JP2018053133A - Resin composition for optical solid molding - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition for molding an optical solid that provides a solid molded article small in shrinkage rate during curing and excellent in dimensional accuracy, high in physical strength and excellent in toughness, having high heat deformation temperature and excellent in heat resistance, high in hardness and high in shape retention property, and low in yellowness, high in light transmissivity and excellent in color tone and transparency.SOLUTION: There is provided a resin composition for molding an optical solid, containing a cationic polymerizable organic compound (A), a radical polymerizable organic compound (B), a cationic polymerization initiator (C), and a radical polymerization initiator (D), and having a ratio (W/W) of the content of the radical polymerizable organic compound (B) (W) (mass) to the content of the cationic polymerizable organic compound (A) (W) (mass) of 0.45 or more, and containing an aromatic polyepoxy compound (A-1) having 3 or more epoxy groups of 30 to 80 mass% based on total mass of the cationic polymerizable organic compound (A) contained in the resin composition for molding an optical solid.SELECTED DRAWING: None

Description

  The present invention provides an optical three-dimensional modeling that provides a three-dimensional molded article that has excellent reactivity during light irradiation, high mechanical strength, excellent toughness, excellent heat resistance and transparency, and is excellent in color tone without yellowing. The present invention relates to a method for producing a three-dimensional model by performing optical three-dimensional modeling using the resin composition for optical and the resin composition for optical three-dimensional modeling.

In recent years, a method for three-dimensional optical modeling of a liquid photocurable resin composition based on three-dimensional data input to a computer has a 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, an ultraviolet laser controlled by a computer is selectively irradiated so that a desired pattern is obtained on the liquid surface of the liquid photocurable resin composition placed in a container. Finally, a predetermined thickness is cured, and then a liquid resin for one layer is supplied onto the cured layer, and similarly cured by irradiation with an ultraviolet laser in the same manner as described above to repeat the lamination operation to obtain a continuous cured layer. The method of obtaining a three-dimensional molded item can be mentioned. By this optical three-dimensional modeling method, it is possible to easily manufacture a model having a considerably complicated shape in a relatively short time.

  About resin or resin composition used for optical three-dimensional modeling, it is required that a three-dimensional model can be manufactured in a short modeling time with high curing sensitivity by active energy rays, and it has low viscosity and excellent handleability at the time of modeling. .

In addition, the three-dimensional model obtained by optical modeling using the resin composition for optical three-dimensional modeling is a model for verifying the appearance design of various industrial products during the design, and for checking the functionality of parts. It is widely used as a model, a resin mold for manufacturing a mold, and a base model for manufacturing a mold.
For three-dimensional objects obtained by optical three-dimensional modeling using a resin composition for optical three-dimensional modeling, mechanical strength such as breaking strength is high and toughness is strong, and it is strong and difficult to break. It has been demanded.
Furthermore, in recent years, excellent heat resistance and high transparency are required for a three-dimensional model obtained by optical three-dimensional modeling using a resin composition for optical three-dimensional modeling. Also, for example, in the arts and crafts field such as automobile and motorcycle lens models, restoration of artworks, imitation and contemporary art, and design presentation models of glass-walled buildings, it is excellent with transparency and no yellowing There is a demand for a resin composition for optical three-dimensional modeling that gives a three-dimensional modeled object having a color tone.

  For the production of a three-dimensional structure having high mechanical strength and excellent toughness, for producing an optical three-dimensional structure containing a cationic polymerizable organic compound having an epoxy group and a radical polymerizable organic compound having an unsaturated double bond Resin for optical three-dimensional modeling which mix | blended the softness | flexibility improver (tensile elongation improver) which consists of a polyether which consists of a tetraethylene oxide unit and / or 2-substituted tetraethylene oxide unit, and has a hydroxyl group at both the terminal in the resin composition A composition has been proposed (Patent Document 1). In Patent Document 1, when optical stereolithography is performed using the resin composition for optical stereolithography blended with polyether, not only the tensile elongation is improved, but also the stereolithography product having excellent load flexibility. It is described that a three-dimensionally shaped object with little decrease in the deflection temperature under load is obtained. However, the present inventors have prepared the resin composition for optical three-dimensional modeling described in Patent Document 1, particularly the resin composition for optical three-dimensional modeling described in Example 1 and Example 10 thereof. When a follow-up experiment was conducted, optical solid modeling was difficult, and even when optical three-dimensional modeling was possible, the resulting three-dimensional model was weak and brittle, load deflection (heat resistance), tensile elongation It was not possible to obtain a practical three-dimensional model having excellent properties and toughness.

In addition, when the present inventors include an oxetane compound and a polyalkylene ether compound in an optical three-dimensional resin composition containing a cationically polymerizable organic compound and a radically polymerizable organic compound, the impact strength is high and the toughness is increased. It was found out that a resin composition for optical three-dimensional modeling that gives a three-dimensional molded product excellent in the above can be obtained (see Patent Document 2).
The three-dimensional structure obtained by optical modeling of this optical three-dimensional resin composition containing an oxetane compound and a polyalkylene ether has high impact strength and excellent toughness, but exhibits a yellowish color tone, Also, because it has turbidity and the light transmittance is not sufficient, it can be used effectively for applications where color tone and transparency are not a problem, but it is not suitable for applications that require good color tone and excellent transparency. In addition, the heat resistance is insufficient.

Moreover, in order to improve the transparency of the three-dimensional modeled object obtained by stereolithography, cationic polymerization mainly comprising an alicyclic epoxy compound such as 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate. Polyalkylene glycol di (meth) acrylate as a part of the radical polymerizable organic compound in the resin composition for optical three-dimensional modeling containing a polymerizable organic compound, a radical polymerizable organic compound, a cationic polymerization initiator and a radical polymerization initiator It has been proposed to contain (Patent Document 3).
However, a three-dimensional model obtained by optical modeling of the optical three-dimensional model resin composition has low impact strength, inferior toughness and durability, and further has insufficient heat resistance.

Furthermore, the resin composition for radically polymerizable optical three-dimensional modeling mainly composed of urethane (meth) acrylate contains polyalkylene glycol (meth) acrylate as a part of the radical polymerizable organic compound, and is subjected to optical modeling. It has been proposed to improve the impact resistance of the resulting three-dimensional structure (Patent Document 4).
However, since this resin composition for optical three-dimensional modeling contains only a radical polymerizable organic compound as a photopolymerizable component and does not contain a cationic polymerizable organic compound, the dimensional accuracy of a three-dimensional model obtained by optical modeling Is low, has deformation due to warping, and the resin near the surface does not cure sufficiently due to oxygen inhibition, and even if the resin itself has sufficient transparency, modeling after optical three-dimensional modeling The surface of an object is rough and does not transmit light sufficiently.

JP 2003-73457 A JP 2005-15739 A Special table 2004-530773 gazette JP-A-9-194540

The object of the present invention is low viscosity, excellent handling at the time of modeling, high sensitivity of curing with active energy rays, and can produce a three-dimensional shaped article with high productivity in a short active energy ray irradiation time, and the resolution of the shaped article In addition to having the basic physical properties necessary for an optical three-dimensional modeling resin composition that gives an optical three-dimensional molded product that is high in modeling accuracy and dimensional accuracy, the shrinkage rate during curing is small and excellent in dimensional accuracy, It is to provide a resin composition for optical three-dimensional modeling that gives a three-dimensional modeled article that has high mechanical strength, excellent toughness, excellent shape retention, heat resistance and transparency, and is excellent in color tone without yellowing. .
Furthermore, an object of the present invention is to provide a three-dimensional structure excellent in low shrinkage, mechanical properties, shape retention, heat resistance, transparency and color tone upon curing, using the above-described resin composition for optical three-dimensional modeling. It is to provide a method of manufacturing.

  As a result of repeated studies by the present inventors to achieve the above object, a so-called hybrid type optical compound containing a cationic polymerizable organic compound, a radical polymerizable organic compound, a cationic polymerization initiator and a radical polymerization initiator is used. In the resin composition for three-dimensional modeling, the ratio of the content (mass) of the radical polymerizable organic compound to the content (mass) of the cationic polymerizable organic compound is 0.45 or more (the content of the radical polymerizable organic compound is Based on the total mass of the cationically polymerizable organic compound contained in the resin composition for optical three-dimensional modeling, and 3 epoxy groups When the aromatic polyepoxy compound having the above content is contained in a predetermined ratio, it is low viscosity and excellent in handling at the time of molding, curing by active energy rays It has a high degree of shrinkage at the time of curing and a size while satisfying the basic physical properties required for a resin composition for optical three-dimensional modeling that can produce a three-dimensional modeled product with high productivity by irradiation of active energy rays in a short time A resin composition for optical three-dimensional modeling that gives a three-dimensional model with excellent accuracy, high mechanical strength, excellent toughness, excellent shape retention, heat resistance and transparency, and excellent color tone without yellowing is obtained. I found out that

In addition, the present inventors in the resin composition for optical three-dimensional modeling,
* As a part of the cationically polymerizable organic compound, an oxetane compound is contained in a predetermined amount;
* As a part of the radical polymerizable organic compound, at least one of polyalkylene glycol di (meth) acrylate and polyalkylene glycol mono (meth) acrylate is contained in a predetermined amount;
* A diepoxy compound is included as part of the cationically polymerizable organic compound;
* If the diglycidyl ether of hydrogenated bisphenols is not included or is included, the content is kept below a predetermined amount;
When one or more of the above requirements are further adopted, the present invention described above that gives an optical three-dimensional object that has small shrinkage during curing and is excellent in shape retention, mechanical properties, heat resistance, transparency, and color tone. The present invention was completed based on these various findings.

That is, the present invention
(1) A resin composition for optical three-dimensional modeling comprising a cationically polymerizable organic compound (A), a radically polymerizable organic compound (B), a cationic polymerization initiator (C) and a radical polymerization initiator (D). ;
The ratio (W _B / W _A ) of the content (W _B ) (mass) of the radical polymerizable organic compound (B) to the content (W _A ) (mass) of the cationic polymerizable organic compound ( _A ) is 0. 45 or more; and
Based on the total mass of the cationically polymerizable organic compound (A) contained in the resin composition for optical three-dimensional modeling, 30 to 80% by mass of the aromatic polyepoxy compound (A-1) having 3 or more epoxy groups. Contained in proportions;
The resin composition for optical three-dimensional modeling characterized by the above-mentioned.

And this invention,
(2) Based on the total mass of the cationically polymerizable organic compound (A) contained in the resin composition for optical three-dimensional modeling, the oxetane compound (A-2) is contained in a proportion of 10 to 40% by mass ( 1) Resin composition for optical three-dimensional modeling;
(3) Based on the total mass of the radical polymerizable organic compound (B) contained in the resin composition for optical three-dimensional modeling, polyalkylene glycol di (meth) acrylate (B-1) and polyalkylene glycol mono (meth) The resin composition for optical three-dimensional modeling according to (1) or (2), which contains at least one acrylate (B-2) in a proportion of 1 to 30% by mass;
(4) The resin composition for optical three-dimensional modeling according to any one of (1) to (3), which contains a diepoxy compound (A-3) as a part of the cationically polymerizable organic compound (A);
(5) The optical component according to any one of (1) to (4), wherein the content of diglycidyl ether of hydrogenated bisphenols is 10% by mass or less based on the total mass of the cationically polymerizable organic compound (A). Three-dimensional modeling resin composition;
It is.

