JPH08323866A - Photo-setting liquid for optical three-dimensional shaping and photo-setting composition for optical three-dimensional shaping containing the same - Google Patents

Abstract

PURPOSE: To obtain a three-dimensional shaped article excellent in mechanical physical properties, thermal physical properties and shape accuracy by using a photo-setting liquid for optical three-dimensional shaping consisting of specific unsaturated ester urethane and a vinyl monomer. CONSTITUTION: A photo-setting liquid for optical three-dimensional shaping consists of unsaturated ester urethane represented by formula I and a vinyl monomer and is characterized by that a wt. ratio of unsaturated ester urethane/ vinyl monomer is 100/25-100/150 and a photo-setting compsn. for optical three- dimensional shaping contains the photo-setting liquid. In the formula I, X is a reside obtained by removing a hydroxyl group from tetravalent alcohol or (poly)ether tetraol, R<1> is a 2-6C alkylene group and A is an org. group represented by either one of formulae II, III (wherein R<2> is a 2-6C alkylene group).

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a photocurable liquid for optical three-dimensional modeling and a photocurable composition for optical three-dimensional modeling containing the same. The NC cutting method has been used for the production of various models and fixed objects such as a model for mold making, a model for copying, and a model for die-sinking electric discharge machining. In recent years, these have photopolymerizability. Attention has been focused on an optical three-dimensional modeling method in which a photocurable liquid for optical three-dimensional modeling or a composition thereof is irradiated with an energy ray to cure and mold a predetermined three-dimensional model. The present invention relates to a photocurable liquid for optical three-dimensional modeling applied to the above-described optical three-dimensional modeling method, particularly a photocurable liquid for optical three-dimensional modeling containing an unsaturated ester urethane and a composition thereof. Is.

[0002]

2. Description of the Related Art Conventionally, as a photocurable liquid for optical stereolithography containing unsaturated ester urethane, 1 mol of an n-valent polyisocyanate compound and a (meth) polyol having one free hydroxyl group in the molecule. Examples containing an unsaturated ester polyurethane obtained from n mol of acrylic acid partial ester (JP-A-2-145616, JP-A-1-20)
4915, JP-A-63-35550, JP-A-61-27.
6863, Japanese Patent Laid-Open No. 63-112551, Japanese Patent Publication No. 63-2
Unsaturation obtained from 1 mol of a partial ester obtained from triol or tetraol and (meth) acrylic acid and having one free hydroxyl group in the molecule, and 1 mol of isocyanatoalkyl (meth) acrylate Example of containing ester monourethane (Japanese Patent Laid-Open No. 4-5380)
There is 9).

However, the above-mentioned conventional photocurable liquids for optical three-dimensional modeling and compositions thereof have a drawback that the obtained three-dimensional molded article has poor physical properties, especially mechanical properties, and poor shape accuracy. There is. As a cause of deteriorating the shape accuracy of the obtained three-dimensional molded article, a volume change in the process of curing the photo-curable liquid for optical three-dimensional modeling or the composition thereof, the photo-curable liquid for optical three-dimensional modeling or its There is heterogeneity of the material in the composition, the shape of the desired three-dimensional molded item, etc., and when these are combined, uneven strain stress occurs inside the three-dimensional molded item. When concentrated on a specific portion or in a specific direction, deformation such as warpage, twisting, or crushing occurs, and structural destruction such as cracking or peeling occurs. In addition, such a three-dimensional molded article having inherent strain stress is potentially unstable in shape, and is likely to be deformed or structurally destroyed over time due to temperature conditions, use with load, or the like. In general, in a three-dimensional object obtained from a photocurable liquid for optical three-dimensional object molding or a composition thereof, one having a low glass transition temperature or a high elastic modulus and a high tensile elongation is likely to be deformed and has a high glass transition temperature. Those having a low tensile elongation are likely to cause structural failure.

[0004] Conventionally, attempts have been made to improve the physical properties of the obtained three-dimensional model, especially the thermal physical properties. For this purpose, for example, 1) an example of increasing the concentration of ethylenic double bonds in a photocurable liquid for optical three-dimensional modeling for the purpose of increasing the crosslink density of the three-dimensional model, 2) in addition to 1) above,
There is an example in which both an acrylate group and a methacrylate group are contained as a polymerizable group (JP-A-6-199962).
However, in these conventional examples, the volumetric shrinkage due to photocuring is rather increased, and the shape accuracy of the obtained three-dimensional model is further deteriorated. Further, in these conventional examples, the mechanical properties of the obtained three-dimensional model, particularly the tensile elongation is low, and as a result, the toughness value represented by the product of tensile strength and tensile elongation is commonly used as a plastics molding material. Compared with the toughness value of a three-dimensional model obtained from a thermoplastic resin such as an ABS resin, the three-dimensional model obtained can be used only for limited purposes.

