JP2008063514A - Resin composition for optical stereolithography - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin composition for optical stereolithography which, when stereolithographically shaped, can give stereolithographic shaping free from warpage and excellent in dimensional accuracy, mechanical properties, and appearance in good productivity with high curing sensitivity and reduced shrinkage. <P>SOLUTION: The resin composition comprises 5-60 mass% di(meth)acrylate compound of (Ia) or (Ib). <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a resin composition for optical three-dimensional modeling, a three-dimensional modeled product, and a manufacturing method thereof. More specifically, the present invention has a small shrinkage at the time of stereolithography (during curing), and does not cause warping of the model at the time of stereolithography, thereby smoothly producing a three-dimensional model with good operability. Optics that can produce optical three-dimensional objects with excellent modeling accuracy, dimensional accuracy, mechanical properties, and appearance smoothly and with high productivity in a short modeling time with high curing sensitivity by active energy rays. The present invention relates to a three-dimensional modeled resin composition, a three-dimensional modeled product made thereof, and a method for producing the same.

In recent years, a method for three-dimensional optical modeling of a liquid photocurable resin composition based on data input to a three-dimensional CAD has achieved good dimensional accuracy without producing a mold or the like. Have been widely adopted.
As a typical example of the optical three-dimensional modeling method, a predetermined thickness is obtained by selectively irradiating an ultraviolet laser controlled by a computer so that a desired pattern is obtained on the liquid surface of the liquid photocurable resin placed in a container. 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. The method of obtaining a molded article can be mentioned. With this optical three-dimensional modeling method, it is possible to easily obtain a model having a considerably complicated shape in a relatively short time.

  In recent years, instead of the above-described conventional method using spot-like ultraviolet laser light, a micro liquid crystal shutter capable of shielding and transmitting light in a micro dot area between the light source and the surface of the photocurable resin composition. Light is applied to the liquid surface of the photocurable resin through a liquid crystal drawing mask in which a plurality of liquid crystal drawing masks are arranged, or a surface drawing mask comprising a so-called DMD (digital micromirror device) in which a plurality of digital micromirror shutters are arranged in a plane shape. A three-dimensional modeling technique has been proposed in which a light-curing resin layer having a predetermined cross-sectional shape pattern is sequentially formed by irradiation. Since the optical three-dimensional modeling technique using a drawing mask can form a cross-sectional shape pattern that is photocured by irradiating light onto a modeling surface made of a photo-curable resin composition at once in a planar shape. It is possible to greatly improve the optical modeling speed as compared with the spotting method using a spot-like ultraviolet laser.

For resin compositions used for optical modeling, low viscosity, good handling during modeling, excellent storage stability, high curing sensitivity with active energy rays, and excellent mechanical properties of cured products At the same time, it is required that a volumetric shrinkage during curing is small, and a three-dimensional molded article having excellent dimensional accuracy and dimensional stability can be manufactured with good operability.
As a resin composition for optical modeling, conventionally, an acrylate photocurable resin composition, a urethane acrylate photocurable resin composition, an epoxy photocurable resin composition, and an epoxy acrylate photocurable resin composition Vinyl ether photocurable resin compositions have been proposed and used.

Among the above-mentioned photo-curable resin compositions, the acrylate-based photo-curable resin composition can be designed with various molecular structures according to the use of the optical modeling object, has high reactivity, and has a hue after curing. Is also widely used for optical three-dimensional modeling. However, since the acrylate photocurable resin composition generally has a high shrinkage ratio of 7 to 10% due to photocuring, “curling” is likely to occur in the cured product during optical modeling. When warping occurs in a modeled object during modeling at the time of optical modeling, for example, the warped part of the modeled object protrudes outward from the liquid modeling surface made of the photocurable resin composition, and the liquid photocurable resin composition A device (such as a recoater) that moves on the surface of the surface to flatten the modeling surface collides with the protruding part, and the device stops, making it difficult for subsequent optical modeling operations to occur. Become. In addition, if you perform optical modeling using a photocurable resin composition with a large shrinkage rate in the modeled object, the dimensional accuracy, modeling accuracy, and appearance of the resulting three-dimensional modeled object will be poor, and the desired three-dimensional modeled object will be obtained. It becomes impossible.
As a conventional technique that eliminates the above-mentioned problems that occur when an acrylate-based photocurable resin composition is used for stereolithography, it has a steric hindrance as a means of reducing shrinkage during molding and preventing warpage. A photocurable resin composition containing a urethane acrylate of a diol compound is known (see Patent Document 1).
However, in the case of the related art, the effect of reducing shrinkage and preventing warpage during stereolithography is still insufficient.

JP-A-8-27236 Japanese Patent No. 3789974 Paul F. Jacobs, “Rapid Prototyping & Manufacturing, Fundamentals of Stereo-Lithography”, “Society of Manufacturing Engineers”, 1992, p. 28-39.

The object of the present invention is that the shrinkage rate during stereolithography (volumetric shrinkage rate during curing) is small, and the modeled object does not warp during stereolithography. It is an object to provide a resin composition for optical three-dimensional modeling that can be smoothly implemented with good productivity without being generated, and that can smoothly produce a three-dimensional modeled article having excellent dimensional accuracy and modeling accuracy.
Further, the object of the present invention is to produce a three-dimensional modeled object with a shortened active energy ray irradiation time with a high curing sensitivity by active energy rays in combination with the above-described characteristics, and a low viscosity during optical modeling. It is to provide a resin composition for optical three-dimensional modeling that is capable of producing a three-dimensional molded article that is excellent in handling property, is stable over time during storage, and is excellent in mechanical properties and water resistance.
And the objective of this invention is providing the three-dimensional molded item which consists of such a resin composition for optical three-dimensional modeling, and its manufacturing method.

In order to solve the above-mentioned problems, the present inventors have intensively studied. As a result, a specific di (meth) acrylate compound in which two (meth) acryloyloxy groups are bonded to p-menthane via a cyclohexylene group is contained in a predetermined amount in the resin composition for optical three-dimensional modeling. And the shrinkage rate during photocuring of the resin composition for optical three-dimensional modeling (the volumetric shrinkage rate during optical modeling) is reduced, so that warpage does not occur in the modeled object during modeling, and the modeling operation is interrupted. It has been found that a molded article excellent in dimensional stability and modeling accuracy can be produced smoothly with good optical modeling operability and with good productivity.
The present inventors also provide a resin composition for optical three-dimensional modeling containing the specific di (meth) acrylate compound in which two (meth) acryloyloxy groups are bonded to p-menthane via a cyclohexylene group. Is highly sensitive to curing with active energy rays, can produce 3D objects with reduced irradiation time of active energy rays, has low viscosity and is easy to handle during stereolithography, and has excellent stability over time during storage It has been found that an optically shaped article formed using the resin composition for optical three-dimensional modeling is excellent in mechanical properties, water resistance, and the like.

  The present inventors also provide a resin composition for optical three-dimensional modeling containing the specific di (meth) acrylate compound in which two (meth) acryloyloxy groups are bonded to p-menthane via a cyclohexylene group. Then, when other radical polymerizable organic compounds are contained together with the di (meth) acrylate compound, or other radical polymerizable organic compounds and cationic polymerizable organic compounds are contained, the shrinkage during photocuring is reduced. It is possible to improve the curing sensitivity, resolution, modeling accuracy, dimensional accuracy of the resin composition for optical three-dimensional modeling, the mechanical properties of the cured product, and the adjustment of various physical properties according to the use of the optical modeling product. The present invention has been completed based on the headings and their various findings.

That is, the present invention
(1) At least one selected from a di (meth) acrylate compound (Ia) represented by the following general formula (Ia) and a di (meth) acrylate compound (Ib) represented by the following general formula (Ib) It is a resin composition for optical three-dimensional model | molding characterized by containing the di (meth) acrylate compound (I) of 5-60 mass%.

（式中、Ｒは水素原子またはメチル基を示す。）

(In the formula, R represents a hydrogen atom or a methyl group.)

And this invention,
(2) The optical steric structure of (1) above, which contains a radical polymerizable organic compound other than the di (meth) acrylate compound (I) and the di (meth) acrylate compound (I) and an energy ray sensitive radical polymerization initiator. Resin composition for modeling;
(3) The above-mentioned di (meth) acrylate compound (I), radical polymerizable organic compound other than di (meth) acrylate compound (I), cationic polymerizable organic compound, active energy ray sensitive radical polymerization initiator and active energy ray The resin composition for optical three-dimensional modeling according to the above (1) or (2) containing a sensitive cationic polymerization initiator; and
(4) The di (meth) acrylate compound (Ia) is a di (meth) acrylate compound (Ia-1) represented by the following general formula (Ia-1), and the di (meth) acrylate compound ( In the resin composition for optical three-dimensional modeling according to any one of (1) to (3), wherein Ib) is a di (meth) acrylate compound (Ib-1) represented by the following general formula (Ib-1): is there.