The present invention also provides:
(6) 30 to 70% by mass of the cationically polymerizable organic compound (A), 25 to 50% by mass of the radically polymerizable organic compound (B), and cationic polymerization based on the total mass of the resin composition for optical three-dimensional modeling. The optical three-dimensional modeling according to any one of (1) to (5), wherein the initiator (C) is contained in an amount of 0.1 to 10% by mass and the radical polymerization initiator (D) is contained in an amount of 0.1 to 10% by mass. Resin composition.
Furthermore, the present invention provides
(7) A method for producing a three-dimensional modeled object, wherein a three-dimensional modeled object is manufactured by performing optical three-dimensional modeling using the resin composition for optical three-dimensional model modeling according to any one of (1) to (6). It is.

The resin composition for optical three-dimensional modeling of the present invention is a resin composition for optical three-dimensional modeling that has high curing sensitivity with active energy rays, low viscosity, excellent handleability, and high resolution during optical three-dimensional modeling. In addition to providing the necessary basic physical properties, by performing optical three-dimensional modeling (hereinafter sometimes referred to as “optical modeling”) using the resin composition for optical three-dimensional modeling, the shrinkage rate during curing is small. Excellent dimensional accuracy, high mechanical strength, excellent toughness, high heat distortion temperature, excellent heat resistance, high initial hardness immediately after stereolithography, excellent shape retention, and low yellowness It is possible to obtain a three-dimensional structure having high light transmittance and excellent color tone and transparency.
In addition, the heat distortion temperature is further increased by heat-treating the three-dimensional object obtained by optical modeling using the resin composition for optical three-dimensional modeling of the present invention at a temperature of 50 ° C. or higher. A further improved three-dimensional model can be obtained.
Therefore, the resin composition for optical three-dimensional modeling of the present invention has high heat resistance, high transparency, no yellow coloring, excellent transparency and color tone, and excellent impact resistance, toughness, durability, and strength. 3D modeling objects that are required, for example, models for verifying the functionality and appearance design of various industrial products during design, resin molds for manufacturing molds, base models for manufacturing molds, automobiles And motorcycle lenses, restoration of art, imitation and modern art, art and craft fields such as glass-based architectural design presentation models, precision parts, electrical and electronic parts, furniture, building structures, automotive parts, various Effective for various uses such as containers, castings, railroad models, construction machinery, industrial robots, airplane control parts, especially for automotive parts It can be used.

The present invention is described in detail below.
The resin composition for optical three-dimensional model | molding of this invention is a resin composition used in order to manufacture a three-dimensional model | molding by irradiating active energy rays, such as light, and carrying out an optical modeling, Comprising: A cationically polymerizable organic compound ( A), a radically polymerizable organic compound (B), a cationic polymerization initiator (C) and a radical polymerization initiator (D).
The cationically polymerizable organic compound (A) used in the present invention is a compound that undergoes a polymerization reaction and / or a crosslinking reaction when irradiated with active energy rays such as light in the presence of the cationic polymerization initiator (C).
The radically polymerizable organic compound (B) used in the present invention is a compound that causes a polymerization reaction and / or a crosslinking reaction when irradiated with an active energy ray such as light in the presence of the radical polymerization initiator (D).
As used herein, the term “active energy rays” refers to energy rays that can cure the resin composition for optical three-dimensional modeling, such as ultraviolet rays, electron beams, X-rays, radiation, and high frequencies.

The resin composition for optical three-dimensional modeling of the present invention is
(Α) Ratio (W _B / W _A ) of the content (W _B ) (mass) of the radical polymerizable organic compound (B) to the content (W _A ) (mass) of the cationic polymerizable organic compound (A) 0.45 or more; and
(Β) 30 to 80 aromatic polyepoxy compound (A-1) having 3 or more epoxy groups based on the total mass of the cationically polymerizable organic compound (A) contained in the resin composition for optical three-dimensional modeling Contained in a proportion by mass;
It is essential to satisfy the requirement (α) and the requirement (β).

In optical three-dimensional modeling using a so-called hybrid type optical three-dimensional modeling resin composition containing a cationic polymerizable organic compound, a radical polymerizable organic compound, a cationic polymerization initiator and a radical polymerization initiator, the shrinkage rate of the resin is reduced. Conventionally, the content (mass) of the radical polymerizable organic compound is 1/3 or less of the content (mass) of the cation polymerizable organic compound because it is necessary to obtain a molded article that is suppressed and has little deformation due to warping. If the content of the radical polymerizable organic compound is higher than that, the curing shrinkage of the resin is large, and there is a problem that a three-dimensional molded article having a desired dimensional accuracy cannot be obtained. .
However, in the hybrid optical resin composition for optical three-dimensional modeling, the content (W _B ) of the radical polymerizable organic compound (B) with respect to the content (W _A ) (mass) of the cationic polymerizable organic compound (A). By making the (mass) ratio (W _B / W _A ) 0.45 or more as defined in the present invention [requirement (α)], it is quite unexpected that a three-dimensional modeled object is obtained by stereolithography. As a result, the mechanical strength of the optical three-dimensional object increased, and the hardness of the optical three-dimensional structure increased and the shape retention was improved.

Radical polymerizable organic compound (B) relative to the content (W _A ) (mass) of the cationic polymerizable organic compound (A) [total mass of the cationic polymerizable organic compound (A) contained in the resin composition for optical three-dimensional modeling] ) Content (W _B ) (mass) [total mass of radical polymerizable organic compound (B) contained in the resin composition for optical three-dimensional modeling] (W _B / W _A ) [hereinafter simply referred to as “ratio” When (W _B / W _A ) ”is sometimes less than 0.45, the mechanical properties of the three-dimensional structure obtained by stereolithography are lowered and the toughness is inferior. On the other hand, if the value of the ratio (W _B / W _A ) becomes too large (particularly exceeding 1.0), the resin shrinks at the time of photocuring, and deformation due to warpage becomes severe, and the desired dimensional accuracy, A 3D object with a shape cannot be obtained.
Therefore, in the resin composition for optical three-dimensional modeling of the present invention, the ratio (W _B / W _A ) is preferably 0.45 to 1.0, and preferably 0.5 to 0.9. More preferably, it is still more preferably 0.55 to 0.8.

The resin composition for optical three-dimensional model | molding of this invention is epoxy group based on "the total mass of the cation polymerizable organic compound (A) contained in the resin composition for optical three-dimensional model | molding" with said requirements ((alpha)). The requirement that the aromatic polyepoxy compound (A-1) having 3 or more [hereinafter, sometimes simply referred to as “aromatic polyepoxy compound (A-1)]” is contained in a proportion of 30 to 80 mass% ( By satisfying β), the three-dimensional object obtained by stereolithography has a high thermal deformation temperature and excellent heat resistance, and the three-dimensional object obtained by stereolithography is heat-treated at a temperature of 50 ° C. or higher. As a result, the heat distortion temperature is further increased, and a three-dimensional shaped object with further improved heat resistance can be obtained, and the shrinkage during photocuring is reduced and the dimensional accuracy is further improved.
If the content ratio of the aromatic polyepoxy compound (A-1) is too small, the thermal deformation temperature of the three-dimensional structure obtained by optical modeling becomes low, and the three-dimensional structure is heat-treated at a temperature of 50 ° C. or higher after the optical modeling. Even so, it becomes difficult to increase the heat distortion temperature. On the other hand, if the content ratio of the aromatic polyepoxy compound (A-1) is too large, it takes time until the viscosity of the resin composition for optical three-dimensional modeling becomes high and the liquid level becomes stable, and the optical modeling time becomes long. The foam is likely to be generated, and the foam is likely to be mixed into the three-dimensional structure, and the toughness of the three-dimensional structure obtained by optical modeling is low and brittle, and the transparency is likely to be low.
In the resin composition for optical three-dimensional model | molding of this invention, it is preferable that the ratio of the aromatic polyepoxy compound (A-1) based on the total mass of a cationically polymerizable organic compound (A) is 30-60 mass%, It is more preferable that it is 35-50 mass%.

In the above requirement (β) in the present invention, the aromatic polyepoxy compound (A-1) having 3 or more epoxy groups may be any compound having 3 or more epoxy groups and having an aromatic ring. Can also be used.
As a typical example of the aromatic polyepoxy compound (A-1), a compound having three or more glycidyl etherified phenol groups represented by the following formula (a) in one molecule [hereinafter referred to as “compound (A-1a) ) ”.

As the compound (A-1a), any compound can be used as long as the viscosity of the resin composition for optical three-dimensional modeling can be maintained at a viscosity suitable for optical modeling even when the compound (A-1a) is contained. .
Specific examples of the compound (A-1a) that can be used in the present invention include polyglycidyl ethers of phenolic resins such as novolak resins and resol resins, tetraglycidyl ethers of tetraphenolethane, triglycidyl ethers of triphenolmethane, VG3101L represented by the chemical formula, that is, 2- [4- (2,3-epoxypropoxy) phenyl] -2- [4- [1,1-bis [4-([2,3-epoxypropoxy] phenyl]] And ethyl] phenyl] propane.

The resin composition for optical three-dimensional model | molding of this invention can contain the 1 type (s) or 2 or more types of an above described aromatic polyepoxy compound (A-1).
Among them, in the present invention, as the aromatic polyepoxy compound (A-1), VG3101L is preferable from the viewpoint that it is easy to obtain, is less colored, and has a three-dimensional structure that is excellent in heat resistance and mechanical properties. Used.

The resin composition for optical three-dimensional model | molding of this invention contains another cationically polymerizable organic compound with an aromatic polyepoxy compound (A-1) as a cationically polymerizable organic compound (A).
As another cationically polymerizable organic compound that can be used in the present invention, one or more of the cationically polymerizable organic compounds used in the resin composition for optical three-dimensional modeling can be used.

As a cationically polymerizable organic compound other than the aromatic polyepoxy compound (A-1) that can be used in the resin composition for optical three-dimensional modeling of the present invention, an epoxy compound other than the aromatic polyepoxy compound (A-1), Examples include oxetane compounds and other cyclic ether compounds, cyclic acetal compounds, cyclic lactone compounds, spiro orthoester compounds, vinyl ether compounds, etc. These cationically polymerizable organic compounds may be used alone or in combination of two or more. May be used in combination.
Among them, in the present invention, as the other cationic polymerizable organic compound used together with the aromatic polyepoxy compound (A-1), other epoxy compounds and oxetane compounds other than the aromatic polyepoxy compound (A-1) are preferably used. It is done.

  Examples of other epoxy compounds that can be used as the cationically polymerizable organic compound (A) in the present invention include epoxy compounds such as alicyclic epoxy compounds, aliphatic epoxy compounds, and aromatic epoxy compounds.