[0005]

The problem to be solved by the present invention is that the conventional photocurable liquid for optical three-dimensional modeling and the composition thereof have physical properties, especially mechanical properties, of the obtained three-dimensional model. It is also bad in shape accuracy.

[0006]

However, the present inventors have
Photocurable liquid for optical stereolithography containing unsaturated ester urethane and its composition obtained from di (meth) acrylate or tri (meth) acrylate of tetravalent polyol and isocyanatoalkyl (meth) acrylate Focusing on unsaturated ester urethane, we studied the relationship between the chemical structure of such unsaturated ester urethane and the vinyl monomer used in combination with the shape accuracy, thermal properties, and mechanical properties of the resulting three-dimensional model. An unsaturated ester urethane having a specific structure, which has both an acryloyl group and a methacryloyl group as the functional group, and these two types of polymerizable groups are linked to the urethane group in a specific bonding manner,
It has been found that it is correct and preferable to use a specific vinyl monomer containing (meth) acrylic acid morpholide in a predetermined ratio.

That is, the present invention comprises an unsaturated ester urethane represented by the following formula 1 and the following vinyl monomer: unsaturated ester urethane / vinyl monomer = 10
The present invention relates to a photocurable liquid for optical three-dimensional modeling characterized by comprising a ratio of 0/25 to 100/150 (weight ratio) and a photocurable composition for optical three-dimensional modeling containing the same.

[0008]

(Equation 1)

(In the formula 1, X: a residue obtained by removing a hydroxyl group from a tetrahydric alcohol or a (poly) ethertetraol R ¹ : an alkylene group having 2 to 6 carbon atoms A: represented by the following formula 2 or formula 3 Organic group)

[0010]

(Equation 2)

(Equation 3)

(In the formula 3, R ^{2 is} an alkylene group having 2 to 6 carbon atoms)

Vinyl monomer: (meth) acrylic acid morpholide or a mixture of (meth) acrylic acid morpholide and diol di (meth) acrylate.

The unsaturated ester urethane represented by the formula 1 is obtained from 1 mol of tetrahydric alcohol or (poly) ether tetraol (hereinafter these are collectively referred to as tetraol) and 3 mol of acrylic acid. Urethane compound obtained by reacting 1 mol of methacryloyloxyalkyl isocyanate with 1 mol of all triacrylate (A in formula 1 is an organic group represented by formula 2, that is, acryloyloxy group), 2) 1 mol of tetraol And 1 mol of tetraol diacrylate obtained from 2 mol of acrylic acid and 2 mol of methacryloyloxyalkyl isocyanate are reacted to form a urethane compound (A in formula 1 is an organic group represented by formula 3, that is, methacryloyloxyalkyl). Is an aminocarboxyl group).

As the tetraol triacrylate, 1) starting materials are tetraacrylates and ether triacrylates of tetrahydric alcohols such as pentaerythritol triacrylate and diglycerin triacrylate, and 2) tetrahydric alcohols and ether tetraols. A triacrylate of polyoxyalkylene tetraol obtained by adding an alkylene oxide having 2 or 3 carbon atoms thereto.

As the tetraol diacrylate, 1) tetraol diacrylate obtained from 1 mol of tetraol and 2 mol of acrylic acid, 2) divalent of ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, etc. Reaction product of alcohol diglycidyl ether / acrylic acid = 1/2 (molar ratio), 3) Diglycidyl ether of acrylic diphenyl / acrylic acid such as 2,2-bishydroxyphenylpropane diglycidyl ether and resorcinol diglycidyl ether = 1/2 (molar ratio), 4) diglycidyl ether of polyether diol such as diethylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether / acrylic acid = 1/2 (molar ratio)
5) Reaction products of alicyclic diepoxide / acrylic acid = 1/2 (molar ratio) such as 5) vinylcyclohexane diepoxide, dicyclopentadiene oxide, and limonene dioxide.