（式中、Ｒは水素原子またはメチル基を示す。）

(In the formula, R represents a hydrogen atom or a methyl group.)

Furthermore, the present invention provides:
(5) Based on the total mass of the resin composition for optical three-dimensional modeling, the content of the di (meth) acrylate compound (I) is 5 to 60% by mass, other than the di (meth) acrylate compound (I). The optical system according to any one of (1), (2) and (4), wherein the content of the radical polymerizable organic compound is 40 to 94% by mass and the content of the active energy ray radical polymerization initiator is 1 to 10% by mass. Resin composition for three-dimensional modeling;
(6) Based on the total mass of the resin composition for optical three-dimensional modeling, the content of the di (meth) acrylate compound (I) is 5 to 40% by mass, other than the di (meth) acrylate compound (I). The content of the radical polymerizable organic compound is 5 to 40% by mass, the content of the cationic polymerizable organic compound is 10 to 60% by mass, the content of the active energy ray sensitive radical polymerization initiator is 1 to 10% by mass and the active energy. The resin composition for optical three-dimensional modeling according to any one of (1), (3) and (4), wherein the content of the line-sensitive cationic polymerization initiator is 1 to 10% by mass;
(7) The resin composition for optical three-dimensional modeling according to any one of (2) to (6), wherein the radical polymerizable organic compound other than the di (meth) acrylate compound (I) is mainly an ethylenically unsaturated compound. ;and,
(8) The resin composition for optical three-dimensional modeling according to any one of (3), (4), (6) and (7), wherein the cationically polymerizable organic compound is mainly an epoxy compound and / or an oxetane compound;
It is.

And this invention,
(9) A three-dimensional structure formed using the resin composition for optical three-dimensional modeling according to any one of (1) to (8); and
(10) Curing having a predetermined shape pattern by forming a modeling surface using the resin composition for optical three-dimensional modeling according to any one of (1) to (8) and irradiating the modeling surface with active energy rays. After forming the resin layer, the optical three-dimensional modeling resin composition is applied on the cured resin layer to form a modeling surface, and the modeling surface is irradiated with active energy rays to have a predetermined shape pattern. A method for producing a three-dimensional structure, characterized by repeating a modeling operation for forming a cured resin layer;
It is.

Since the resin composition for optical three-dimensional modeling of the present invention has a small shrinkage ratio during photocuring (volumetric shrinkage ratio during optical modeling), warping of the molded article does not occur during optical modeling, thereby causing an unexpected device. Therefore, it is possible to smoothly manufacture a three-dimensional modeled object with good productivity by an excellent optical modeling operation.
The optically shaped product obtained from the resin composition for optical three-dimensional modeling of the present invention is excellent in dimensional accuracy and appearance because the volumetric shrinkage rate at the time of curing is small.
The resin composition for optical three-dimensional modeling of the present invention has high curing sensitivity by active energy rays, can produce a three-dimensional modeled product with a shortened irradiation time of active energy rays, has low viscosity, and is easy to handle during optical modeling. The optically shaped article formed using the resin composition for optical three-dimensional modeling of the present invention has excellent mechanical properties, water resistance, etc. Is excellent.
Among the resin compositions for optical three-dimensional modeling of the present invention, for optical three-dimensional modeling containing the above di (meth) acrylate compound (I) and another radical polymerizable organic compound and an active energy ray radical polymerization initiator The resin composition and the above-mentioned di (meth) acrylate compound (I) contain other radical polymerizable organic compound, cationic polymerizable organic compound, active energy ray radical polymerization initiator and active energy ray sensitive cationic polymerization initiator Optical three-dimensional modeling resin composition improves curing sensitivity, resolution, modeling accuracy, dimensional accuracy, mechanical properties of cured products, etc., and uses of optical modeling products while reducing volume shrinkage during optical modeling Various physical properties can be adjusted according to the conditions.

The present invention is described in detail below.
The resin composition for optical three-dimensional modeling of the present invention includes a di (meth) acrylate compound (Ia) represented by the following general formula (Ia) and a di (meth) acrylate represented by the following general formula (Ib). At least one di (meth) acrylate compound (I) selected from the compound (Ib) is contained in a proportion of 5 to 60% by mass based on the total mass of the resin composition for optical three-dimensional modeling.

（式中、Ｒは水素原子またはメチル基を示す。）

(In the formula, R represents a hydrogen atom or a methyl group.)

The resin composition for optical three-dimensional modeling of the present invention comprises at least one di (meth) acrylate compound (I) selected from di (meth) acrylate compound (Ia) and di (meth) acrylate compound (Ib), By containing at a ratio of 5 to 60% by mass described above, the volume shrinkage rate at the time of photocuring (at the time of optical modeling) is small, and the occurrence of warpage, deformation, etc. in the modeled object is prevented, and the optical modeling operation is performed. A molded article can be manufactured with high productivity without causing a stop, and the dimensional accuracy and appearance of the resulting molded article are improved.
If the content of the di (meth) acrylate compound (I) is less than the above range, the volume shrinkage rate during photocuring (during photofabrication) will not be reduced, and warping and deformation will easily occur during photofabrication. As a result, a decrease in productivity due to the stop of the optical modeling operation, a dimensional accuracy of the resulting model, a poor appearance, and the like are likely to occur. On the other hand, when the content of the di (meth) acrylate compound (I) is more than the above range, the viscosity of the optical three-dimensional resin composition increases, resulting in a decrease in modeling speed, a decrease in handling property during modeling, and the like. Arise.
The content of the di (meth) acrylate compound (I) is preferably 5 to 40% by mass based on the total mass of the resin composition for optical three-dimensional modeling.

The di (meth) acrylate compound (Ia) represented by the above general formula (Ia) and the di (meth) acrylate compound (Ib) represented by the above general formula (Ib) are prepared by adding p-cyclohexane to p-menthane. It is a compound in which two (meth) acrylate groups are bonded via a silene group, and is generally called (p-menthadiyl) dicyclohexyl di (meth) acrylate. Here, “(p-menthadiyl)” is a common name meaning that two cyclohexane rings are bonded to p-menthane.
In the di (meth) acrylate compound (Ia) represented by the general formula (Ia) and the di (meth) acrylate compound (Ib) represented by the general formula (Ib), R represents a hydrogen atom or a methyl group. It is. Among them, it is preferable that two Rs are both hydrogen atoms from the viewpoint that the reactivity of the di (meth) acrylate compound (Ia) and the di (meth) acrylate compound (Ib) is high and the optical modeling speed can be increased. .

In the di (meth) acrylate compound (Ia), each of the two (meth) acryloyloxy groups [CH ₂ ═C (R) —COO—] is substituted with p-menthane cyclohexane via a p-cyclohexylene group. It is bonded to any two of the six carbon atoms forming the ring.
Among them, as the di (meth) acrylate compound (Ia), two (meth) acryloyloxy groups are bonded to the 1-position and 3-position carbon atoms in p-menthane via p-cyclohexylene groups, respectively. The di (meth) acrylate compound (Ia-1) represented by the following general formula (Ia-1) is preferably used from the viewpoints of ease of synthesis, availability, storage stability, and the like.

（式中、Ｒは水素原子またはメチル基を示す。）

(In the formula, R represents a hydrogen atom or a methyl group.)

In the di (meth) acrylate compound (Ib), one (meth) acryloyloxy group [CH ₂ ═C (R) —COO—] out of two (meth) acryloyloxy groups is p It is bonded to any one of the six carbon atoms forming the cyclohexane ring of p-menthane via the cyclohexylene group and the other (meth) acryloyloxy group [CH ₂ = C (R) -COO-] is bonded to the carbon atom of the isopropyl group (carbon atom at the 8-position) in p-menthane via the p-cyclohexylene group.
Among them, as the di (meth) acrylate compound (Ib), one (meth) acryloyloxy group is bonded to the carbon atom at the 2-position of p-menthane via the p-cyclohexylene group, and the other Di (meth) represented by the following general formula (Ib-1), wherein the (meth) acryloyloxy group is bonded to the carbon atom at the 8-position in p-menthane via the p-cyclohexylene group. The acrylate compound (Ib-1) is preferable from the viewpoints of ease of synthesis, availability, storage stability, and the like.