  Examples of the alicyclic epoxy compound include a cyclohexene oxide structure-containing compound or a cyclopentene oxide structure-containing compound obtained by epoxidizing a cyclohexene ring-containing compound or a cyclopentene ring-containing compound with an appropriate oxidizing agent such as hydrogen peroxide or peracid; And polyglycidyl ethers of polyhydric alcohols having at least one alicyclic ring.

More specifically, examples of the cyclohexene oxide structure-containing compound or the cyclopentene oxide structure-containing compound include 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate and 3,4-epoxy-1-methyl. Cyclohexyl-3,4-epoxy-1-methylcyclohexanecarboxylate, 6-methyl-3,4-epoxycyclohexylmethyl-6-methyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-3-methylcyclohexyl Methyl-3,4-epoxy-3-methylcyclohexanecarboxylate, 3,4-epoxy-5-methylcyclohexylmethyl-3,4-epoxy-5-methylcyclohexanecarboxylate, 2- (3,4-epoxycyclohexane Xyl-5,5-spiro-3,4-epoxy) cyclohexane-metadioxane, bis (3,4-epoxycyclohexylmethyl) adipate, 3,4-epoxy-6-methylcyclohexylcarboxylate, dicyclopentadiene diepoxide, Examples thereof include ethylenebis (3,4-epoxycyclohexanecarboxylate), epoxyhexahydrophthalate dioctyl, epoxyhexahydrophthalate di-2-ethylhexyl, and the like.
Further, ε-caprolactone-modified 3 ′, 4′-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate, 1,2-bis (hydroxymethyl) -1-butanol 1,2 sold by Daicel Chemical Industries Mention may also be made of epoxy-4- (2-oxiranyl) cyclohexane adducts.
Further, bis (3,4-epoxycyclohexyl) methane, 2,2-bis (3,4-epoxycyclohexyl) propane, 1,1-bis (3,4-epoxycyclohexyl) ethane, alpha pinene oxide, camphorene aldehyde , Limonene monooxide, limonene dioxide, 4-vinylcyclohexene monooxide, 4-vinylcyclohexene dioxide, and the like.

Specific examples of polyglycidyl ether of polyhydric alcohol having at least one alicyclic ring include, for example, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol E diglycidyl ether, hydrogenated bisphenol F diglycidyl ether. And alicyclic diglycidyl ether compounds such as hydrogenated bisphenol AD diglycidyl ether, hydrogenated bisphenol Z diglycidyl ether, cyclohexane dimethanol diglycidyl ether, and tricyclodecane dimethanol diglycidyl ether.
However, when diglycidyl ethers of hydrogenated bisphenols are included as a part of the cationically polymerizable organic compound (A), there are problems such as a decrease in rigidity and heat resistance of a three-dimensional structure obtained by optical modeling. Therefore, the content of the diglycidyl ether of the hydrogenated bisphenols is preferably 10% by mass or less, preferably 5% by mass or less, based on the total mass of the cationically polymerizable organic compound (A). More preferably, it is more preferably 3% by mass or less, and even more preferably 0% by mass (not including diglycidyl ether of hydrogenated bisphenols).

The aliphatic epoxy compound that can be used as a part of the cationically polymerizable organic compound (A) is not particularly limited. Examples of the aliphatic epoxy compound include aliphatic polyhydric alcohols or polyalkylene oxide adducts thereof. Glycidyl ether, polyglycidyl ester of aliphatic long-chain polybasic acid, homopolymer synthesized by vinyl polymerization of glycidyl acrylate or glycidyl methacrylate, copolymer synthesized by vinyl polymerization of glycidyl acrylate and / or glycidyl methacrylate and other vinyl monomers, etc. Can be mentioned.
Representative compounds include, for example, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, glycidyl ether of higher alcohol, diglycidyl ether of 1,4-butanediol, diglycidyl ether of 1,6-hexanediol, neopentyl glycol Diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane diglycidyl ether, trimethylolpropane triglycidyl ether, sorbitol tetraglycidyl ether, dipentaerythritol hexaglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol Diglycidyl ethers of polyhydric alcohols such as diglycidyl ether of polytetramethylene glycol Mention may be made of the ether.
Furthermore, a polyglycidyl ether of a polyether polyol obtained by adding one or more alkylene oxides to an aliphatic polyhydric alcohol such as propylene, trimethylolpropane and glycerin, and a diglycidyl aliphatic long-chain dibasic acid. Examples include esters.
Furthermore, monoglycidyl ether of higher aliphatic alcohol, phenol, cresol, butylphenol or monoglycidyl ether of polyether alcohol obtained by adding alkylene oxide to these, glycidyl ester of higher fatty acid, epoxidized soybean oil, epoxy stearic acid Examples thereof include butyl, epoxidized polybutadiene, and glycidylated polybutadiene.
In addition, as the epoxy alkane, 1,2-epoxydecane, 1,2-epoxydodecane, 1,2-epoxytetradecane, 1,2-epoxycetane, 1,2-epoxyoctadecane, 1,2-epoxyicosane Can be mentioned.

In addition, the aromatic epoxy compound is not particularly limited, and examples thereof include polyglycidyl ethers and polyglycidyl esters of polyhydric phenols or alkylene oxide adducts thereof. Specifically, for example, bisphenol A, Bisphenol E, bisphenol F, bisphenol AD, bisphenol Z, or glycidyl ether, phenyl glycidyl ether, tert-butylphenyl glycidyl ether, resorcinol diglycidyl ether, or phenols obtained by adding an alkylene oxide such as ethylene oxide or propylene oxide to these. Glycidylated product of the condensation product of propane and isopropenylacetophenone, glycidylated product of the reaction product of phenols and dicyclopentadiene, terephthalic acid jig Examples include lysidyl ester, diglycidyl ester of isophthalic acid, and diglycidyl ester of o-phthalic acid.
Furthermore, the diglycidyl ether of biphenol, the diglycidyl ether of tetramethylbiphenol, etc. can be mentioned.

The resin composition for optical three-dimensional model | molding of this invention is for optical three-dimensional model | molding by containing another epoxy compound with an aromatic polyepoxy compound (A-1) as a cationically polymerizable organic compound (A). The effect of lowering the viscosity of the resin composition, improving the photocurability, and improving the toughness of the three-dimensional structure obtained by optical modeling can be obtained.
The other epoxy compound may contain one or more of the above-described epoxy compounds, particularly a diepoxy compound having two or more epoxy groups [hereinafter referred to as “diepoxy compound (A-3)”. Or a compound having three or more diepoxy compounds (A-3) and epoxy groups is preferably used.
The content of the other epoxy compound is preferably 15 to 40% by mass and more preferably 20 to 37% by mass based on the total mass of the cationic polymerizable organic compound (A) contained in the resin composition for optical three-dimensional modeling. Preferably, it is 25 to 35% by mass.
In particular, the resin composition for optical three-dimensional modeling of the present invention is a cationic polymerization in which the diepoxy compound (A-3) is contained in the resin composition for optical three-dimensional modeling as a part of the cationic polymerizable organic compound (A). Based on the total mass of the organic compound (A), it is 15 to 40% by mass, more preferably 20 to 37% by mass, and particularly 25 to 35% by mass. It is preferable in that a cured product having high rigidity and heat resistance can be obtained, and a molded product having high transparency can be obtained.

Moreover, as an oxetane compound [hereinafter referred to as “oxetane compound (A-2)]” that can be used in the resin composition for optical three-dimensional modeling of the present invention, a monooxetane compound having one oxetane group in one molecule and 1 One or more of the polyoxetane compounds having two or more oxentane groups in the molecule can be used.
In particular, the resin composition for optical three-dimensional modeling of the present invention preferably contains an oxetane compound (A-2) as a part of the cationically polymerizable organic compound (A). In that case, the oxetane compound (A- 2), a monooxetane compound (A-2a) having one oxetane group in one molecule and a polyoxetane compound (A-2b) having two or more oxentane groups in one molecule are converted into a monooxetane compound (A- 2a): a polyoxetane compound (A-2b) = 95: 5 to 5:95, a mass ratio of 10:90 to 90:10, particularly a mass ratio of 20:80 to 80:20. The solid and optical three-dimensional modeling resin composition in a high humidity state has a reduced moisture and moisture absorption rate, can maintain the initial high curing sensitivity over a long period of time, and can be obtained by stereolithography. Toughness form thereof is improved.

At that time, any monooxetane compound (A-2a) can be used as long as it is a compound having one oxetane group in one molecule, and in particular, it has one oxetane group in one molecule and is alcoholic. A monooxetane monoalcohol compound having one hydroxyl group is preferably used.
Among such monooxetane monoalcohol compounds, the monooxetane monoalcohol compound (A-2a ₁ ) represented by the following general formula (A-2a ₁ ) and the following general formula (A-2a ₂ ) At least one of the represented monooxetane monoalcohol compounds (A-2a ₂ ) is more preferably used as a monooxetane compound from the viewpoints of availability, high reactivity, and low viscosity.

（式中、Ｒ¹およびＲ²は炭素数１〜５のアルキル基、Ｒ³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 ¹ and R ² represent an alkyl group having 1 to 5 carbon atoms, and R ³ represents an alkylene group having 2 to 10 carbon atoms which may have an ether bond.)

In the above general formula (A-2a ₁ ), examples of R ¹ include methyl, ethyl, propyl, butyl, and pentyl.
Specific examples of monooxetane alcohol (A-2a ₁ ) include 3-hydroxymethyl-3-methyloxetane, 3-hydroxymethyl-3-ethyloxetane, 3-hydroxymethyl-3-propyloxetane, 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 (A-2a ₂ ), examples of R ² include methyl, ethyl, propyl, butyl, and pentyl.
In the above general formula (A-2a ₂ ), R ³ 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. A C2-C10 chain or branched alkylene group having an ether bond (ether oxygen atom) in the middle of the (alkylene chain) may be used. Specific examples of R ³ include ethylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, heptamethylene group, 3-oxypentylene group and the like. Among these, R ³ 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 (A-2b), 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. A dioxetane compound having one is preferably used, and among them, the following general formula (A-2b ₀ );

（式中、２個のＲ⁴は互いに同じかまたは異なる炭素数１〜５のアルキル基、Ｒ⁵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、ｓは０または１を示す。）
で表されるジオキセタン化合物（Ａ−２ｂ₀）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（Ａ−２ｂ₀）において、Ｒ⁴の例としては、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、Ｒ⁵の例としては、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ＡＤ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、テレフタル酸残基、イソフタル酸残基、ｏ−フタル酸残基などを挙げることができる。

(In the formula, two R ^{4 s} are the same or different from each other and are each an alkyl group having 1 to 5 carbon atoms, R ⁵ is a divalent organic group having or not having an aromatic ring, and s is 0 or 1) Is shown.)
The dioxetane compound (A-2b ₀ ) represented by the formula is preferably used from the viewpoints of availability, reactivity, low hygroscopicity, mechanical properties of the cured product, and the like.
In the above general formula (A-2b ₀ ), examples of R ⁴ include methyl, ethyl, propyl, butyl, and pentyl. Examples of R ⁵ 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 —, hydrogenated bisphenol A residue, hydrogenated bisphenol F residue, hydrogenated Examples thereof include bisphenol AD residue, hydrogenated bisphenol Z residue, cyclohexanedimethanol residue, tricyclodecane dimethanol residue, terephthalic acid residue, isophthalic acid residue, o-phthalic acid residue and the like.