The methacryloyloxyalkyl isocyanates to be reacted with the tetraol triacrylate or diacrylate as exemplified above include methacryloyloxyethyl isocyanate, methacryloyloxypropyl isocyanate and methacryloyloxy-2.
-Methylethyl isocyanate, methacryloyloxyhexyl isocyanate and the like can be mentioned, but among them, methacryloyloxyethyl isocyanate or methacryloyloxypropyl isocyanate can be advantageously used.

The present invention does not particularly limit the method for synthesizing the unsaturated ester urethane represented by the formula 1, and a known method for the synthesis thereof, for example, a method as described in JP-A-4-53809. Can be applied.

The unsaturated ester urethane represented by the formula 1 has a total of four organic groups which are linked to a tetraol by an ester bond, three of which are essential organic groups, and the remaining one is selected. It has a specific organic group. The three essential organic groups are two acrylate groups and one methacryloyloxyalkylaminocarboxylate group, and the remaining one optional organic group is an acrylate group represented by formula 2 or a formula 3. It is a methacryloyloxyalkylaminocarboxylate group shown.

According to the present invention, the methacryloyl group in the methacryloyloxyalkylaminocarboxylate group is different from the methacryloyl group contained in general methacrylic acid esters and is as high in photopolymerization as the acryloyl group due to the influence of the aminocarbonyl group. Have activity. Therefore, the unsaturated ester urethane represented by the formula 1 has a high photopolymerization activity in spite of having a methacryloyl group as a polymerizable group in the molecule, but it has an organic group which is linked to tetraol by an ester bond. As 2
Those having one acrylate group and two methacryloyloxyalkylaminocarboxylate groups are particularly preferable from the viewpoint of mechanical properties and thermal properties of the obtained three-dimensional model.

Even an unsaturated ester urethane in which a total of four organic groups are linked to tetraol by an ester bond is unsaturated such that the number of acrylate groups having high photopolymerization activity is less than 2 on average in the molecule. When ester urethane is used, since sufficient cross-linking is not formed in photopolymerization, the obtained three-dimensional modeled product has poor mechanical and thermal physical properties. On the contrary, if unsaturated ester urethane in which all of the four organic groups are all acrylate groups is used, the obtained three-dimensional molded article is inferior in thermal physical properties, although the photopolymerization activity is extremely high. Become. In the present invention, the unsaturated ester urethane represented by the formula 1, that is, 2 or 3 out of a total of 4 organic groups are originally acrylate groups having high photopolymerization activity and the remaining 2 or 1 The use of an unsaturated ester urethane, which is a methacryloyl group having a photopolymerization activity enhanced by a special bonding mode as described above, is effective in preparing a photocurable liquid for optical stereolithography and a high photopolymerization composition thereof. This is because it imparts activity and simultaneously imparts excellent mechanical and thermal physical properties to the three-dimensional model obtained at the same time.

The photocurable liquid for optical three-dimensional modeling of the present invention comprises an unsaturated ester urethane represented by the formula 1 and a vinyl monomer, and the vinyl monomer is (meth).
It is composed of a single system of acrylic acid morpholide or a mixed system of (meth) acrylic acid morpholide and diol di (meth) acrylate.

As the (meth) acrylic acid morpholide,
Acrylic acid morpholide and methacrylic acid morpholide are mentioned, but acrylic acid morpholide is preferable.

As the diol di (meth) acrylate used when mixed with (meth) acrylic acid morpholide, 1) ethylene glycol, propylene glycol,
1,4-butanediol, neopentyl glycol,
A diacrylate or dimethacrylate of an alkanediol having 2 to 6 carbon atoms such as 1,6-hexanediol,
2) Diacrylates or dimethacrylates of diols having an alicyclic hydrocarbon group having 6 to 12 carbon atoms such as cyclohexanedimethanol, cyclohexene dimethanol, dicyclopentyl dimethanol, and 3) Alkane diols and diols described above. Obtained by reacting an aliphatic lactone or an aliphatic oxycarboxylic acid having 4 to 6 carbon atoms,
Diacrylates or dimethacrylates of (poly) ester diols, such as diacrylates or dimethacrylates of 1,6-hexanediol hydroxycaprate, diacrylates or dimethacrylates of neopentyl glycol hydroxypivalate, 4) 2,2-bis Alkoxylated bisphenol having 2 to 3 carbon atoms in an alkoxyl group such as (hydroxyethoxyphenyl) propane, 2,2-bis (hydroxydiethoxyphenyl) propane, bis (hydroxypropoxyphenyl) methane and bis (hydroxydipropoxyphenyl) methane Examples thereof include diacrylates and dimethacrylates.