（式中、Ｒは水素原子またはメチル基を示す。）

(In the formula, R represents a hydrogen atom or a methyl group.)

  In particular, in the present invention, the di (meth) acrylate compound (I) is a mixture of the di (meth) acrylate compound (Ia-1) and the di (meth) acrylate compound (Ib-1). A mixture in which the mass ratio of (meth) acrylate compound (Ia-1)]: [di (meth) acrylate compound (Ib-1)] is 65:35 to 75:25 is easy to manufacture, easily available, and stored. It is preferably used from the viewpoint of stability.

The production method of the di (meth) acrylate compound (Ia) and the di (meth) acrylate compound (Ib) used in the present invention is not particularly limited.
The di (meth) acrylate compound (Ia-1) is, for example, a compound (IIa) represented by the following general formula (IIa) as a raw material, that is, six carbon atoms forming a cyclohexane ring in p-menthane (Meth) acrylic acid is added and esterified in an organic solvent (for example, p-xylene, toluene, etc.) to compound (IIa) in which a p-hydroxycyclohexyl group is bonded to two carbon atoms. Alternatively, it can be produced by transesterifying by adding methyl (meth) acrylate to convert two hydroxyl groups in compound (IIa) into (meth) acryloyloxy groups.
The di (meth) acrylate compound (Ib-1) is, for example, a compound (IIb) represented by the following general formula (IIb) as a raw material, that is, six cyclohexane rings in p-menthane. A p-hydroxycyclohexyl group is bonded to one of the carbon atoms, and one p-hydroxycyclohexyl group is bonded to the carbon atom at the 8-position of p-menthane to the compound (IIb) with an organic solvent ( (E.g., p-xylene, toluene, etc.) and (ester) by adding (meth) acrylic acid or transesterifying by adding (meth) acrylic acid, It can be produced by converting a hydroxyl group to a (meth) acryloyloxy group.

In the production of di (meth) acrylate compound (Ia) and di (meth) acrylate compound (Ib) by adding (meth) acrylic acid to compound (IIa) and compound (IIb) and carrying out esterification reaction, An acid catalyst (such as p-toluenesulfonic acid) is used in a proportion of 0 to 0.1 mol and (meth) acrylic acid is added in a proportion of 2 to 3 mol with respect to 1 mol of (IIa) and compound (IIb). The reaction is preferably carried out at 80 to 120 ° C.
In addition, in the production of the di (meth) acrylate compound (Ia) and the di (meth) acrylate compound (Ib) by adding methyl (meth) acrylate to the compound (IIa) and compound (IIb) and causing a transesterification reaction. Uses an alkali catalyst (potassium hydroxide, sodium hydroxide, etc.) in a proportion of 0 to 0.1 mol with respect to 1 mol of compound (IIa) and compound (IIb), and methyl (meth) acrylate is 2 to 2. It is preferable to carry out the reaction at 60 to 100 ° C. by adding 3 mol.

  Compound (IIa) and compound (IIb), which are raw material compounds, are obtained by hydrogenating a compound in which two phenol groups are bonded to p-menthane represented by the following general formulas (IIIa) and (IIIb). Can be manufactured by.

Compound (IIa) and compound (IIb), and di (meth) acrylate compound (Ia) and di (meth) acrylate compound (Ib) are all known compounds (see Patent Document 2), and actual production In this case, it can be produced according to the method described in Patent Document 2.
In Test Example 2 in Patent Document 2, 2,8-bis (4-hydroxycyclohexyl) -p-menthane was reacted with methyl methacrylate [di (meth) acrylate compound (Ib- The photocurable resin composition for resists using the compound corresponding to 1)] is described, but Patent Document 2 discloses a three-dimensionally molded photocurable resin composition containing the dimethacrylate body. It is not described that it is used as a resin composition for optical three-dimensional modeling for manufacturing, and therefore the dimethacrylate body has an effect of reducing the volumetric shrinkage ratio in the resin composition for optical three-dimensional modeling. Not listed.

The di (meth) acrylate compound (I) is polymerized and / or crosslinked when irradiated with active energy rays in the presence of an active energy ray-sensitive radical polymerization initiator (hereinafter simply referred to as “radical polymerization initiator”). Therefore, the resin composition for optical three-dimensional modeling of the present invention contains a radical polymerization initiator together with the di (meth) acrylate compound (I).
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 model | molding of this invention is a resin composition for optical three-dimensional model | molding containing the di (meth) acrylate compound (I) in the ratio of 5-60 mass%, and containing a radical polymerization initiator. Any other components may be used, and the types and contents of the other components are not particularly limited, and other components can be selected and used in combination depending on the type and use of the three-dimensional model to be manufactured. .
Among them, the resin composition for optical three-dimensional modeling of the present invention includes a di (meth) acrylate compound (I), a radical polymerizable organic compound other than the di (meth) acrylate compound (I), and an energy ray sensitive radical polymerization initiator. Or a resin composition for optical three-dimensional modeling [hereinafter sometimes referred to as “resin composition for optical three-dimensional modeling (A)”], or a di (meth) acrylate compound (I), di ( Resin composition for optical three-dimensional modeling containing a radically polymerizable organic compound other than the (meth) acrylate compound (I), a cationically polymerizable organic compound, an active energy ray sensitive radical polymerization initiator, and an active energy ray sensitive cationic polymerization initiator [ Hereinafter, this is sometimes referred to as “resin composition for optical three-dimensional modeling (B)”.
By using such a composition, the volume shrinkage rate during photocuring (at the time of photofabrication) can be kept low, and the curing sensitivity, resolution, modeling accuracy, mechanical properties, etc. can be improved, and the use of photofabrication It is possible to smoothly adjust various physical properties according to the conditions.

Examples of the radical polymerizable organic compound other than the di (meth) acrylate compound (I) used in the above-described resin composition for optical three-dimensional modeling (A) and resin composition for optical three-dimensional modeling (B) of the present invention include radicals. Any radically polymerizable organic compound other than the di (meth) acrylate compound (I) that causes a polymerization reaction and / or a crosslinking reaction when irradiated with active energy rays in the presence of a polymerization initiator can be used.
Representative examples of other radical polymerizable organic compounds include (meth) acrylate compounds other than di (meth) acrylate compound (I), unsaturated polyester compounds, and the like. 1 type (s) or 2 or more types can be used.
Among them, as the other radical polymerizable organic compound, compounds having at least one (meth) acryl group in one molecule other than the di (meth) acrylate compound (I) are preferably used. , A reaction product of an epoxy compound and (meth) acrylic acid, a (meth) acrylic acid ester of an alcohol, a polyester (meth) acrylate, a polyether (meth) acrylate, and the like.

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

  Examples of the (meth) acrylic acid esters of the above-described alcohols that can be used as other radical polymerizable organic compounds include aromatic alcohols, aliphatic alcohols having at least one hydroxyl group in the molecule, and the above-described compound (IIa). And (meth) acrylates obtained by reacting alicyclic alcohols other than (IIb) and / or their alkylene oxide adducts with (meth) acrylic acid.

More specifically, for example, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, isooctyl (meth) Acrylate, tetrahydrofurfuryl (meth) acrylate, isobornyl (meth) acrylate, benzyl (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, diethylene glycol di (meth) ) Acrylate, triethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) a Relate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate and other dipentaerythritol poly (meth) acrylates, diols described above (Meth) acrylates of alkylene oxide adducts of polyhydric alcohols such as triol, tetraol, hexaol, ethylene oxide-modified bisphenol A diacrylate, propylene oxide-modified bisphenol A diacrylate, and the like.
Among them, (meth) acrylates of alcohols include two or more (meth) acrylates in one molecule obtained by the reaction of polyhydric alcohols other than the above-mentioned compounds (IIa) and (IIb) with (meth) acrylic acid. ) (Meth) acrylate having an acrylic group, for example, pentaerythritol tetra (meth) acrylate, ethylene oxide modified pentaerythritol tetra (meth) acrylate, propylene oxide modified pentaerythritol tetra (meth) acrylate, dipentaerythritol poly (meth) acrylate, etc. Is preferably used.
Of the (meth) acrylate compounds described above, an acrylate compound is preferably used in view of the polymerization rate rather than a methacrylate compound.

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

  Among the above, in the present invention, as a radical polymerizable organic compound other than the di (meth) acrylate compound (I), an epoxy acrylate obtained by reacting bisphenol A diglycidyl ether and acrylic acid (for example, Showa "VR-77" manufactured by Kobunshi Co., Ltd.), isobornyl acrylate, lauryl acrylate, isostearyl acrylate, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, ethylene oxide modified pentaerythritol tetraacrylate, propylene oxide modified pentaerythritol tetraacrylate, Ethylene oxide-modified trimethylolpropane triacrylate is preferably used from the viewpoint of reactivity, mechanical properties of the cured product, etc.