Specific examples of the dioxetane compound (A-2b ₀ ) include a dioxetane compound represented by the following formula (A-2b ₁ ) or formula (A-2b 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 (A-2b 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.
Specific examples of the dioxetane compounds represented by the above formula (A-2b _2), the two R ⁶ are both methyl in the above formula (A-2b _2), ethyl, propyl, butyl or pentyl group 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 A divalent group represented by —CH ₂ —, hydrogenated bisphenol A residue, hydrogenated bisphenol F residue, hydrogenated bisphenol AD residue, hydrogenated bisphenol Z residue, cyclohexanedimethanol residue, tricyclode The dioxetane compound which is a candimethanol residue, a terephthalic acid residue, an isophthalic acid residue, and an o-phthalic acid residue can be mentioned.
Among them, as the polyoxetane compound (A-2b ₀ ), in the above formula (A-2b ₁ ), bis (3-methyl-3-oxetanylmethyl) in which two R ^{6 s} are both methyl groups or ethyl groups. ) 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.

  The resin composition for optical three-dimensional modeling of the present invention is a photo-curing performance of the resin composition for optical three-dimensional modeling, an improvement in optical three-dimensional modeling by lowering the viscosity, a toughness of a three-dimensional model obtained by optical modeling, From the viewpoint of improving heat resistance, the oxetane compound (A-2) is added at a ratio of 10 to 40% by mass based on the total mass of the cationically polymerizable organic compound (A) contained in the resin composition for optical three-dimensional modeling. It is preferable to contain, it is more preferable to contain in the ratio of 15-35 mass%, and it is still more preferable to contain in the ratio of 20-30 mass%.

  Representative examples of the radical polymerizable organic compound (B) include compounds having a (meth) acrylate group, unsaturated polyester compounds, allyl urethane compounds, polythiol compounds, and the like. 1 type (s) or 2 or more types can be used. Among them, a compound having at least one (meth) acryloyloxy group in one molecule is preferably used. Specific examples include a reaction product of an epoxy compound and (meth) acrylic acid, and a (meth) alcohol (meth) An acrylic ester, urethane (meth) acrylate, polyester (meth) acrylate, polyether (meth) acrylate, etc. can be mentioned.

  As a reaction product of the above-mentioned epoxy compound and (meth) acrylic acid, it can be obtained by reaction of an aromatic epoxy compound, an alicyclic epoxy compound and / or an aliphatic epoxy compound with (meth) acrylic acid (meta) ) Acrylate-based reaction products, and specific examples thereof include bisphenol compounds such as bisphenol A and bisphenol S, bisphenol compounds such as bisphenol A and bisphenol S in which the benzene ring is substituted with an alkoxy group, etc. A (meth) acrylate obtained by reacting a glycidyl ether obtained by reaction of an alkylene oxide adduct of a bisphenol compound or a substituted bisphenol compound with an epoxidizing agent such as epichlorohydrin with (meth) acrylic acid, Kishinoborakku resin and (meth) reacting the acrylic acid and the like are (meth) acrylate reaction product obtained.

Examples of the (meth) acrylic acid esters of the alcohols described above include aromatic alcohols, aliphatic alcohols, alicyclic alcohols and / or their alkylene oxide adducts having at least one hydroxyl group in the molecule; Mention may be made of (meth) acrylates obtained by reaction with (meth) acrylic acid.
More specifically, for example, bisphenol compounds such as bisphenol A and bisphenol S, or di (meth) acrylates of bisphenol compounds such as bisphenol A and bisphenol S in which the benzene ring is substituted with an alkoxy group, 2-ethylhexyl (meta ) 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, neopentylglycol Di (meth) acrylate, polyalkylene glycol mono (meth) acrylate, polyalkylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, Poly (meth) acrylates of polyhydric alcohols having three or more hydroxyl groups such as dipentaerythritol hexa (meth) acrylate, and alkylene oxide adducts of polyhydric alcohols such as diols, triols, tetraols, hexaols ( And (meth) acrylate.

  Examples of the urethane (meth) acrylate described above include (meth) acrylate obtained by reacting a hydroxyl group-containing (meth) acrylic acid ester with an isocyanate compound. As the hydroxyl group-containing (meth) acrylic acid ester, a hydroxyl group-containing (meth) acrylic acid ester obtained by an esterification reaction of an aliphatic dihydric alcohol and (meth) acrylic acid is preferable. As a specific example, 2-hydroxy Examples thereof include ethyl (meth) acrylate. The isocyanate compound is preferably a polyisocyanate compound having two or more isocyanate groups in one molecule, such as tolylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate and the like.

Furthermore, examples of the polyester (meth) acrylate described above 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.

  The resin composition for optical three-dimensional modeling of the present invention includes a polyalkylene glycol di (meth) acrylate (B-1) and a polyalkylene glycol mono (meth) acrylate (B) as part of the radical polymerizable organic compound (B). It is preferable to contain at least one of -2.

Polyalkylene glycol di (meth) acrylate (B-1) at that time includes polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, polypropylene glycol diacrylate, polypropylene glycol dimethacrylate, and poly (oxyethylene / oxypropylene random copolymer). ) Diacrylate of diol, poly (oxyethylene / oxypropylene random copolymer) dimethacrylate of diol, block copolymer having hydroxyl groups at both ends where polyoxyethylene polymer block / polyoxypropylene polymer block are bonded ( Diacrylate or dimethacrylate of block copolymer diol), polytetramethylene glycol diacrylate, polytetramethylene glycol dimethacrylate Random copolymer diol diacrylate or dimethacrylate with polyoxyethylene polymer block / polytetramethylene glycol polymer block Examples thereof include a diacrylate or dimethacrylate of a block copolymer having a hydroxyl group at both ends (block copolymer diol).
Among them, as polyalkylene glycol di (meth) acrylate (B-1), it is easy to obtain, is liquid at room temperature and has excellent handleability, and a molded product obtained from an optical three-dimensional model has excellent transparency and One of polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, polypropylene glycol diacrylate, polypropylene glycol dimethacrylate, polytetramethylene glycol diacrylate, polytetramethylene glycol dimethacrylate from the point of being flexible and excellent in toughness and durability Two or more types are preferably used, and polyethylene glycol diacrylate, polypropylene glycol diacrylate and polytetramethylene glycol diacrylate are more preferably used. In particular, when polytetramethylene glycol diacrylate is used as the polyalkylene glycol di (meth) acrylate (B-1), in addition to the above-described properties, the impact resistance of the three-dimensional structure obtained by optical modeling is more excellent. In addition, the absorption of moisture and moisture is smaller and the dimensional stability is more excellent.

From the viewpoints of various properties such as solubility in optical three-dimensional modeling resin composition, miscibility, impact strength, toughness, and durability of the three-dimensional modeled product obtained by photocuring. The average molecular weight of the alkylene glycol di (meth) acrylate (B-1) is preferably 300 to 2000, more preferably 500 to 1500, and still more preferably 600 to 1200.
If the molecular weight of the polyalkylene glycol di (meth) acrylate (B-1) is too small, the impact strength of the three-dimensional structure obtained by stereolithography is reduced, resulting in low toughness and flexibility, while the polyalkylene glycol di ( When the molecular weight of the (meth) acrylate (B-1) is too large, the solubility in the resin composition for optical three-dimensional modeling is reduced, or the optical system in which polyalkylene glycol di (meth) acrylate (B-1) is added. The viscosity of the three-dimensional modeled resin composition is increased, the light transmittance of the three-dimensional modeled product obtained by optical modeling is lowered, and in some cases, it tends to be opaque.

  Polyalkylene glycol mono (meth) acrylate (B-2) includes polyethylene glycol monoacrylate, polyethylene glycol monomethacrylate, polypropylene glycol monoacrylate, polypropylene glycol monomethacrylate, and poly (oxyethylene / oxypropylene random copolymer). Diol monoacrylate, poly (oxyethylene / oxypropylene random copolymer) diol monomethacrylate, polyoxyethylene polymer block / polyoxypropylene polymer block bonded block copolymer having a hydroxyl group at both ends Copolymer monool) monoacrylate or monomethacrylate, polytetramethylene glycol monoacrylate, polytetramethylene A monoacrylate or monomethacrylate of a random copolymer diol, a polyoxyethylene polymer block / polytetramethylene glycol polymer block, which is a random copolymer diol having ethylene oxide units and tetramethylene oxide units randomly bonded and having hydroxyl groups at both ends. Examples thereof include a monoacrylate or monomethacrylate of a block copolymer (block copolymer monool) having hydroxyl groups at both ends bonded thereto.

  Among them, as the polyalkylene glycol mono (meth) acrylate (B-2), it is easy to obtain, is liquid at room temperature and has excellent handleability, and a molded product obtained from an optical three-dimensional model has excellent transparency and One of polyethylene glycol monoacrylate, polyethylene glycol monomethacrylate, polypropylene glycol monoacrylate, polypropylene glycol monomethacrylate, polytetramethylene glycol monoacrylate, polytetramethylene glycol monomethacrylate from the point of being flexible and excellent in toughness and durability Two or more are preferably used, and polyethylene glycol monoacrylate, polypropylene glycol monoacrylate and polytetramethylene glycol monoacrylate are more preferred. Used. In particular, when polypropylene glycol monoacrylate is used as the polyalkylene glycol mono (meth) acrylate (B-2), in addition to the above-described properties, the photocurable resin composition has excellent photocurability, and light The impact resistance of the three-dimensional model obtained by modeling becomes more excellent.

From the viewpoints of various properties such as solubility in optical three-dimensional modeling resin composition, miscibility, impact strength, toughness, and durability of the three-dimensional modeled product obtained by photocuring. The average molecular weight of the alkylene glycol mono (meth) acrylate (B-2) is preferably 150 to 1200, more preferably 150 to 1000, and even more preferably 200 to 700.
If the molecular weight of the polyalkylene glycol mono (meth) acrylate (B-2) is too small, the impact strength of the three-dimensional modeled object obtained by stereolithography is reduced and the toughness and flexibility are lowered, while the polyalkylene glycol mono ( If the molecular weight of the (meth) acrylate (B-2) is too large, the solubility in the resin composition for optical three-dimensional modeling is reduced, or the optical system in which the polyalkylene glycol mono (meth) acrylate (B-2) is added. The viscosity of the three-dimensional modeled resin composition is increased, the photocurability is lowered, and the hardness of the three-dimensional modeled product obtained by optical modeling is likely to be soft.