In the present invention, when a mixed system of (meth) acrylic acid morpholide and diol di (meth) acrylate is used as the vinyl monomer, (meth) acrylic acid morpholide is contained in the vinyl monomer in an amount of 50% by weight or more. The content is preferably contained in a ratio, and more preferably 70% by weight or more.

In the photocurable liquid for optical three-dimensional modeling of the present invention, the ratio of unsaturated ester urethane and vinyl monomer is such that unsaturated ester urethane / vinyl monomer = 1.
00/25 to 100/150 (weight ratio), but 10
It is preferably 0/40 to 100/100 (weight ratio).

The photocurable composition for optical three-dimensional modeling of the present invention contains the photocurable liquid for optical three-dimensional modeling as described above and a filler. This filler is one or more selected from solid fine particles having an average particle diameter of 0.1 to 50 μm and inorganic fiber whiskers having an average fiber length of 1 to 70 μm. When using solid fine particles as the filler, those having an average particle diameter of 3 μm or more are preferable, and when using inorganic fiber whiskers as the filler, the average fiber diameter is 0.3 to 1 μm and the average fiber length is 1 μm.
It is preferably 0 μm or more. Such fillers include 1) silica, alumina, clay, calcium carbonate,
Inorganic solid particles such as glass beads, 2) Organic solid particles such as crosslinked polystyrene, polymethylmethacrylate, polymethylsiloxane, 3) Potassium titanate fiber, magnesium sulfate fiber, magnesium borate fiber, aluminum borate fiber, carbon fiber, etc. Inorganic fiber whiskers can be mentioned. These fillers are contained in an amount of 50 to 400 parts by weight per 100 parts by weight of the photocurable liquid for optical three-dimensional modeling of the present invention. These fillers may be used alone or in combination of two or more, but it is preferable to use both inorganic solid fine particles and inorganic fiber whiskers as the filler. In this case, the photocurable liquid 100 for optical three-dimensional modeling of the present invention is used. 40 to 300 parts by weight of inorganic solid fine particles and 10 to 1 of inorganic fiber whiskers per part by weight.
It is more preferable to use it in a ratio of 00 parts by weight.

When the photocurable liquid for optical three-dimensional modeling or the composition thereof of the present invention is subjected to optical three-dimensional modeling, a photopolymerization initiator is previously added to them. The present invention does not limit the kind of the photopolymerization initiator to be used, but the photopolymerization initiator includes 1) carbonyl compounds such as benzoin, α-methylbenzoin, anthraquinone, chloroanthraquinone and acetophenone, and 2) diphenyl. Sulfur compounds such as sulfide, diphenyl disulfide and dithiocarbamate, 3) α-chloromethylnaphthalene,
Examples thereof include polycyclic aromatic compounds such as anthracene. The content of the photopolymerization initiator in the photocurable liquid for optical three-dimensional modeling and the composition thereof is usually 0.1 to 10 parts by weight per 100 parts by weight of the photocurable liquid for optical three-dimensional modeling. , Preferably 1 to 5 parts by weight.
A photosensitizer such as n-butylamine, triethanolamine, N, N-dimethylaminobenzenesulfonic acid diallylamide, or N, N-dimethylaminoethyl methacrylate can be used together with the photopolymerization initiator.

The present invention does not particularly limit the optical three-dimensional modeling method to which the photocurable liquid for optical three-dimensional modeling of the present invention or the composition thereof is applied. Various methods are known as such an optical three-dimensional molding method (JP-A-56-1444).
78, JP-A-60-247515, JP-A-1-2049.
15, JP-A-3-41126, etc.), in which, for example, a cured layer of a photocurable liquid for optical three-dimensional modeling or a composition thereof is first formed, and then an optical three-dimensional layer is newly formed on the cured layer. There is a method of forming a desired three-dimensional model by repeating the operation of supplying a photocurable liquid for modeling or a composition thereof to form a cured layer thereof. This three-dimensional object can be further post-cured if necessary. Examples of energy rays used for curing include visible rays, ultraviolet rays, and electron rays, and ultraviolet rays are preferable.