  The cationically polymerizable organic compound used in the above-described resin composition for optical three-dimensional modeling (B) of the present invention includes a polymerization reaction and / or a crosslink when irradiated with active energy rays in the presence of a cationic polymerization initiator. Any compound that causes a reaction can be used, and representative examples include epoxy compounds, cyclic ether compounds, cyclic acetal compounds, cyclic lactone compounds, cyclic thioether compounds, spiro orthoester compounds, vinyl ether compounds, and the like. The resin composition for optical three-dimensional modeling (B) of the present invention can contain one or more of these cationically polymerizable organic compounds.

More specifically, as an example of a cationically polymerizable organic compound that the optical three-dimensional modeling resin composition (B) can contain,
(1) Epoxy compounds such as alicyclic epoxy resins, aliphatic epoxy resins, aromatic epoxy resins;
(2) Oxetane compounds, oxolane compounds such as tetrahydrofuran, 2,3-dimethyltetrahydrofuran, cyclic ethers or cyclic acetal compounds such as trioxane, 1,3-dioxolane, 1,3,6-trioxane cyclooctane;
(3) cyclic lactone compounds such as β-propiolactone and ε-caprolactone;
(4) thiirane compounds such as ethylene sulfide and thioepichlorohydrin;
(5) Thietane compounds such as 1,3-propyne sulfide and 3,3-dimethylthietane;
(6) Vinyl ether compounds such as ethylene glycol divinyl ether, alkyl vinyl ether, 3,4-dihydropyran-2-methyl (3,4-dihydropyran-2-carboxylate), triethylene glycol divinyl ether;
(7) Spiro orthoester compound obtained by reaction of epoxy compound and lactone;
(8) ethylenically unsaturated compounds such as vinylcyclohexane, isobutylene, polybutadiene;
And so on.

Among the above, in the present invention, one or two or more of an epoxy compound and an oxetane compound are preferably used as the cationic polymerizable organic compound, and the epoxy compound particularly has two or more epoxy groups in one molecule. The polyepoxy compound having is more preferably used.
Examples of the epoxy compound that is preferably used as the cationically polymerizable organic compound include alicyclic epoxy compounds, aliphatic epoxy compounds, and aromatic epoxy compounds.

  Examples of the alicyclic epoxy compound include hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol Z diglycidyl ether, cyclohexane dimethanol diglycidyl ether, or tricyclodecane dimethanol diglycidyl ether, A polyglycidyl ether of a polyhydric alcohol having at least one alicyclic ring, a cyclohexene ring or a cyclopentene oxide-containing compound obtained by epoxidizing a cyclohexene ring or a cyclopentene ring-containing compound with a suitable oxidizing agent such as hydrogen peroxide or peracid, 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, 2- (3,4-epoxycyclohexyl-5,5-spiro-3 4-epoxy) cyclohexane-meta-dioxane, bis (3,4-epoxycyclohexylmethyl) adipate, vinylcyclohexene dioxide, 4-vinylepoxycyclohexane, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, 3 , 4-Epoxy-6-methylcyclohexyl-3,4-epoxy-6-methylcyclohexanecarboxylate, methylenebis (3,4-epoxycyclohexane), dicyclopentadiene diepoxide, di (3,4-epoxycyclohexyl) of ethylene glycol Methyl) ether, ethylene bis (3,4-epoxycyclohexanecarboxylate), dioctyl epoxy hexahydrophthalate, di-2-ethylhexyl epoxy hexahydrophthalate, etc. It is possible.

  Examples of the aliphatic epoxy compounds include polyglycidyl ethers of aliphatic polyhydric alcohols or alkylene oxide adducts thereof, and polyglycidyl esters of aliphatic long-chain polybasic acids. More specifically, for example, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, sorbitol tetraglycidyl ether, Adding one or more alkylene oxides to aliphatic polyhydric alcohols such as hexaglycidyl ether of dipentaerythritol, diglycidyl ether of polyethylene glycol, diglycidyl ether of polypropylene glycol, ethylene glycol, propylene glycol and glycerin Polyglycidyl ether of polyether polyol obtained by the above, diglycidyl ester of aliphatic long-chain dibasic acid, and the like. In addition to the above epoxy compounds, for example, monoglycidyl ethers of higher aliphatic alcohols, glycidyl esters of higher fatty acids, epoxidized soybean oil, butyl epoxy stearate, octyl epoxy stearate, epoxidized linseed oil, epoxidized polybutadiene And so on.

Examples of the aromatic epoxy compound include mono- or polyglycidyl ethers of monovalent or polyhydric phenols having at least one aromatic nucleus or alkylene oxide adducts thereof. Glycidyl ether, epoxy novolac resin, phenol, cresol, butylphenol obtained by reaction of bisphenol A, bisphenol F or its alkylene oxide adduct with epichlorohydrin, or monoglycidyl ether of polyether alcohol obtained by adding alkylene oxide to these And so on.
In the present invention, one or more of the above-described alicyclic epoxy compounds, aliphatic epoxy compounds and aromatic epoxy compounds can be used as the cationically polymerizable organic compound.

Further, the oxetane compound preferably used as the cationically polymerizable organic compound in the optical three-dimensional modeling resin composition (B) of the present invention may be either a monooxetane compound or a polyoxetane compound.
Examples of the monooxetane compound include trimethylene oxide, 3,3-dimethyloxetane, 3,3-dichloromethyloxetane, 3-methyl-3-phenoxymethyloxetane, and 3-ethyl-3- (2-ethylhexyloxymethyl). Oxetane, the following general formula (IV):

（式中、Ｒ¹は炭素数１〜５のアルキル基およびＲ²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。）
で表されるオキセタンモノアルコール化合物［具体例としては、３−エチル−３−（４−ヒドロキシブチル）オキシメチル−オキセタン、３−エチル−３−（５−ヒドロキシペンチル）オキシメチル−オキセタン、３−エチル−３−（３−ヒドロキシｎ−プロピル）オキシメチル−オキセタンなど］、下記の一般式（Ｖ）；

(In the formula, R ¹ represents an alkyl group having 1 to 5 carbon atoms and R ² represents an alkylene group having 2 to 10 carbon atoms which may have an ether bond.)
Oxetane monoalcohol compounds represented by the following: [Specific examples include 3-ethyl-3- (4-hydroxybutyl) oxymethyl-oxetane, 3-ethyl-3- (5-hydroxypentyl) oxymethyl-oxetane, 3- Ethyl-3- (3-hydroxyn-propyl) oxymethyl-oxetane and the like], the following general formula (V);

（式中、Ｒ³はアルキル基、アリール基またはアラルキル基を示し、ｎは１〜６の整数を示す。）
で表されるオキセタンモノアルコール化合物［具体例としては３−ヒドロキシメチル−３−メチルオキセタン、３−ヒドロキシメチル−３−エチルオキセタン、３−ヒドロキシメチル−３−プロピルオキセタン、３−ヒドロキシメチル−３−ノルマルブチルオキセタン、３−ヒドロキシメチル−３−プロピルオキセタンなど］などを挙げることができる。

(In the formula, R ³ represents an alkyl group, an aryl group or an aralkyl group, and n represents an integer of 1 to 6)
Oxetane monoalcohol compounds represented by the following: [Specific examples 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.].

  Moreover, as a polyoxetane compound which can be used with the resin composition for optical three-dimensional model | molding of this invention, following general formula (VI);

（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、ｐは０または１を示す。）
で表されるジオキセタン化合物、具体的には、１，４−ビス［（３−エチル−３−オキセタニルメトキシ）メチル］ベンゼン、１，４−ビス（３−エチル−３−オキセタニルメトキシ）ブタン、１，４−ビス［（３−メチル−３−オキセタニルメトキシ）メチル］シクロヘキサン、ビス（３−メチル−３−オキセタニルメチル）エーテル、ビス（３−エチル−３−オキセタニルメチル）エーテル、ビス（３−プロピル−３−オキセタニルメチル）エーテル、ビス（３−ブチル−３−オキセタニルメチル）エーテルなどを挙げることができる。
本発明の光学的立体造形用樹脂組成物（Ｂ）は、前記したモノオキセタン化合物およびポリオキセタン化合物の１種または２種以上を含有することができる。

(In the formula, two R ^{4 s} are the same or different from each other, and the alkyl group having 1 to 5 carbon atoms, R ⁵ is a divalent organic group having or not having an aromatic ring, and p is 0 or 1) Is shown.)
, Specifically, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, 1,4-bis (3-ethyl-3-oxetanylmethoxy) butane, , 4-bis [(3-methyl-3-oxetanylmethoxy) methyl] cyclohexane, 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.
The resin composition for optical three-dimensional model | molding (B) of this invention can contain the 1 type (s) or 2 or more types of an above described monooxetane compound and a polyoxetane compound.