  In the resin composition for optical three-dimensional modeling of the present invention, at least one of polyalkylene glycol di (meth) acrylate (B-1) and polyalkylene glycol mono (meth) acrylate (B-2) is optically three-dimensional modeled. Based on the total mass of the radically polymerizable organic compound (B) contained in the resin composition for use, 5 to 60% by mass, further 10 to 55% by mass, particularly 20 to 50% by mass, This is preferable in terms of impact resistance, dimensional stability, and the like of a three-dimensional modeled object obtained by optical modeling.

In the present invention, as the cationic polymerization initiator (C), any polymerization initiator capable of initiating cationic polymerization of the cationic polymerizable organic compound (A) when irradiated with active energy rays such as light can be used. Among them, as the cationic polymerization initiator (C), an onium salt that releases a Lewis acid when irradiated with active energy rays is preferably used. Examples of such an onium salt include an aromatic sulfonium salt of a Group VIIa element, an aromatic onium salt of a Group VIa element, an aromatic onium salt of a Group Va element, and the like.
As a typical example, the general formula: [(R ⁸ ) (R ⁹ ) (R ¹⁰ ) S ⁺ ] [wherein R ⁸ , R ⁹ and R ¹⁰ are each independently monovalent bonded to sulfur (S). Or an organic group of the general formula: [(R ¹¹ ) (R ¹² ) I ⁺ ] [wherein R ¹¹ and R ¹² are each independently a monovalent group bonded to iodine (I). An iodonium ion represented by an organic group] is represented by a general formula: [(Rf) _m PF _6-m ⁻ ] (wherein Rf is a fluoroalkyl group, m is an integer of 0 to 6) ( Phosphate ion), an anion (antimonate ion) represented by the general formula: [(Rf) _n SbF _6-n ⁻ ] (wherein Rf is a fluoroalkyl group, n is an integer of 0 to 6), [BF ₄ ^-] represented by anions, wherein: [AsF ₆ ^-] a cationic polymerization initiator bound such anions as represented by And the like.

  Although it is not limited at all, more specifically, as the cationic polymerization initiator (C), for example, a phosphorus-based sulfonium compound (C-1) represented by the following general formula (C-1), An antimony sulfonium compound (C-2) represented by the following general formula (C-2) can be exemplified.

［上記の一般式（Ｃ−１）および（Ｃ−２）中、Ｒ⁸、Ｒ⁹およびＲ¹⁰は１価の有機基、Ｒｆはフルオロアルキル基、ｍおよびｎは０〜６の整数、ｐは上記の一般式（Ｃ−１）における「カチオン［Ｓ⁺（Ｒ⁸）（Ｒ⁹）（Ｒ¹⁰）］が有する陽イオン価と同じ数、ｑは上記の一般式（Ｃ−２）における「カチオン［Ｓ⁺（Ｒ⁸）（Ｒ⁹）（Ｒ⁰）］が有する陽イオン価と同じ数である。］

[In the above general formulas (C-1) and (C-2), R ⁸ , R ⁹ and R ¹⁰ are monovalent organic groups, Rf is a fluoroalkyl group, m and n are integers of 0 to 6, p Is the same number as the cation number of the “cation [S ⁺ (R ⁸ ) (R ⁹ ) (R ¹⁰ )]” in the above general formula (C-1), q is the same as in the above general formula (C-2) “It is the same number as the cation number of the cation [S ⁺ (R ⁸ ) (R ⁹ ) (R ⁰ )].]

In the phosphorus-based sulfonium compound (C-1) and antimony-based sulfonium compound (C-2) represented by the above general formula, typical examples of R ⁹ , R ¹⁰ and R ¹¹ are the following formulas << 1 >> to The group shown by << 11 >> can be mentioned.

［式中、Ｒ¹¹、Ｒ¹²、Ｒ¹³、Ｒ¹⁴、Ｒ¹⁵、Ｒ¹⁶、Ｒ¹⁷、Ｒ¹⁸、Ｒ¹⁹、Ｒ²⁰、Ｒ²¹およびＲ²²は、それぞれ独立して、置換基を有していてもよいアルキル基またはアリール基であり、Ｘ¹、Ｘ²、Ｘ³、Ｘ⁴、Ｘ⁵、Ｘ⁶、Ｘ⁷、Ｘ⁸、Ｘ⁹、Ｘ¹⁰、Ｘ¹¹、Ｘ¹²、Ｘ¹³、Ｘ¹⁴、Ｘ¹⁵、Ｘ¹⁶、Ｘ¹⁷、Ｘ¹⁸、Ｘ¹⁹、Ｘ²⁰、Ｘ²¹およびＸ²²は、それぞれ独立して、アルキル基、アリール基、アルコキシ基、アリールオキシ基、ヒドロキシ（ポリ）アルキレンオキシ基、水酸基、シアノ基、ニトロ基およびハロゲン原子から選ばれる基であり、Ｚ¹、Ｚ²、Ｚ³およびＺ⁴は、それぞれ独立して、式：−Ｓ−、−ＳＯ−および−Ｏ−から選ばれる２価の基であり、それぞれ独立して、ｄ¹は０〜５の整数、ｄ²、ｄ³およびｄ⁴は０〜４の整数、ｄ⁵は０〜５の整数、ｄ⁶、ｄ⁷、ｄ⁸、ｄ⁹、ｄ¹⁰、ｄ¹¹、ｄ¹²、ｄ¹³、ｄ¹⁴、ｄ¹⁵およびｄ¹⁶は０〜４の整数、ｄ¹⁷は０〜５の整数、ｄ¹⁸は０〜４の整数、ｄ¹⁹は０〜５の整数、ｄ²⁰、ｄ²¹およびｄ²²は０〜４の整数である。］

[Wherein R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ and R ²² each independently have a substituent. An alkyl group or an aryl group which may be X ¹ , X ² , X ³ , X ⁴ , X ⁵ , X ⁶ , X ⁷ , X ⁸ , X ⁹ , X ¹⁰ , X ¹¹ , X ¹² , X ¹³ , X ¹⁴ , X ¹⁵ , X ¹⁶ , X ¹⁷ , X ¹⁸ , X ¹⁹ , X ²⁰ , X ²¹ and X ²² are each independently an alkyl group, aryl group, alkoxy group, aryloxy group, hydroxy ( A poly) alkyleneoxy group, a hydroxyl group, a cyano group, a nitro group and a halogen atom, and Z ¹ , Z ² , Z ³ and Z ⁴ are each independently a group represented by the formula: —S—, —SO—. and a divalent group selected from -O-, each independently, d ¹ is an integer of 0~5, d ^2, d ³ and d ⁴ are integers of 0 to 4 Number, d ⁵ is an integer of ^{0~5, d 6, d 7,} d 8, d 9, d 10, d 11, d 12, d 13, d 14, d 15 and d ¹⁶ are an integer of 0 to 4, d ¹⁷ is an integer of 0 to 5, d ¹⁸ is an integer of 0 to 4, d ¹⁹ is an integer of 0 to 5, d ^20, d ²¹ and d ²² represents an integer of 0-4. ]

  Although not limited at all, specific examples of the phosphorus-based sulfonium compound (C-1) represented by the above general formula include triphenylsulfonium tris (perfluoroethyl) trifluorophosphate, the following formula (C -1α) (“CPI-500K” manufactured by San Apro Co., Ltd.), a compound represented by the following formula (C-1β) (“CPI-500P” manufactured by San Apro Co., Ltd.), and the following formula (C −1γ) (“CPI-200K” manufactured by San Apro Co., Ltd.), 4- (2-chloro-4-benzoylphenylthio) phenylbis (4-fluorophenyl) sulfonium hexafluorophosphate) (ADEKA Corporation) Manufactured "SP-152").

  Specific examples of the antimony sulfonium compound (C-2) represented by the above general formula include bis- [4- (monophenylsulfonio) phenyl] sulfide bismonohexafluoroantimonate, bis- [ 4- (mono-4′-hydroxyethoxyphenylsulfonio) phenyl] sulfide bismonohexafluoroantimonate, 4- (phenylthio) phenylmonophenylsulfonium hexafluoroantimonate represented by the following formula (C-2α) (“CPI-101A” or “CPI-110S” manufactured by San Apro Co., Ltd.), 4- (2-chloro-4-benzoylphenylthio) phenylbis (4-fluorophenyl) sulfonium hexafluoroantimonate) (ADEKA Corporation) "SP-172" manufactured) It is possible.

In the present invention, one or more of the above cationic polymerization initiators can be used. Among them, aromatic sulfonium salts are more preferably used in the present invention.
In the present invention, for the purpose of improving the reaction rate, a photosensitizer such as benzophenone, alkoxyanthracene, monoalkoxyanthracene, thioxanthone and the like may be used together with the cationic polymerization initiator (C) as necessary.

  As the radical polymerization initiator (D), any polymerization initiator capable of initiating radical polymerization of the radical polymerizable organic compound (B) when irradiated with an active energy ray such as light can be used. Examples thereof include monoalkyl acetal compounds, phenyl ketone compounds, acetophenone compounds, benzoin or alkyl ether compounds thereof, benzophenone compounds, and thioxanthone compounds.

Specifically, examples of benmonol or a monoalkyl acetal compound thereof include benmonol monomethyl ketal and benmonol-β-methoxyethyl acetal.
Examples of the phenyl ketone compound include 1-hydroxy-cyclohexyl phenyl ketone.
Examples of the acetophenone compound include monoethoxyacetophenone, 2-hydroxymethyl-1-phenylpropan-1-one, 4′-isopropyl-2-hydroxy-2-methyl-propiophenone, and 2-hydroxy-2. -Methyl-propiophenone, p-monomethylaminoacetophenone, p-tert-butylmonochloroacetophenone, p-tert-butyltrichloroacetophenone, p-ammonodobenzalacetophenone and the like.

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

In this invention, 1 type, or 2 or more types of radical polymerization initiator (D) can be mix | blended and used according to desired performance.
Among them, in the present invention, 1-hydroxycyclohexyl phenyl ketone is preferably used as the radical polymerization initiator (D) from the viewpoint that the three-dimensional model obtained by photo-modeling has a small yellowness and a good hue. .

  The resin composition for optical three-dimensional modeling of the present invention includes the viscosity of the composition, the reaction rate, the modeling speed, the shrinkage rate at the time of curing, the mechanical properties of the three-dimensional modeled product, toughness, impact resistance, durability, and heat. From the viewpoints of deformation temperature (heat resistance), dimensional accuracy, transparency, color tone (reduction in yellowness), etc., 30 cationically polymerizable organic compounds (A) are added based on the total mass of the resin composition for optical three-dimensional modeling. It is contained in a proportion of ˜70 mass%, further 40 to 70 mass%, particularly 45 to 65 mass%, and the radical polymerizable organic compound (B) is 25 to 50 mass%, further 25 to 45 mass%, especially 30 To 43 mass%, and the cationic polymerization initiator (C) is contained in an amount of 0.1 to 10 mass%, further 0.5 to 8 mass%, particularly 1 to 5 mass%, and radical polymerization. The initiator (D) is 0.1 to 10% by mass, more preferably 0.5 to 8% by mass, especially 1 to 4%. It is preferably contained in a proportion of amount%.

