examples or comparative examples are as follows.
(1) Epoxy compound (I)
EHPE-3150:
1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct of 2,2-bis (hydroxymethyl) -1-butanol (“EHPE-3150” manufactured by Daicel Chemical Industries, Ltd.)
(2) Elastomer particles:
・ RKB-2023:
Core-shell type elastomer particles made of rubber-modified epoxy resin (“Reginas Bond RKB-2023” manufactured by Resinas Kasei Co., Ltd., elastomer component content 40% by mass, bisphenol A diglycidyl ether resin content 60% by mass, average particle size 200 nm)

(3) Other cationically polymerizable organic compounds:
(I) EX-321:
A mixture of diglycidyl ether and triglycidyl ether of trimethylolpropane (“Deconal EX-321” manufactured by Nagase ChemteX Corporation) [corresponding to epoxy compounds (II-A) and (II-B)]
(Ii) ERISYS GE30:
Triglycidyl ether of trimethylolpropane (iii) Bisphenol A diglycidyl ether (iv) HBE-100:
・ Diglycidyl ether of hydrogenated bisphenol (“Rikaresin HBE-100” manufactured by Shin Nippon Rika Co., Ltd.)
(V) 2021P:
3,4-epoxycyclohexyl-3 ′, 4′-epoxycyclohexanecarboxylate (“Celoxide 2021P” manufactured by Daicel Chemical Industries, Ltd.)
(Vi) GE-30:
・ Trimethylolpropane triglycidyl ether (PI-TI / R Japan Co., Ltd. “GE-30”)
(Vii) OXT221:
Bis (3-ethyl-3-oxetanylmethyl) ether (“Aron Oxetane OXT221” manufactured by Toagosei Co., Ltd.)

(4) Radical polymerizable organic compound:
(I) A-BPE-4:
・ Ethylene oxide modified bisphenol A diacrylate (“NK Ester A-BPE-4” manufactured by Shin-Nakamura Chemical Co., Ltd.)
(Ii) A-9530:
Dipentaerythritol polyacrylate (“NK-Ester A-9530” manufactured by Shin-Nakamura Chemical Co., Ltd.)
(Iii) ATM-4E:
・ Ethylene oxide-modified pentaerythritol tetraacrylate (“NK Ester ATM-4E” manufactured by Shin-Nakamura Chemical Co., Ltd.)

(5) Polymerization initiator:
(I) CPI-101A:
Triarylsulfonium hexafluoroantimonate-based cationic polymerization initiator (“CIP-101A” manufactured by San Apro Co., Ltd.)
(Ii) Irgacure 184:
1-hydroxy-octhexyl phenyl ketone (“Irgacure 184” manufactured by Ciba Specialty Chemicals, radical polymerization initiator)

<< Examples 1 to 9 >>
(1) The above-described components are mixed in the proportions shown in Table 1 below, and stirred well at 25 ° C. until completely dissolved (stir mixing time: about 6 hours), and the resin composition for optical three-dimensional modeling Was prepared.
When the viscosity of the resin composition for optical three-dimensional modeling obtained by this was measured by the above-described method, it was as shown in Table 1 below.
(2) When the curing depth (Dp), critical curing energy (Ec), and work curing energy (E ₁₀ ) of the resin composition for optical three-dimensional modeling obtained in (1) above were measured by the above-described methods, As shown in Table 1.
Moreover, it was as having shown in following Table 1 when the shrinkage rate at the time of photocuring of the resin composition for optical three-dimensional modeling obtained by said (1) was measured by the above-mentioned method.