  In the resin composition for optical three-dimensional modeling of the present invention, any of polymerization initiators that can start radical polymerization of a radical polymerizable organic compound when irradiated with active energy rays can be used as the radical polymerization initiator. Benzyl or its dialkyl acetal compound, phenyl ketone compound, acetophenone compound, benzoin or its alkyl ether compound, benzophenone compound, thioxanthone compound and the like.

Specific examples of benzyl or a dialkyl acetal compound that can be used as a radical polymerization initiator include benzyl dimethyl ketal and benzyl-β-methoxyethyl acetal.
Examples of the phenyl ketone compound include 1-hydroxy-cyclohexyl phenyl ketone.
Examples of the acetophenone compound include diethoxyacetophenone, 2-hydroxymethyl-1-phenylpropan-1-one, 4′-isopropyl-2-hydroxy-2-methyl-propiophenone, and 2-hydroxy-2. -Methyl-propiophenone, p-dimethylaminoacetophenone, p-tert-butyldichloroacetophenone, p-tert-butyltrichloroacetophenone, p-azidobenzalacetophenone and the like.

Examples of 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'-bisdiethylaminobenzophenone, 4,4'-dichlorobenzophenone, and the like.
Examples of the thioxanthone compound include thioxanthone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, and 2-isopropylthioxanthone.

  In the resin composition for optical three-dimensional modeling of the present invention, one or more of the above radical polymerization initiators can be used. Among them, as radical polymerization initiators, 1-hydroxycyclohexyl phenyl ketone (such as “Irgacure 184” manufactured by Ciba Specialty Chemicals), 2,2-dimethoxy-1,2-diphenylethane-1-one (the company) “Irgacure 651”, etc.) are preferably used from the viewpoint that the resulting cured product has a good hue (such as a small yellowness).

The cationic polymerization initiator used in the resin composition for optical three-dimensional modeling (B) of the present invention may be a polymerization initiator capable of initiating cationic polymerization of a cationic polymerizable organic compound when irradiated with active energy rays. Any onium salt that releases a Lewis acid when irradiated with active energy rays is preferably used. Examples of such onium salts include aromatic sulfonium salts of Group VIIa elements, aromatic onium salts of Group VIa elements, aromatic onium salts of Group Va elements, and the like. Specifically, for example, triphenylsulfonium hexafluoroantimonate, triphenylphenacylphosphonium tetrafluoroborate, diphenyl [4- (phenylthio) phenyl] sulfonium hexafluoroantimonate, bis- [4- (diphenylsulfonio) ) Phenyl] sulfide bisdihexafluoroantimonate, bis- [4- (di4′-hydroxyethoxyphenylsulfonio) phenyl] sulfide bisdihexafluoroantimonate, bis- [4- (diphenylsulfonio) phenyl And sulfide bisdihexafluorophosphate, diphenyliodonium tetrafluoroborate, and the like.
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, benzoin alkyl ether, thioxanthone and the like may be used together with the cationic polymerization initiator as necessary.

The resin composition for optical three-dimensional model | molding of this invention is the resin composition for optical three-dimensional model | molding (A) containing di (meth) acrylate compound (I), another radically polymerizable organic compound, and a radical polymerization initiator. In some cases, the content of each component may vary depending on the type of component, the use of the optical modeling object, etc., but in general, based on the total mass of the optical three-dimensional modeling resin composition, The content of the (meth) acrylate compound (I) is 5 to 60% by mass, of which 8 to 55% by mass, particularly 10 to 50% by mass, of the radical polymerizable organic compound other than the di (meth) acrylate compound (I). The content is 40 to 94% by mass, of which 45 to 90% by mass, especially 50 to 87% by mass, and the content of the radical polymerization initiator is 1 to 10% by mass, of which 2 to 8% by mass, especially 3 to 3%. 5% by mass It is preferred.
In addition, the resin composition for optical three-dimensional modeling of the present invention contains a di (meth) acrylate compound (I), another radical polymerizable organic compound, a cationic polymerizable organic compound, a radical polymerization initiator, and a cationic polymerization initiator. In the case of the resin composition for optical three-dimensional modeling (B), the content of the di (meth) acrylate compound (I) is 5 to 40 mass based on the total mass of the resin composition for optical three-dimensional modeling. %, Among which 8-35% by mass, especially 10-30% by mass, the content of radically polymerizable organic compounds other than di (meth) acrylate compound (I) is 5-40% by mass, among which 8-35% by mass In particular, 10 to 30% by mass, the content of the cationically polymerizable organic compound is 10 to 60% by mass, of which 20 to 60% by mass, particularly 30 to 60% by mass, and the content of the radical polymerization initiator is 1 10% by weight, of which 2 to 8% by weight, in particular 3 to 5% by weight, and the content of the cationic polymerization initiator is 1 to 10% by weight, of which 2 to 8% by weight, in particular 3 to 5% by weight. It is preferable.

  As long as the effects of the present invention are not impaired, the resin composition for optical three-dimensional modeling of the present invention, if necessary, colorants such as pigments and dyes, antifoaming agents, leveling agents, thickeners, flame retardants, oxidation agents An appropriate amount of one or two or more of an inhibitor, a filler (crosslinked polymer particles, silica, glass powder, ceramic powder, metal powder, etc.) and a modifying resin may be contained.

Any of the conventionally known optical three-dimensional modeling methods and apparatuses can be used for optical three-dimensional modeling using the resin composition for optical three-dimensional modeling of the present invention. As a representative example of the optical three-dimensional modeling method that can be preferably adopted, the active energy ray is selectively irradiated so that a cured layer having a desired pattern can be obtained in the liquid resin composition for optical three-dimensional modeling of the present invention. Then, a cured layer is formed, and then the uncured liquid optical three-dimensional resin composition is supplied to the cured layer, and similarly, the cured layer continuous with the cured layer is irradiated by irradiating active energy rays. The method of finally obtaining the target three-dimensional molded item can be mentioned by repeating the lamination | stacking operation to form.
Examples of 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 three-dimensional modeling of the present invention can be widely used in the field of optical three-dimensional modeling, and is not limited at all, but as a typical application field, the appearance design is verified during the design. Such as a shape confirmation model for checking, a functional test model for checking the functionality of parts, a master model for producing molds, a master model for producing molds, a direct mold for prototype molds, etc. it can. In particular, the resin composition for optical three-dimensional modeling according to the present invention is effective for producing a shape confirmation model or a function test model of a precise part or the like. More specifically, for example, it can be effectively used for applications such as precision parts, electrical / electronic parts, furniture, building structures, automotive parts, various containers, castings, models, mother dies, processing, etc. .

EXAMPLES The present invention will be specifically described below with reference to examples and the like, but the present invention is not limited to the examples. In the following examples, “parts” means parts by mass.
Moreover, in the following examples, the viscosity, the curing depth (Dp), the critical curing energy (Ec), and the work curing energy (hereinafter, sometimes referred to as “photolithographic resin composition”) of the optical three-dimensional modeling resin E ₁₀ ), measurement of shrinkage rate (volumetric shrinkage rate), and mechanical properties of optically shaped objects obtained by stereolithography [tensile properties (tensile rupture strength, tensile rupture elongation, tensile elastic modulus), yield strength, Bending properties (bending strength, flexural modulus)], surface hardness and thermal deformation temperature were measured or calculated as follows.

(1) Viscosity of resin composition for optical modeling:
The resin composition for optical modeling was placed in a constant temperature bath at 25 ° C., and the temperature of the resin composition for optical modeling was adjusted to 25 ° C., and then measured using a B-type viscometer (manufactured by Tokyo Keiki Co., Ltd.).