  Moreover, the resin composition for optical three-dimensional model | molding of this invention may contain the polyalkylene glycol and the etherified product of the polyalkylene glycol which etherified the hydroxyl group of the one terminal or both ends as needed. By including the polyalkylene glycol and / or the etherified product of polyalkylene glycol obtained by etherifying the terminal hydroxyl group, the impact strength of the three-dimensional structure obtained by optical modeling is improved.

Examples of the etherified product of polyalkylene glycol and / or polyalkylene glycol obtained by etherifying a terminal hydroxyl group can be contained in the resin composition for optical three-dimensional modeling of the present invention include polyethylene glycol, polypropylene glycol, poly (oxyethylene / Oxypropylene random copolymer) diol, polyoxyethylene polymer block / polyoxypropylene polymer block-bonded block copolymer having hydroxyl groups at both ends (block copolymer diol), polytetramethylene glycol, ethylene oxide unit Random copolymer diol, polyoxyethylene polymer block / polytetramethylene glycol polymer block having hydroxyl groups at both ends and tetramethylene oxide units bonded at random. Examples include block copolymers having hydroxyl groups at both ends (block copolymer diols), etherified products in which the hydroxyl groups at one or both ends of these diols are etherified with alkyl groups, cycloalkyl groups, aryl groups, or the like. it can.
Among them, polyethylene glycol, since it is easy to obtain, is liquid at room temperature, has excellent handleability, and a molded product obtained from an optical three-dimensional model has excellent transparency, flexibility, toughness, and durability. One or more of polypropylene glycol and polytetramethylene glycol are preferably used, and polytetramethylene glycol is more preferably used.

  The average molecular weight of the polyalkylene glycol and the etherified product thereof is preferably 200 to 4000, more preferably 300 to 2000, and further preferably 400 to 1000. From the standpoints of various properties such as solubility, miscibility, and photocuring of the three-dimensional structure obtained by photocuring, such as impact strength, toughness, and durability, in the optical three-dimensional structure resin composition described above. The average molecular weight of the polyalkylene glycol and its terminal hydroxyl group etherified product is preferably 500 to 1000, more preferably 600 to 900.

  The content ratio of the polyalkylene glycol and / or the polyalkylene glycol etherified product obtained by etherifying the terminal hydroxyl group is preferably 0 to 10% by mass based on the total mass of the resin composition for optical three-dimensional modeling, and the content ratio If the amount is too large, a decrease in photocurability, a decrease in heat deformation temperature of a three-dimensional structure obtained by optical modeling, a decrease in heat resistance associated therewith, a decrease in transparency, and the like are caused.

  As long as the effect of the present invention is not impaired, the resin composition for optical three-dimensional modeling of the present invention includes, as necessary, a colorant such as a dye, an antifoaming agent, a leveling agent, a thickener, a flame retardant, and an antioxidant. Further, it may contain an appropriate amount of one type or two or more types such as a modifying resin.

Any of the conventionally known optical three-dimensional modeling methods and apparatuses can be used for optical three-dimensional modeling using the optical modeling resin composition of the present invention. As a representative example of the optical three-dimensional modeling method that can be preferably employed, a cured layer having a desired shape / pattern on the surface or bottom of the optical molding resin composition based on three-dimensional three-dimensional data stored in a computer The active energy ray is selectively irradiated to form a cured layer for one layer, and then an uncured resin composition for optical modeling is supplied to the cured layer, which is also stored in the computer. A stacking operation for newly forming a cured layer continuous with the cured layer by selectively irradiating active energy rays so as to obtain a cured layer having a desired shape / pattern based on the three-dimensional solid data. The method of manufacturing a three-dimensional molded item can be mentioned by repeating many times until the target three-dimensional molded item is obtained.
Examples of the active energy rays at that time include ultraviolet rays, electron beams, X-rays, radiation, and high frequencies as described above. 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.

  When forming a cured resin layer having a predetermined shape pattern by irradiating an active energy ray on 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 modeling of the present invention can be widely used in the field of optical three-dimensional modeling, and is not limited at all. However, as a typical application field, the appearance design is verified during the design. Shape confirmation model, functional test model for checking the functionality of parts, master model for producing mold, master model for producing mold, direct mold for prototype mold, automobile and motorcycle Lenses, restoration of art, imitation and contemporary art, art and craft fields such as design presentation models for glass-walled buildings, precision parts, electrical and electronic parts, furniture, building structures, automotive parts, various containers, It can be effectively used for applications such as models such as castings, mother dies, and processing.

The three-dimensional object obtained by optical modeling of the resin composition for optical three-dimensional modeling of the present invention has a high heat deformation temperature and heat resistance compared to the conventional optical three-dimensional model even without heat treatment after the optical modeling. Therefore, it can be used as it is without being subjected to heat treatment.
And since the three-dimensional molded article obtained by performing optical modeling using the resin composition for optical three-dimensional modeling of the present invention has a higher heat distortion temperature and is more excellent in heat resistance when subjected to heat treatment. In the case where a three-dimensional model that is more excellent in heat resistance is required, a three-dimensional model obtained using the optical three-dimensional model resin composition of the present invention is heat-treated to obtain a three-dimensional model that has improved heat resistance. Good.
The heat treatment for further increasing the thermal deformation temperature of the three-dimensional structure is preferably performed at a temperature of 50 ° C. or higher, more preferably at a temperature of 60 to 150 ° C., and preferably at a temperature of 80 to 120 ° C. Further preferred. When heat-treating at a temperature of 100 ° C. or higher, without first heating to 100 ° C. or higher, the temperature is first preheated to a temperature lower than 100 ° C. (for example, a temperature of about 40 to 60 ° C.) and then 100 ° C. or higher. When heated at, it is possible to effectively prevent dimensional changes and deformation of the three-dimensional structure.
The heat treatment can be performed by a method of heating a three-dimensional structure obtained by optical modeling in a heating chamber, a method of heating with a heat medium such as silicone oil, or the like.
The heat treatment after stereolithography is effective for manufacturing prototypes such as automobile engine parts that require high heat resistance.

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to the examples.
In the following examples, the viscosity of the resin composition for optical three-dimensional modeling, the shrinkage rate during optical modeling, and the mechanical properties of the three-dimensional model obtained by optical modeling using the resin composition for optical three-dimensional modeling (breaking Strength, yield strength, elongation, bending strength, flexural modulus, impact strength, Shore D hardness), heat distortion temperature, yellowness, and total light transmittance were measured as follows.

(1) Viscosity of the resin composition for optical three-dimensional modeling:
After adjusting the temperature of the resin composition for optical three-dimensional modeling to 25 ° C. in a thermostatic bath at 25 ° C., measurement was performed using a B-type viscometer (“LVDV2T” manufactured by Brookfield).

(2) Shrinkage during stereolithography:
For stereolithography resin composition prior to the stereolithography specific gravity (d ₀₎ and three-dimensional object obtained by stereolithography (three-dimensional object prior to heat treatment at 100 ° C.) of (liquid) density (d ₁ ), The shrinkage rate was determined by the following formula.

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

(2) Breaking strength, yield strength and elongation of the three-dimensional structure:
Three-dimensional modeled object manufactured in the following examples or comparative examples (test pieces having a dumbbell shape in accordance with JIS K-7113) (test pieces before heat treatment and heat treatment at 100 ° C. for 120 minutes after preheating at 50 ° C. for 1 hour) ), The breaking strength, yield strength and elongation of the three-dimensional structure (test piece) were measured according to JIS K-7113.

(3) Bending strength and bending elastic modulus of the three-dimensional structure:
Three-dimensional modeled object (bar-shaped test piece conforming to JIS K-7171) produced in the following examples or comparative examples (test piece before heat treatment and preheated at 50 ° C for 1 hour and then heat treated at 100 ° C for 120 minutes The bending strength and bending elastic modulus of the three-dimensional structure (test piece) were measured according to JIS K-7171.

(4) Impact strength of 3D objects:
Three-dimensional modeled object (test piece with notch according to JIS K-7110) produced in the following examples or comparative examples (test piece before heat treatment and preheated at 50 ° C for 1 hour and then heat treated at 100 ° C for 120 minutes The Izod impact strength was measured with a notch according to JIS K-7110 using a digital impact tester “model DG-18” manufactured by Toyo Seiki Co., Ltd.

(5) Shore D hardness of the three-dimensional structure:
Using the three-dimensional modeled object (dumbbell-shaped test piece conforming to JIS K-7113) produced in the following examples and comparative examples, an “Asker D-type hardness meter” manufactured by Kobunshi Keiki Co., Ltd. was used. In accordance with K-6253, the Shore D hardness of the test piece was measured over time [immediately after stereolithography, 1 hour, 2 hours and 1 day (24 hours later)] by the durometer method.

(6) Thermal deformation temperature of the three-dimensional structure:
Three-dimensional modeled object (bar-shaped test piece conforming to JIS K-7171) produced in the following examples or comparative examples (test piece before heat treatment and preheated at 50 ° C for 1 hour and then heat treated at 100 ° C for 120 minutes In accordance with JIS K-7207 (Method A) by applying a load of 1.81 MPa to the test piece using “HDT Tester 6M-2” manufactured by Toyo Seiki Co., Ltd. The heat deformation temperature of the test piece was measured, and a load of 0.45 MPa was further applied to the test piece, and the heat deformation temperature of the three-dimensional structure (test piece) was measured according to JIS K-7207 (Method B).

(7) Yellowness of the three-dimensional structure:
Three-dimensional model produced in the following examples or comparative examples [cubic test pieces having a width of 20 mm, a height of 45 mm, and a thickness of 10 mm (measurement surface)] (test pieces before heat treatment and after preheating at 50 ° C. for 1 hour) Using a UV-visible spectrophotometer “U-3900H” manufactured by Hitachi High-Technology Co., Ltd. and an integrating sphere using a test piece subjected to a heat treatment at 100 ° C. for 120 minutes, it was specified in JISK7373 by color analysis. The yellow index (YI) with respect to the standard illuminant D65 and the 2-degree field of view was determined and used as the yellowness of the three-dimensional structure (test piece).

(8) Total light transmittance of the three-dimensional structure:
Three-dimensional model produced in the following examples or comparative examples [cubic test pieces having a width of 20 mm, a height of 45 mm, and a thickness of 10 mm (measurement surface)] (test pieces before heat treatment and after preheating at 50 ° C. for 1 hour) Using a UV-visible spectrophotometer “UV-3900H” manufactured by Hitachi High-Technology Corporation and an integrating sphere, a standard illuminant D65 and a two-degree field of view were used. The total light transmittance prescribed | regulated to JISR-3106 was calculated | required.