(3) A semiconductor laser (rated output: 1000 mW; wavelength: 355 nm) using an ultrahigh-speed stereolithography system (“SOLIFORM500B” manufactured by Nabtesco Corporation) using the resin composition for stereolithography obtained in (1) above; Spectra Physics "semiconductor-excited solid laser BL6 type", with a liquid level of 500 mW and a liquid level irradiation energy of 80 mJ / cm ² , a slice pitch (lamination thickness) of 0.10 mm and an average modeling time of 2 minutes per layer Are subjected to optical three-dimensional modeling, dumbbell-shaped test pieces conforming to JIS K-7113 for measuring physical properties, bar-shaped test specimens conforming to JIS K-7171, test model A for self-tapping property test and moisture absorption elongation The test model B for measuring the rate was prepared, and the physical properties were measured or evaluated by the method described above. To show.

<< Comparative Examples 1-4 >>
(1) The above-described components are mixed in the proportions shown in Table 2 below, and stirred well at 25 ° C. until completely dissolved (stir mixing time: about 6 hours). Was prepared.
When the viscosity of the resin composition for optical three-dimensional modeling obtained by this was measured by the method described above, it was as shown in Table 2 below.
(2) When the curing depth (Dp), critical curing energy (Ec), and work curing energy (E ₁₀ ) of the resin composition for optical three-dimensional modeling obtained in (1) above were measured by the above-described methods, Table 2 shows the results.
Moreover, it was as showing in following Table 2 when the shrinkage rate at the time of photocuring of the resin composition for optical three-dimensional modeling obtained by said (1) was measured by the above-mentioned method.
(3) Using the resin composition for optical modeling obtained in (1) above, optical three-dimensional modeling is performed in the same manner as in (1) of Examples 1 to 8, and JIS K-7113 for measuring physical properties is applied. A method for producing a test specimen having a dumbbell shape conforming to the above, a bar-shaped test piece conforming to JIS K-7171, a test model A for a self-tapping property test, and a test model B for measuring a hygroscopic elongation rate, and the physical properties described above. Measured with The results are shown in Table 2 below.

<< Examples 10 to 12 >>
After heat-treating the three-dimensional structure (various test pieces) obtained in (3) of Examples 1 to 3 at 60 ° C. for 1 hour, the physical properties thereof were measured by the methods described above, and as shown in Table 3 below. there were.

Example 13
(1) The components shown in Table 4 below were mixed in the proportions shown in Table 4 below to prepare a liquid composition [a composition containing no epoxy compound (I) and elastomer particles].
(2) The amount described in Table 5 below for epoxy compound (I) (EHPE-3150) and / or elastomer particles (RKB-2023) with respect to 85 parts by mass of the liquid composition prepared in (1) above ( The resin composition for optical three-dimensional model | molding of Experiment 1-45 is prepared, respectively, and is similar to (3) of Examples 1-8 using each resin composition for optical three-dimensional model | molding. A three-dimensional optical modeling was performed to prepare a bar-shaped test piece and a test model A for a self-tapping test in accordance with JIS K-7171.
And about the modeling thing (bar-shaped test piece) obtained using each of the resin compositions for optical three-dimensional modeling of Experiments 1-45, the thermal deformation temperature (load deflection temperature) is measured by the method described above, When the deflection temperature under load is 50 ° C. or higher at high load and 65 ° C. or higher at low load, the heat resistance is evaluated as good (◯), and when it is lower (less than 50 ° C. at high load and (Or less than 65 ° C. at low load) was evaluated as having poor heat resistance (x).
Moreover, about the test model A obtained using each of the resin compositions for optical three-dimensional modeling of Experiments 1-45, the self-tapping property was evaluated by the method described above.
The results are shown in Table 5 below.

By performing optical three-dimensional modeling using the resin composition for optical three-dimensional modeling of the present invention, it has a high heat distortion temperature (deflection temperature), is excellent in heat resistance, and is excellent in toughness, impact, 3D objects that are resistant to damage even when subjected to external forces such as bending, compression, and screwing, are durable, and have excellent dimensional accuracy, appearance, and mechanical properties. Can be manufactured.
Therefore, using the resin composition for optical three-dimensional modeling of the present invention, for precision parts, electrical / electronic parts, furniture, building structures, automotive parts, various containers, castings, molds, mother dies, etc. Produces high-productivity models, machining models, parts for designing complex heat transfer circuits, parts for analyzing and planning heat medium behavior with complex structures, and other various three-dimensional objects with complex shapes and structures can do.