(2) Curing depth (Dp), critical curing energy (Ec) and work curing energy (E ₁₀ ) of the resin composition for stereolithography:
The curing depth (Dp), critical curing energy (Ec), and work curing energy (E ₁₀ ) of the resin compositions for optical modeling of Examples 1 to 6 and Comparative Examples 1 to 3 are the following methods (2-i) The curing depth (Dp), critical curing energy (Ec), and work curing energy (E ₁₀ ) of the resin composition for stereolithography of Example 7 and Comparative Example 4 were measured by the following method (2-ii). It was measured.
(2-i) Measured according to the theory described in Non-Patent Document 1. Specifically, a modeling surface (liquid surface) made of a photocurable resin composition is irradiated with light from an ultrahigh pressure mercury lamp (ultraviolet light in a wavelength range of 340 to 380 nm, energy intensity ² mW / cm ² ). A photo-cured film corresponding to the layer was formed. By changing the light irradiation time during the formation of the cured film between 1 to 5 seconds, for example, 1 second, 2 seconds, 3 seconds, 4 seconds, and 5 seconds, this operation is performed on the modeling surface. The amount of irradiation energy was changed, the photocured film produced by each amount of irradiation energy was taken out from the photocurable resin composition liquid, the uncured resin was removed, the thickness of each cured film was measured with a constant pressure caliper, and the photocured film Is plotted with the Y-axis and the irradiation energy amount as the X-axis, and the cure depth is obtained from the slope of the straight line obtained by plotting, and the intercept of the X-axis is defined as the critical cure energy [Ec (mJ / cm ² )]. The amount of exposure energy required for curing to a thickness of 0.25 mm was defined as work curing energy (E ₁₀ / mJ / cm ² ).
(2-ii) Measured according to the theory described in Non-Patent Document 1. Specifically, a laser beam (ultraviolet light with a wavelength of 355 nm, a liquid surface laser intensity of 100 mW) of a semiconductor-excited solid laser is applied to a modeling surface (liquid surface) made of a resin composition for optical modeling, and the irradiation speed is changed in six steps ( The photocured film was formed by irradiating with the irradiation energy amount changed by 6 levels. The produced photocured film was taken out from the photocurable resin composition liquid, the uncured resin was removed, and the thickness of the cured film corresponding to 6 levels of energy was measured with a vernier caliper. Plotting the photocured film thickness as the Y-axis and the irradiation energy amount as the X-axis (logarithmic axis), obtaining the cure depth [Dp (mm)] from the slope of the straight line obtained by plotting, and intercepting the X-axis Was the critical curing energy [Ec (mJ / cm ² )], and the exposure energy required to cure to a thickness of 0.25 mm was the work curing energy [(E ₁₀ / (mJ / cm ² )].

(3) Shrinkage rate:
From the specific gravity (d ₀ ) of the resin composition for optical modeling (liquid) before photo-curing and the specific gravity (d ₁ ) of the photo-cured product obtained by photo-curing, the shrinkage rate was determined by the following formula.

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

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

(4) Tensile properties of the optically shaped article (tensile breaking strength, tensile breaking elongation, tensile elastic modulus):
Using the optical modeling thing (the dumbbell-shaped test piece based on JIS K-7113) produced in the following examples or comparative examples, according to JIS K-7113, the tensile breaking strength (tensile strength) of the test piece, the tensile strength The breaking elongation (tensile elongation) and tensile modulus were measured.

(5) Yield strength of stereolithography:
In the tensile property test of (3) above, the yield strength was defined as the strength at which the optically shaped article moves from elasticity to plasticity.

(6) Bending characteristics (bending strength, flexural modulus) of stereolithography:
The bending strength and the flexural modulus of the test piece were measured according to JIS K-7171 using the optically shaped article (bar-shaped test piece conforming to JIS K-7171) produced in the following examples or comparative examples. .

(7) Surface hardness after modeling:
Using the "ASKER D-type hardness meter" manufactured by Kobunshi Keiki Co., Ltd., using the stereolithography (dumbbell-shaped test piece conforming to JIS K-7113) produced in the following examples and comparative examples, Based on K-6253, the surface hardness of the test piece (4 days after producing the optically shaped article) was measured by the durometer method.

(8) Thermal deformation temperature of stereolithography:
Using the stereolithography produced in the following examples or comparative examples (bar-shaped test piece according to JIS K-7171), using “HDT Tester 6M-2” manufactured by Toyo Seiki Co., Ltd. A load of 1.81 MPa was applied, and the heat distortion temperature of the test piece was measured according to JIS K-7207 (A method).

Example 1
(1) (p-Mentadiyl) dicyclohexyl diacrylate [the diacrylate compound (Ia-1) in which R is a hydrogen atom in the above general formula (Ia-1) and the general formula (Ib-1), wherein R is a hydrogen atom Mixture of 70:30 (molar ratio) of a certain diacrylate compound (Ib-1)] (“A-HYP” manufactured by Yashara Chemical Co., Ltd.), 50 parts, tricyclodecane diacrylate (“A- manufactured by Shin-Nakamura Chemical Co., Ltd.) DCP ") and 50 parts of radical polymerization initiator (2,2-dimethoxy-1,2-diphenylethane-1-one;" Irgacure 651 "manufactured by Ciba Specialty Chemicals) were mixed well at room temperature. Thus, a resin composition for stereolithography was prepared.
When the viscosity of this resin composition for optical modeling was measured by the method described above, it was as shown in Table 1 below.

(2) The above-described method [of (2-i) above] is applied to the curing depth (Dp), critical curing energy (Ec), and work curing energy (E ₁₀ ) of the resin composition for optical modeling obtained in (1) above. Method] was measured as shown in Table 1 below.
Moreover, when the shrinkage | contraction rate at the time of photocuring of the resin composition for optical shaping | molding obtained by said (1) was measured by the above-mentioned method, it was as showing in following Table 1.
(3) An optical modeling apparatus (Seamet Co., Ltd.) equipped with an ultra-high pressure mercury lamp (120 W, manufactured by Iwasaki Electric Co., Ltd.) as a light source and a TFT-type VGA (640 × 480 pixels) liquid crystal manufactured by Epson as a planar drawing mask. "LE3000" manufactured) and using the photocurable resin composition obtained in (1) above, the projection size on the modeling surface (the surface of the photocurable resin composition) = 35 mm (advancing direction of the apparatus) ) X 47 mm (perpendicular to the direction of travel) (square), about 7 mm with a light source, a condensing lens, a planar drawing mask, and a projection lens integrated under the condition of a light energy intensity of ² mW / cm ^{2 on} the modeling surface The image of the planar drawing mask is moved in accordance with the cross-sectional shape pattern to be formed at the speed of / sec. Dumbbell-shaped three-dimensional shaped object and bending characteristics conforming to JIS K-7113 for measuring tensile properties by irradiating light with a layer thickness of 0.1 mm while continuously changing the image pattern in a moving image. A bar-shaped three-dimensionally shaped article conforming to JIS K-7171 for measurement was prepared. In this stereolithography operation, the irradiation time in each part of the photocured layer was 5 seconds, and the light irradiation amount in each part was 8 to 15 mJ. Using the obtained test piece, the tensile properties, bending properties, surface hardness and heat distortion temperature were measured in accordance with JIS K-7113 and JIS K-7171 according to the method described above. It was as shown.

<< Examples 2 to 4 and Comparative Example 1 >>
(1) Same as (1) of Example 1, except that the amount of (p-mentadiyl) dicyclohexyl diacrylate and tricyclodecane diacrylate used in (1) of Example 1 was changed to the amounts shown in Table 1 below. Thus, resin compositions for optical modeling of Examples 2 to 4 and Comparative Example 1 were prepared. The viscosities of these resin molding resin compositions were measured by the method described above, and were as shown in Table 1 below.
(2) The above-mentioned method (the above (2-i)) of the curing depth (Dp), critical curing energy (Ec) and work curing energy (E ₁₀ ) of each resin composition for optical modeling obtained in (1) above. ))] Was measured as shown in Table 1 below.
Moreover, when the shrinkage | contraction rate at the time of photocuring of the resin composition for optical shaping | molding obtained by said (1) was measured by the above-mentioned method, it was as showing in following Table 1.
(3) Using each of the resin compositions for optical modeling obtained in (1) above, optical three-dimensional modeling is performed in the same manner as in (3) of Example 1, and JIS K-7113 for measuring physical properties is performed. The bar-shaped test piece based on JIS K-7171 and the physical property were measured by the method mentioned above. The results are shown in Table 1 below.

  As seen in Table 1 above, the resin compositions for optical three-dimensional modeling of Examples 1 to 4 are (p-menthanediyl) cyclohexyl diacrylate based on the total mass of the resin composition for optical three-dimensional modeling. By containing 60% by mass, the shrinkage rate is small and the volume shrinkage due to photocuring is small compared to the resin composition for optical three-dimensional modeling of Comparative Example 1 that does not contain (p-menthanediyl) cyclohexyl diacrylate. .