Example 1
(1) As shown in Table 1 below, 13.0 parts by mass of 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate (“Celoxide 2021P” manufactured by Daicel Corporation), 2- [4 -(2,3-epoxypropoxy) phenyl] -2- [4- [1,1-bis [4-([2,3-epoxypropoxy] phenyl] ethyl] phenyl] propane (VG3101L described above) 24.0 Parts by mass, polytetramethylene glycol diglycidyl ether (“Epogosei PT” manufactured by Yokkaichi Synthesis Co., Ltd., number of bonds of tetramethylene oxide unit≈9, average molecular weight≈780) 1.9 parts by mass, 3-ethyl-3-hydroxy 4.5 parts by mass of methyl oxetane (“OXT-101” manufactured by Toagosei Co., Ltd.), bis (3-ethyl-3-oxeta) 7. 1 part by mass of rumethyl) ether (“OXT-221” manufactured by Toagosei Co., Ltd.), dipentaerythritol polyacrylate (“A-9550W” manufactured by Shin-Nakamura Chemical Co., Ltd., a mixture of pentaacrylate and hexaacrylate) 0 parts by mass, 10.0 parts by mass of polytetramethylene glycol diacrylate (“A-PTMG-65” manufactured by Shin-Nakamura Chemical Co., Ltd., average molecular weight≈650), polypropylene glycol monoacrylate (“Blemmer AP manufactured by Nippon Oil & Fats Co., Ltd.” -150 "6.0 parts by mass, 12.0 parts by mass of tricyclodecane dimethanol diacrylate (" A-DCP "manufactured by Shin-Nakamura Chemical Co., Ltd.), cationic polymerization initiator (" CPI-200K "manufactured by San Apro Co., Ltd.) ) 3.0 parts by weight, 1-hydroxy-cyclohexylphenylke (BASF "Irgacure 184") (radical polymerization initiator) 3.0 parts by mass, polytetramethylene ether glycol (Hodogaya Chemical Co., Ltd. "PTG-850SN" 2.0 parts by mass, 2-naphthalenethiol 0.020 parts by mass and 0.3 parts by mass of distilled water were mixed well to prepare a resin composition for optical three-dimensional modeling.
It was 370 MPa * s (25 degreeC) when the viscosity of this resin composition for optical three-dimensional modeling was measured by the above-mentioned method.

(2) Using the resin composition for optical three-dimensional modeling obtained in (1) above, a semiconductor laser (rated output 200 mW; wavelength) using an ultra-high-speed optical modeling system (“SOLIFORM250” manufactured by Nabtesco Corporation) 355 nm; manufactured by Spectra Physics Co., Ltd.), under the condition of a liquid surface irradiation energy of 100 mJ / cm ² , a slice pitch (lamination thickness) of 0.10 mm, and an average modeling time of 2 minutes per layer, Test piece for measuring physical properties (test piece for dumbbell shape according to JIS K-7113, test piece for bar shape according to JIS K-7171, test piece for Izod impact test according to JIS K-7110), yellow A 10 mm-thick test piece for measuring the degree of light and the total light transmittance was prepared. The obtained test piece was post-cured by irradiation with ultraviolet rays (metal halide lamp, wavelength 365 nm, intensity 3.0 mW / cm ² ) for 20 minutes.
Shrinkage ratio and mechanical properties (post-hardening strength, yield strength, elongation, bending strength, flexural modulus, impact strength, Shore D hardness) of post-curing test pieces (test pieces before heat treatment) during stereolithography, heat The deformation temperature, yellowness and total light transmittance were measured by the methods described above, and as shown in Table 2 below.
(3) The test piece (test piece post-cured with ultraviolet rays) obtained in (2) above is placed in a thermostatic bath at a temperature of 50 ° C., preheated for 1 hour, and then heat-treated at 100 ° C. for 120 minutes, and then the thermostatic bath And left at room temperature (25 ° C.) for 24 hours, and then the mechanical properties (breaking strength, yield strength, elongation, bending strength, flexural modulus, impact strength), thermal deformation temperature, yellowness and When the total light transmittance was measured by the method described above, it was as shown in Table 2 below.

Example 2
(1) As shown in Table 1 below, 9.0 parts by mass of 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate (“Celoxide 2021P” manufactured by Daicel Corporation), ε-caprolactone-modified 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate (“Celoxide 2081” manufactured by Daicel Corporation) 4.0 parts by mass, 2- [4- (2,3-epoxypropoxy) phenyl]- 2- [4- [1,1-bis [4-([2,3-epoxypropoxy] phenyl] ethyl] phenyl] propane (VG3101L) 22.4 parts by mass, polytetramethylene glycol diglycidyl ether (Yokkaichi Synthetic Shares) “Epo Gosei PT” manufactured by company company, number of bonds of tetramethylene oxide units ≈ 9, average Molecular weight≈780) 2.0 parts by mass, trimethylolpropane polyglycidyl ether (“EX-321” manufactured by Nagase ChemteX Corporation) 4.0 parts by mass, 3-ethyl-3-hydroxymethyloxetane (manufactured by Toagosei Co., Ltd.) “OXT-101”) 5.0 parts by mass, bis (3-ethyl-3-oxetanylmethyl) ether (“OXT-221” manufactured by Toagosei Co., Ltd.) 11.2 parts by mass, dipentaerythritol polyacrylate (Shin Nakamura) “A-9550W” manufactured by Chemical Industries, Ltd., 8.0 parts by mass of a mixture of pentaacrylate and hexaacrylate), polytetramethylene glycol diacrylate (“FA-PTG9A” manufactured by Hitachi Chemical Co., Ltd., average molecular weight≈650) 0 parts by mass, polypropylene glycol monoacrylate (manufactured by NOF Corporation Mer AP-150 "6.0 parts by weight, tricyclodecane dimethanol diacrylate (" A-DCP "manufactured by Shin-Nakamura Chemical Co., Ltd.) 12.0 parts by weight, cationic polymerization initiator (" CPI- "manufactured by San Apro Corporation) 200K ") 3.0 parts by weight, 1-hydroxy-cyclohexyl phenyl ketone (" IRGACURE 184 "manufactured by BASF) (3.0 radicals by radical polymerization initiator), 0.020 parts by weight of 2-naphthalenethiol and 0 distilled water The resin composition for optical three-dimensional modeling was prepared by thoroughly mixing 3 parts by mass.
When the viscosity of this resin composition for optical three-dimensional modeling was measured by the method described above, it was 330 MPa · s (25 ° C.).
(2) Using the resin composition for optical three-dimensional modeling obtained in (1) above, a test piece for measuring physical properties was prepared in the same manner as in (2) of Example 1, and the obtained test piece was used. The film was post-cured by irradiation with ultraviolet rays (metal halide lamp, wavelength 365 nm, intensity 3.0 mW / cm ² ) for 20 minutes.
Shrinkage ratio and mechanical properties (post-hardening strength, yield strength, elongation, bending strength, flexural modulus, impact strength, Shore D hardness) of post-curing test pieces (test pieces before heat treatment) during stereolithography, heat The deformation temperature, yellowness and total light transmittance were measured by the methods described above, and as shown in Table 2 below.
(3) The test piece (test piece post-cured with ultraviolet rays) obtained in (2) above is placed in a thermostatic bath at a temperature of 50 ° C., preheated for 1 hour, and then heat-treated at 100 ° C. for 120 minutes, and then the thermostatic bath And left at room temperature (25 ° C.) for 24 hours, and then the mechanical properties (breaking strength, yield strength, elongation, bending strength, flexural modulus, impact strength), thermal deformation temperature, yellowness and When the total light transmittance was measured by the method described above, it was as shown in Table 1 below.

Example 3
(1) As shown in Table 1 below, in Example 1 (1), instead of 4.0 parts by mass of trimethylolpropane polyglycidyl ether (“EX-321” manufactured by Nagase ChemteX Corporation), neo A resin composition for optical three-dimensional modeling was prepared in the same manner as (1) of Example 2 except that 4.0 parts by mass of pentyl glycol diglycidyl ether (“EX- 211L” manufactured by Nagase ChemteX Corporation) was used. did.
It was 300 mPa * s (25 degreeC) when the viscosity of this resin composition for optical three-dimensional modeling was measured by the above-mentioned method.
(2) Using the resin composition for optical three-dimensional modeling obtained in (1) above, a test piece for measuring physical properties was prepared in the same manner as in (2) of Example 1, and the obtained test piece was used. The film was post-cured by irradiation with ultraviolet rays (metal halide lamp, wavelength 365 nm, intensity 3.0 mW / cm ² ) for 20 minutes.
Shrinkage ratio and mechanical properties (post-hardening strength, yield strength, elongation, bending strength, flexural modulus, impact strength, Shore D hardness) of post-curing test pieces (test pieces before heat treatment) during stereolithography, heat The deformation temperature, yellowness and total light transmittance were measured by the methods described above, and as shown in Table 2 below.
(3) The test piece (test piece post-cured with ultraviolet rays) obtained in (2) above is placed in a thermostatic bath at a temperature of 50 ° C., preheated for 1 hour, and then heat-treated at 100 ° C. for 120 minutes, and then the thermostatic bath And left at room temperature (25 ° C.) for 24 hours, and then the mechanical properties (breaking strength, yield strength, elongation, bending strength, flexural modulus, impact strength), thermal deformation temperature, yellowness and When the total light transmittance was measured by the method described above, it was as shown in Table 2 below.