It is a figure which shows the shape and dimension of the three-dimensional molded item (test model A) used for the self-tap property test. It is a figure which shows the shape and dimension of the three-dimensional molded item (test model B) used for the measurement of moisture absorption elongation.

Explanation of symbols

1 Base 2 Cylinder 3 Strip Base 4 Vertical Wall

Claims (8)

A resin composition for optical three-dimensional modeling comprising a cationically polymerizable organic compound, a photocationic polymerization initiator, and elastomer particles, wherein the cationic polymerizable organic compound is based on the total mass of the resin composition for optical three-dimensional modeling , The following general formula (I);

(In the formula, R ¹ represents an a-valent organic group, a is an integer of 1 to 6, b is an integer of 1 to 30, and the average value of a b is in the range of 1 to 30. .)
The epoxy compound (I) represented by the formula is contained in a proportion of 1% by mass or more and less than 10% by mass, the photocationic polymerization initiator is contained in a proportion of 0.1 to 10% by mass, and the elastomer particles are contained in 1 to 20%. The resin composition for optical three-dimensional modeling characterized by containing in the ratio of the mass%.   2. The cation polymerizable organic compound (II) other than the epoxy compound (I) is further contained at a ratio of 1 to 85% by mass based on the total mass of the resin composition for optical three-dimensional modeling. A resin composition for optical three-dimensional modeling.   As other cationically polymerizable organic compound (II), an aliphatic or alicyclic epoxy compound (II-A) having three or more glycidyl groups and / or two or more glycidyl groups and one hydroxyl group The aliphatic or alicyclic epoxy compound (II-B) having the above is the total of the epoxy compound (II-A) and the epoxy compound (II-B), based on the total mass of the resin composition for optical three-dimensional modeling. And the resin composition for optical three-dimensional model | molding of Claim 2 contained in the ratio of 5-30 mass%. As other cationically polymerizable organic compound (II), the following general formula (II-C);

(In the formula, R ² represents a hydrogen atom or a methyl group.)
The diglycidyl ether (II-C) of hydrogenated bisphenol represented by formula (3) is contained in a proportion of 3 to 30% by mass based on the total mass of the resin composition for optical three-dimensional modeling. A resin composition for optical three-dimensional modeling.   As another cationically polymerizable organic compound (II), 3,4-epoxycyclohexyl-3 ′, 4′-epoxycyclohexanecarboxylate (II-D) is based on the total mass of the resin composition for optical three-dimensional modeling. The resin composition for optical three-dimensional model | molding of any one of Claims 2-4 contained in the ratio of 1-60 mass%.   The oxetane compound (II-E) is contained as the other cationic polymerizable organic compound (II) in a proportion of 1 to 20% by mass based on the total mass of the resin composition for optical three-dimensional modeling. 5. The resin composition for optical three-dimensional modeling according to any one of 5 above.   1 to 50% by mass of a radical polymerizable organic compound and 0.01 to 10% by mass of a radical photopolymerization initiator based on the total mass of the optical three-dimensional resin composition. 6. The resin composition for optical three-dimensional modeling according to any one of 6 above.   Based on the total mass of the resin composition for optical three-dimensional modeling, the epoxy compound (I) represented by the general formula (I) is 1% by mass or more and less than 10% by mass, other than the epoxy compound (I). 1 to 85% by mass of the cationically polymerizable organic compound (II), 0.1 to 10% by mass of the cationic photopolymerization initiator, 1 to 50% by mass of the radically polymerizable organic compound, and 0.01 to the photoradical polymerization initiator. The resin composition for optical three-dimensional model | molding of any one of Claims 1-7 which contains 10-10 mass% and an elastomer particle in the ratio of 1-20 mass%.

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