Example 5
(1) 15 parts of (p-mentadiyl) dicyclohexyl diacrylate, 15 parts of tricyclodecane diacrylate, and tetraacrylate of pentaerythritol ethylene oxide 4 mol adduct as used in (1) of Example 1 (Shin Nakamura Chemical) "ATM-4E" manufactured by Kogyo Co., Ltd.), 20 parts of diacrylate of bisphenol A ethylene oxide 4 mol adduct ("A-BPE-4" manufactured by Shin-Nakamura Chemical Co., Ltd.) and radical polymerization initiator (2, 2-Dimethoxy-1,2-diphenylethane-1-one; “Irgacure 651” manufactured by Ciba Specialty Chemicals) was mixed well at room temperature to prepare a resin composition for optical modeling.
When the viscosity of this resin composition for optical modeling was measured by the method described above, it was as shown in Table 2 below.
(2) The above-described method [of (2-i) above] is applied to the curing depth (Dp), critical curing energy (Ec), and work curing energy (E ₁₀ ) of the resin composition for optical modeling obtained in (1) above. Method] was measured as shown in Table 2 below.
Moreover, it was as showing in following Table 2 when the shrinkage rate at the time of photocuring of the resin composition for optical shaping | molding obtained by said (1) was measured by the above-mentioned method.
(3) Using the resin composition for optical modeling obtained in (1) above, optical three-dimensional modeling is performed in the same manner as in (3) of Example 1, and conforms to JIS K-7113 for measuring physical properties. The dumbbell-shaped test piece and the bar-shaped test piece based on JIS K-7171 were produced, and the physical properties were measured by the method described above. The results are shown in Table 2 below.

<< Comparative Example 2 >>
(1) 30 parts of the same tricyclodecane diacrylate used in (1) of Example 1 and tetraacrylate of pentaerythritol ethylene oxide 4 mol adduct (“ATM-4E” manufactured by Shin-Nakamura Chemical Co., Ltd.) 50 Part, 20 parts of diacrylate of bisphenol A ethylene oxide 4 mol adduct (“A-BPE-4” manufactured by Shin-Nakamura Chemical Co., Ltd.) and radical polymerization initiator (2,2-dimethoxy-1,2-diphenylethane- 1-on; 5 parts of “Irgacure 651” manufactured by Ciba Specialty Chemicals Co., Ltd.) were mixed well at room temperature to prepare a resin composition for stereolithography.
When the viscosity of this resin composition for optical modeling was measured by the method described above, it was as shown in Table 2 below.
(2) The above-described method [of (2-i) above] is applied to the curing depth (Dp), critical curing energy (Ec), and work curing energy (E ₁₀ ) of the resin composition for optical modeling obtained in (1) above. Method] was measured as shown in Table 2 below.
Moreover, it was as showing in following Table 2 when the shrinkage rate at the time of photocuring of the resin composition for optical shaping | molding obtained by said (1) was measured by the above-mentioned method.
(3) Using the resin composition for optical modeling obtained in (1) above, optical three-dimensional modeling is performed in the same manner as in (3) of Example 1, and conforms to JIS K-7113 for measuring physical properties. The dumbbell-shaped test piece and the bar-shaped test piece based on JIS K-7171 were produced, and the physical properties were measured by the method described above. The results are shown in Table 2 below.

  As seen in Table 2 above, the resin composition for optical three-dimensional modeling of Example 5 is (p-menthanediyl) cyclohexyl diacrylate based on the total mass of the resin composition for optical three-dimensional modeling. By containing in the range of%, the shrinkage rate is small and the volume shrinkage due to photocuring is small as compared with the resin composition for optical three-dimensional modeling of Comparative Example 2 that does not contain (p-menthanediyl) cyclohexyl diacrylate.

Example 6
(1) 10 parts of (p-mentadiyl) dicyclohexyl diacrylate, 10 parts of tricyclodecane diacrylate, and diacrylate of bisphenol A ethylene oxide 4 mol adduct (Shin Nakamura Chemical Co., Ltd.) used in (1) of Example 1 "A-BPE-4" manufactured by Kogyo Co., Ltd.), 30 parts of isobornyl acrylate ("IBXA" manufactured by Osaka Organic Chemical Industry Co., Ltd.), acryloylmorpholine ("A-Mo" manufactured by Shin-Nakamura Chemical Co., Ltd.) ) 15 parts, 35 parts of urethane acrylate compound (Shin Nakamura Chemical Co., Ltd. “U8-231”) and radical polymerization initiator (2,2-dimethoxy-1,2-diphenylethane-1-one; Ciba Specialty)・ "Irgacure 651" manufactured by Chemicals Co., Ltd.) was mixed well at room temperature to prepare a resin composition for stereolithography. Made.
When the viscosity of this resin composition for optical modeling was measured by the method described above, it was as shown in Table 3 below.
(2) The above-described method [of (2-i) above] is applied to the curing depth (Dp), critical curing energy (Ec), and work curing energy (E ₁₀ ) of the resin composition for optical modeling obtained in (1) above. Method] was measured as shown in Table 3 below.
Moreover, it was as showing in following Table 3 when the shrinkage rate at the time of photocuring of the resin composition for optical shaping | molding obtained by said (1) was measured by the above-mentioned method.
(3) Using the resin composition for optical modeling obtained in (1) above, optical three-dimensional modeling is performed in the same manner as in (3) of Example 1, and conforms to JIS K-7113 for measuring physical properties. The dumbbell-shaped test piece and the bar-shaped test piece based on JIS K-7171 were produced, and the physical properties were measured by the method described above. The results are shown in Table 3 below.

<< Comparative Example 3 >>
(1) 20 parts of tricyclodecane diacrylate, 20 parts of diacrylate of bisphenol A ethylene oxide 4 mol adduct (“A-BPE-4” manufactured by Shin-Nakamura Chemical Co., Ltd.), isobornyl acrylate (Osaka Organic Chemical Industry) 30 parts "IBXA" manufactured by Co., Ltd., 15 parts acryloylmorpholine ("A-Mo" manufactured by Shin-Nakamura Chemical Co., Ltd.), 35 parts urethane acrylate compound ("U8-231" manufactured by Shin-Nakamura Chemical Co., Ltd.) Resin composition for optical modeling by thoroughly mixing 5 parts of radical polymerization initiator (2,2-dimethoxy-1,2-diphenylethane-1-one; “Irgacure 651” manufactured by Ciba Specialty Chemicals) at room temperature A product was prepared.
When the viscosity of this resin composition for optical modeling was measured by the method described above, it was as shown in Table 3 below.
(2) The above-described method [of (2-i) above] is applied to the curing depth (Dp), critical curing energy (Ec), and work curing energy (E ₁₀ ) of the resin composition for optical modeling obtained in (1) above. Method] was measured as shown in Table 3 below.
Moreover, it was as showing in following Table 3 when the shrinkage rate at the time of photocuring of the resin composition for optical shaping | molding obtained by said (1) was measured by the above-mentioned method.
(3) Using the resin composition for optical modeling obtained in (1) above, optical three-dimensional modeling is performed in the same manner as in (3) of Example 1, and conforms to JIS K-7113 for measuring physical properties. The dumbbell-shaped test piece and the bar-shaped test piece based on JIS K-7171 were produced, and the physical properties were measured by the method described above. The results are shown in Table 3 below.

  As seen in Table 3 above, the resin composition for optical three-dimensional modeling of Example 6 contains (p-menthanediyl) cyclohexyl diacrylate in an amount of 5 to 60 mass based on the total mass of the resin composition for optical three-dimensional modeling. By containing in the range of%, the shrinkage rate is small and the volume shrinkage due to photocuring is small as compared with the resin composition for optical three-dimensional modeling of Comparative Example 3 that does not contain (p-menthanediyl) cyclohexyl diacrylate.