<< Comparative Example 1 >>
(1) As shown in Table 1 below, 13.0 parts by mass of 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate (“Celoxide 2021P” manufactured by Daicel Corporation), poly (2- Oxiranyl) -1,2-cyclohexanediol-2-ethyl-2- (hydroxymethyl) -1,3-propanediol ether and the above-mentioned Celoxide 2021P (“EHPE-3150CE” manufactured by Daicel Corporation) 4.8 mass 2- [4- (2,3-epoxypropoxy) phenyl] -2- [4- [1,1-bis [4-([2,3-epoxypropoxy] phenyl] ethyl] phenyl] propane (VG3101L) ) 24.0 parts by mass, polytetramethylene glycol diglycidyl ether (manufactured by Yokkaichi Synthesis Co., Ltd. POGOSE PT ", number of bonds of tetramethylene oxide units≈9, average molecular weight≈780) 4.0 parts by mass, trimethylolpropane polyglycidyl ether (“ EX-321 ”manufactured by Nagase ChemteX Corporation) 5.0 parts by mass, , 6-hexanediol diglycidyl ether (“EX-212” manufactured by Nagase ChemteX Corporation) 2.0 parts by mass, hydrogenated bisphenol A diglycidyl ether (“Rikaresin HBE-100” manufactured by Shin Nippon Rika Co., Ltd.) 1 part by mass, 4.5 parts by mass of 3-ethyl-3-hydroxymethyloxetane (“OXT-101” manufactured by Toagosei Co., Ltd.), bis (3-ethyl-3-oxetanylmethyl) ether (manufactured by Toagosei Co., Ltd. “ OXT-221 ") 12.0 parts by mass, dipentaerythritol polyacrylate (Shin Nakamura Chemical) “A-9550W” manufactured by Kogyo Co., Ltd., 4.0 parts by mass of a mixture of pentaacrylate and hexaacrylate), ethylene oxide-modified dipentaerythritol hexaacrylate (“A-DPH-12E” manufactured by Shin-Nakamura Chemical Co., Ltd.) 0 parts by mass, polytetramethylene glycol diacrylate (Hitachi Chemical Co., Ltd. “FA-PTG9A”, average molecular weight ≈ 650) 7.0 parts by mass, polypropylene glycol monoacrylate (Nippon Yushi Co., Ltd. “Blemmer AP-150” 4 0.0 parts by mass, propylene oxide-modified pentaerythritol tetraacrylate (“NTM-4P” manufactured by Shin-Nakamura Chemical Co., Ltd., 4 mol of propylene oxide added), 4.0 parts by mass, cationic polymerization initiator (manufactured by San Apro Co., Ltd.) "CPI-200K") 3.0 parts by mass, 1-hydroxy-cyclohexyl phenyl ketone (“IRGACURE 184” manufactured by BASF) (radical polymerization initiator) 2.0 parts by mass, polytetramethylene ether glycol (“PTG-850SN” manufactured by Hodogaya Chemical Co., Ltd. 2.0 mass) Part, 0.020 parts by mass of 2-naphthalenethiol and 0.5 parts by mass of distilled water were mixed well to prepare a resin composition for optical three-dimensional modeling.
It was 460 Mpa * s (25 degreeC) when the viscosity of this resin composition for optical three-dimensional modeling was measured by the above-mentioned method.
(2) Using the resin composition for optical three-dimensional modeling obtained in (1) above, a test piece for measuring physical properties was prepared in the same manner as in (2) of Example 1, and the obtained test piece was used. The film was post-cured by irradiation with ultraviolet rays (metal halide lamp, wavelength 365 nm, intensity 3.0 mW / cm ² ) for 20 minutes.
Shrinkage ratio and mechanical properties (post-hardening strength, yield strength, elongation, bending strength, flexural modulus, impact strength, Shore D hardness) of post-curing test pieces (test pieces before heat treatment) during stereolithography, heat The deformation temperature, yellowness and total light transmittance were measured by the methods described above, and as shown in Table 2 below.
(3) The test piece (test piece post-cured with ultraviolet rays) obtained in (2) above is placed in a thermostatic bath at a temperature of 50 ° C., preheated for 1 hour, and then heat-treated at 100 ° C. for 120 minutes, and then the thermostatic bath And left at room temperature (25 ° C.) for 24 hours, and then the mechanical properties (breaking strength, yield strength, elongation, bending strength, flexural modulus, impact strength), thermal deformation temperature, yellowness and When the total light transmittance was measured by the method described above, it was as shown in Table 2 below.

<< Comparative Example 2 >>
(1) As shown in Table 1 below, in (1) of Example 1, 2- [4- (2,3-epoxypropoxy) phenyl] -2- [4- [1,1-bis [4] -([2,3-epoxypropoxy] phenyl] ethyl] phenyl] propane (VG3101L) in place of 24.0 parts by mass, 16.0 parts by mass of “VG3101L” and bisphenol A bis (propylene glycol glycidyl ether) ether (New Nippon Rika Co., Ltd. “Rika Resin BPO-20E”) 12.0 parts by mass, and further bis (3-ethyl-3-oxetanylmethyl) ether (Toagosei Co., Ltd. “OXT-221”) A resin composition for optical three-dimensional modeling was prepared in the same manner as (1) of Example 1 except that the amount was changed to 8.0 parts by mass.
It was 440 mPa * s (25 degreeC) when the viscosity of this resin composition for optical three-dimensional modeling was measured by the above-mentioned method.
(2) Using the resin composition for optical three-dimensional modeling obtained in (1) above, a test piece for measuring physical properties was prepared in the same manner as in (2) of Example 1, and the obtained test piece was used. The film was post-cured by irradiation with ultraviolet rays (metal halide lamp, wavelength 365 nm, intensity 3.0 mW / cm ² ) for 20 minutes.
Shrinkage ratio and mechanical properties (post-hardening strength, yield strength, elongation, bending strength, flexural modulus, impact strength, Shore D hardness) of post-curing test pieces (test pieces before heat treatment) during stereolithography, heat The deformation temperature, yellowness and total light transmittance were measured by the methods described above, and as shown in Table 2 below.
(3) The test piece (test piece post-cured with ultraviolet rays) obtained in (2) above is placed in a thermostatic bath at a temperature of 50 ° C., preheated for 1 hour, and then heat-treated at 100 ° C. for 120 minutes, and then the thermostatic bath And left at room temperature (25 ° C.) for 24 hours, and then the mechanical properties (breaking strength, yield strength, elongation, bending strength, flexural modulus, impact strength), thermal deformation temperature, yellowness and When the total light transmittance was measured by the method described above, it was as shown in Table 2 below.

As shown in Table 1 and Table 2 above, an optical system containing a cationically polymerizable organic compound (A), a radically polymerizable organic compound (B), a cationic polymerization initiator (C), and a radical polymerization initiator (D) Ratio of the content (W _B ) (mass) of the radical polymerizable organic compound (B) to the content (W _A ) (mass) of the cationic polymerizable organic compound (A) (W _B / W _A ) is 0.45 or more, and the content of the aromatic polyepoxy compound (A-1) having three or more epoxy groups is contained in the optical three-dimensional modeling resin composition. The resin compositions for optical three-dimensional modeling of Examples 1 to 3, which are in the range of 30 to 80% by mass based on the total mass of the organic compound (A), are low in viscosity and excellent in handleability during optical modeling and are cured. The shrinkage rate of the time (during stereolithography) It has excellent% less than the smaller dimension accuracy.
In addition, the three-dimensional model obtained by optical modeling using the optical three-dimensional model resin compositions of Examples 1 to 3 has high fracture strength, bending strength, flexural modulus, and the like, and is excellent in toughness.
Furthermore, the three-dimensional modeled object obtained by optical modeling using the resin composition for optical three-dimensional modeling of Examples 1 to 3 has a high heat distortion temperature, is excellent in heat resistance, and is immediately after optical modeling. High hardness and excellent shape retention.
In addition, the three-dimensional object obtained by optical modeling using the resin composition for optical three-dimensional modeling of Examples 1 to 3 has a yellowness value smaller than 10 and excellent in color tone, and further transmits all light. The rate is 85% or more and the transparency is excellent.

On the other hand, the resin composition for optical three-dimensional modeling of Comparative Example 1 has a content (W) of the radical polymerizable organic compound (B) with respect to the content (W _A ) (mass) of the cationic polymerizable organic compound (A). _B ) When the (mass) ratio (W _B / W _A ) is smaller than 0.45, a three-dimensional object (particularly heat treatment) obtained by optical modeling using the optical three-dimensional resin composition. The rupture strength, bending strength, and bending elastic modulus of the three-dimensional model not performed) are significantly lower and inferior to the toughness than the three-dimensional model obtained from the optical three-dimensional resin composition of Examples 1-3. In addition, the Shore hardness immediately after stereolithography is as low as 50 or less, and the shape retention is poor.

In addition, the resin composition for optical three-dimensional modeling of Comparative Example 2 has a content (W _B ) of the radical polymerizable organic compound (B) with respect to the content (W _A ) (mass) of the cationic polymerizable organic compound (A). Although the requirement that the (mass) ratio (W _B / W _A ) is 0.45 or more is satisfied, the content of the aromatic polyepoxy compound (A-1) having 3 or more epoxy groups is optical. Based on the total mass of the cationically polymerizable organic compound (A) contained in the resin composition for three-dimensional modeling, it is less than 30% by mass and does not satisfy the requirements of the present invention. Dimensional accuracy is low.
And the three-dimensional molded item obtained by optical modeling using the resin composition for optical three-dimensional modeling of the comparative example 2 has low heat deformation temperature, and is inferior to heat resistance.

  The resin composition for optical three-dimensional modeling of the present invention is a resin for optical three-dimensional modeling that has high curing sensitivity due to active energy rays, low viscosity, excellent handling at the time of modeling, high resolution of a modeled object, and excellent modeling accuracy. In addition to having the basic physical properties necessary for the composition, by performing optical modeling using the resin composition for optical three-dimensional modeling of the present invention, the shrinkage ratio during curing is small, the dimensional accuracy is excellent, and the mechanical strength 3D modeling that is high in toughness, excellent in toughness, has high heat distortion temperature, excellent in heat resistance, high in hardness, excellent in shape retention, low in yellowness, high in light transmittance, and excellent in color tone and transparency Therefore, the resin composition for optical three-dimensional modeling of the present invention has high heat resistance, high transparency and good color tone, and dynamics such as strength, elastic properties, impact resistance, and toughness. With excellent physical properties A model for verifying the appearance design of various industrial products in the middle of design, a model for checking the functionality of parts, a resin mold for manufacturing a mold, and a mold are required. Base model for automobile, motorcycle lens, restoration of art, imitation and modern art, art and craft fields such as design presentation model of glass construction, precision parts, electrical / electronic parts, furniture, building structures It can be effectively used in various applications such as automobile parts, various containers, models such as castings, railways, construction machines, industrial robots, airplanes and other control parts.

Claims (7)

A resin composition for optical three-dimensional modeling comprising a cationic polymerizable organic compound (A), a radical polymerizable organic compound (B), a cationic polymerization initiator (C) and a radical polymerization initiator (D);
The ratio (W _B / W _A ) of the content (W _B ) (mass) of the radical polymerizable organic compound (B) to the content (W _A ) (mass) of the cationic polymerizable organic compound ( _A ) is 0. 45 or more; and
Based on the total mass of the cationically polymerizable organic compound (A) contained in the resin composition for optical three-dimensional modeling, 30 to 80% by mass of the aromatic polyepoxy compound (A-1) having 3 or more epoxy groups. Contained in proportions;
A resin composition for optical three-dimensional modeling characterized by the above.   The oxetane compound (A-2) is contained in a proportion of 10 to 40% by mass based on the total mass of the cationically polymerizable organic compound (A) contained in the resin composition for optical three-dimensional modeling. A resin composition for optical three-dimensional modeling.   Based on the total mass of the radical polymerizable organic compound (B) contained in the resin composition for optical three-dimensional modeling, polyalkylene glycol di (meth) acrylate (B-1) and polyalkylene glycol mono (meth) acrylate (B The resin composition for optical three-dimensional model | molding of Claim 1 or 2 which contains at least 1 sort (s) of -2) in the ratio of 1-30 mass%.   The resin composition for optical three-dimensional model | molding of any one of Claims 1-3 containing the diepoxy compound (A-3) which has two epoxy groups as some cationically polymerizable organic compounds (A). .   The optical three-dimensional modeling according to any one of claims 1 to 4, wherein the content of diglycidyl ether of hydrogenated bisphenols is 10% by mass or less based on the total mass of the cationically polymerizable organic compound (A). Resin composition.   Based on the total mass of the resin composition for optical three-dimensional modeling, the cationically polymerizable organic compound (A) is 30 to 70% by mass, the radically polymerizable organic compound (B) is 25 to 50% by mass, and the cationic polymerization initiator ( The resin for optical three-dimensional modeling according to any one of claims 1 to 5, comprising 0.1 to 10% by mass of C) and 0.1 to 10% by mass of a radical polymerization initiator (D). Composition.   The manufacturing method of the three-dimensional molded item characterized by manufacturing an optical three-dimensional model | molding using the resin composition for optical three-dimensional model | molding of any one of Claims 1-6.