Example 7
(1) (p-Mentadiyl) dicyclohexyl diacrylate [the diacrylate compound (Ia-1) in which R is a hydrogen atom in the above general formula (Ia-1) and the general formula (Ib-1), wherein R is a hydrogen atom Mixture of 70:30 (molar ratio) of a certain diacrylate compound (Ib-1)] (“A-HYP” manufactured by Yashara Chemical Co., Ltd.), 5 parts, tricyclodecane diacrylate (“A- manufactured by Shin-Nakamura Chemical Co., Ltd.) DCP ") 5 parts, tetraacrylate of pentaerythritol ethylene oxide 4 mol adduct (" ATM-4E "manufactured by Shin-Nakamura Chemical Co., Ltd.), diacrylate of bisphenol A ethylene oxide 4 mol adduct (Shin Nakamura Chemical Co., Ltd.) "A-BPE-2" manufactured by Co., Ltd.) 5 parts, epoxy acrylate ("VR-77" manufactured by Showa Polymer Co., Ltd.) 6 parts, di 6 parts of pentaerythritol hexaacrylate (“A-9530” manufactured by Shin-Nakamura Chemical Co., Ltd.), 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate (“UVR-6105” manufactured by Dow Chemical Company) 43 parts, 10 parts of trimethylolpropane triglycidyl ether (“Tenacol EX-321” manufactured by Nagase ChemteX Corporation), 2.5 parts of alicyclic solid epoxy resin (“EHPE3150” manufactured by Daicel Chemical Industries, Ltd.), hydrogenated bisphenol 10 parts of A diglycidyl ether (“HBE-100” manufactured by Shin Nippon Rika Kogyo Co., Ltd.), 5 parts of 1,4-bis (3-ethyl-3-oxetanylmethoxy) butane (“OXT221” manufactured by Toagosei Co., Ltd.) Radical polymerization initiator [1-hydroxy-cyclohexyl-pheny 2.5 parts of ketone (“Irgacure 184” manufactured by Ciba Specialty Chemicals)] and 5 parts of cationic polymerization initiator [triarylsulfonium hexafluoroantimonate (“CPI 101A” manufactured by San Apro Co., Ltd.)] may be used at room temperature. The resin composition for stereolithography was prepared by mixing.
When the viscosity of this resin composition for optical modeling was measured by the method described above, it was as shown in Table 4 below.

(2) The above-described method [of (2-ii) above] is used to determine the curing depth (Dp), critical curing energy (Ec), and work curing energy (E ₁₀ ) of the resin composition for optical modeling obtained in (1) above. Measurement by [Method] was as shown in Table 4 below.
Moreover, it was as showing in following Table 4 when the shrinkage rate at the time of photocuring of the resin composition for optical shaping | molding obtained by said (1) was measured by the above-mentioned method.
(3) A semiconductor laser (rated output: 1000 mW; wavelength: 355 nm) using an ultrahigh-speed stereolithography system (“SOLIFORM500B” manufactured by Nabtesco Corporation) using the resin composition for stereolithography obtained in (1) above; Spectra Physics "semiconductor-excited solid laser BL6 type", with a liquid level of 500 mW and a liquid level irradiation energy of 80 mJ / cm ² , a slice pitch (lamination thickness) of 0.10 mm and an average modeling time of 2 minutes per layer The optical three-dimensional modeling is performed to produce a dumbbell-shaped test piece according to JIS K-7113 for measuring physical properties, a bar-shaped test piece according to JIS K-7171, and a rectangular string-shaped shaped article. The physical properties were measured by the methods described above, and the results are shown in Table 4 below.

<< Comparative Example 4 >>
(1) A resin composition for optical modeling was prepared by employing the same formulation as (1) of Example 7 except that (p-menthadiyl) dicyclohexyl diacrylate was not used.
When the viscosity of this resin composition for optical modeling was measured by the method described above, it was as shown in Table 4 below.
(2) The above-described method [of (2-ii) above] is used to determine the curing depth (Dp), critical curing energy (Ec), and work curing energy (E ₁₀ ) of the resin composition for optical modeling obtained in (1) above. Measurement by [Method] was as shown in Table 4 below.
Moreover, it was as showing in following Table 4 when the shrinkage rate at the time of photocuring of the resin composition for optical shaping | molding obtained by said (1) was measured by the above-mentioned method.
(3) Using the resin composition for optical modeling obtained in (1) above, optical three-dimensional modeling is performed in the same manner as (3) of Example 7, and conforms to JIS K-7113 for measuring physical properties. The dumbbell-shaped test piece and the bar-shaped test piece based on JIS K-7171 were produced, and the physical properties were measured by the method described above. The results are shown in Table 4 below.

  As seen in Table 4 above, the resin composition for optical three-dimensional modeling of Example 7 contains (p-menthanediyl) cyclohexyl diacrylate in an amount of 5 to 60 mass based on the total mass of the resin composition for optical three-dimensional modeling. By containing in the range of%, the shrinkage rate is small and the volume shrinkage due to photocuring is small as compared with the resin composition for optical three-dimensional modeling of Comparative Example 4 that does not contain (p-menthanediyl) cyclohexyl diacrylate.

The resin composition for optical three-dimensional modeling of the present invention has a small shrinkage at the time of optical modeling (at the time of curing), does not generate warpage at the time of optical modeling, and can smoothly manufacture a three-dimensional modeled object with good operability. In addition, it is possible to smoothly obtain an optical three-dimensional object that is excellent in modeling accuracy, dimensional accuracy, mechanical properties, and appearance in a shortened modeling time due to high curing sensitivity by active energy rays.
Therefore, using the resin composition for optical three-dimensional modeling of the present invention, for precision parts, electrical / electronic parts, furniture, building structures, automotive parts, various containers, castings, molds, mother dies, etc. Models, processing models, parts for designing complex heat medium circuits, parts for analyzing and planning the behavior of heat mediums with complex structures, and other various three-dimensional objects with complex shapes and structures during stereolithography It can be manufactured with high productivity without causing troubles such as stoppage of the apparatus.

Claims (10)

At least one di (meth) acrylate compound (Ia) represented by the following general formula (Ia) and di (meth) acrylate compound (Ib) represented by the following general formula (Ib): A resin composition for optical three-dimensional modeling, comprising (meth) acrylate compound (I) in a proportion of 5 to 60% by mass.

(In the formula, R represents a hydrogen atom or a methyl group.)   The optical three-dimensional modeling according to claim 1, comprising a radical polymerizable organic compound other than the di (meth) acrylate compound (I) and the di (meth) acrylate compound (I) and an energy ray sensitive radical polymerization initiator. Resin composition.   Di (meth) acrylate compound (I), radical polymerizable organic compound other than di (meth) acrylate compound (I), cationic polymerizable organic compound, active energy ray sensitive radical polymerization initiator, and active energy ray sensitive cationic polymerization The resin composition for optical three-dimensional model | molding of Claim 1 or 2 containing an initiator. The di (meth) acrylate compound (Ia) is a di (meth) acrylate compound (Ia-1) represented by the following general formula (Ia-1), and the di (meth) acrylate compound (Ib) is The resin composition for optical three-dimensional modeling according to any one of claims 1 to 3, which is a di (meth) acrylate compound (Ib-1) represented by the following general formula (Ib-1).

(In the formula, R represents a hydrogen atom or a methyl group.)   Based on the total mass of the resin composition for optical three-dimensional modeling, the content of the di (meth) acrylate compound (I) is 5 to 60% by mass, and radical polymerization other than the di (meth) acrylate compound (I). 5. The optical three-dimensional modeling according to claim 1, wherein the content of the organic compound is 40 to 94% by mass and the content of the active energy ray radical polymerization initiator is 1 to 10% by mass. Resin composition.   Based on the total mass of the resin composition for optical three-dimensional modeling, the content of the di (meth) acrylate compound (I) is 5 to 40% by mass, and radical polymerizability other than the di (meth) acrylate compound (I). The content of the organic compound is 5 to 40% by mass, the content of the cationic polymerizable organic compound is 10 to 60% by mass, the content of the active energy ray sensitive radical polymerization initiator is 1 to 10% by mass, and the active energy ray sensitive cation. 5. The resin composition for optical three-dimensional modeling according to claim 1, wherein the content of the polymerization initiator is 1 to 10% by mass.   The resin composition for optical three-dimensional modeling according to any one of claims 2 to 6, wherein the radical polymerizable organic compound other than the di (meth) acrylate compound (I) is mainly an ethylenically unsaturated compound.   The resin composition for optical three-dimensional modeling according to any one of claims 3, 4, 6, and 7, wherein the cationically polymerizable organic compound is mainly an epoxy compound and / or an oxetane compound.   The three-dimensional molded item formed using the resin composition for optical three-dimensional modeling of any one of Claims 1-8.   A cured resin layer having a predetermined shape pattern by forming a modeling surface using the resin composition for optical three-dimensional modeling according to any one of claims 1 to 8, and irradiating the modeling surface with active energy rays. Then, the resin composition for optical three-dimensional modeling is formed on the cured resin layer to form a modeling surface, and the modeling surface is irradiated with active energy rays to have a predetermined shape pattern. A method for producing a three-dimensional structure, characterized in that a modeling operation for forming a layer is repeated.