Hereinafter, the constitution and effects of the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples. In the following Examples and Comparative Examples, parts mean parts by weight and% means% by weight unless otherwise specified.

[0030]

【Example】

Test Category 1 (Preparation of photocurable liquid for optical three-dimensional modeling) -Preparation of Examples 1-8 and Comparative Examples 1-4 Unsaturated ester urethane A according to the synthesis method described in JP-A-4-53809. -1 (2,2-bishydroxyphenyl propane diglycidyl ether 1 mol and tetraol diacrylate obtained by reacting acrylic acid 2 mol, and methacryloyloxyethyl isocyanate, tetraol diacrylate / methacryloyloxyethyl isocyanate = (Reacted at a molar ratio of 1/2) was synthesized. 100 parts of the synthesized unsaturated ester urethane A-1 and 6 parts of acrylic acid morpholide
7 parts were mixed and dissolved at room temperature to prepare a photocurable liquid for optical stereolithography of Example 1. In the same manner as in Example 1, the photocurable liquids for optical stereolithography of Examples 2 to 8 and Comparative Examples 1 to 4 were prepared. These compositions are summarized in Table 1.

[0031]

[Table 1]

In Table 1, A-1: Tetraol diacrylate / methacryloyloxyethyl isocyanate obtained by reacting 1 mol of 2,2-bishydroxyphenylpropane diglycidyl ether with 2 mol of acrylic acid = 1/2 ( Molar ratio of reactant A-2: diethylene glycol diglycidyl ether 1
Reaction product of tetraol diacrylate / methacryloyloxyethyl isocyanate = 1/2 (molar ratio) obtained by reacting 2 mol of acrylic acid with acrylic acid A-3: pentaerythritol diacrylate / methacryloyloxypropyl isocyanate = 1/2 (Mole ratio) reaction product A-4: Diglycerin triacrylate / methacryloyloxyethyl isocyanate = 1/1 (molar ratio) reaction product B-1: acrylic acid morpholide B-2: methacrylic acid morpholide C-1: di Cyclopentyl dimethylene diacrylate C-2: neopentyl glycol hydroxypivalate diacrylate R-1: 2,2-bis- (p-hydroxyphenyl) propane diglycidyl ether reacted with 1 mol of methacrylic acid 2 mol Tetrao obtained by Dimethacrylate / methacryloyloxyethyl isocyanate = 1 /
2 (molar ratio) of reactant R-2: diethylene glycol diglycidyl ether 1
Tetraol diacrylate / acryloyloxyethyl isocyanate = 1/2 (molar ratio) reaction product obtained by reacting 2 mol of acrylic acid with acrylic acid R-3: pentaerythritol monoacrylate / methacryloyloxypropyl isocyanate = 1/3 ( (Mole ratio) R-4: Diglycerin trimethacrylate / acryloyloxyethyl isocyanate = 1/1 (Mole ratio)

Test Category 2 (Production and evaluation of three-dimensional object) 1) Production of three-dimensional object Mainly composed of a three-dimensional NC table equipped with a container and a helium / cadmium laser light (output 25 mW, wavelength 3250 angstrom) control system. The optical three-dimensional modeling apparatus described above was used. One in which 3 parts of 1-hydroxycyclohexyl phenyl ketone was dissolved as a photopolymerization initiator per 100 parts of the photocurable liquid for optical three-dimensional modeling prepared in Test Category 1 (hereinafter, simply referred to as a mixed solution) Was charged, and the mixed solution was supplied from the container to a horizontal plane (X-Y axis plane) with a thickness of 0.10 mm, and the surface (X-
The helium-cadmium laser beam focused from the direction (Z-axis direction) perpendicular to the Y-axis plane) was scanned to cure the photocurable liquid for optical three-dimensional modeling. The mixed solution was newly supplied on the cured product in a thickness of 0.10 mm and cured in the same manner. Thereafter, in the same manner, a total of 200 layers were laminated to form a conical solid body having a design value of a bottom surface diameter of 200.00 mm and a height of 20.00 mm. After washing the obtained model with isopropyl alcohol, it was cleaned with a 3Kw ultraviolet lamp.
It was irradiated for 0 minutes and post-cured to obtain a three-dimensional object.

2) Evaluation of mechanical properties In the same manner as in 1), a dumbbell shape having a thickness of 3 mm specified in JIS-K7113 is optically modeled, and the modeled object is washed with isopropyl alcohol and then at 98 ° C. for 2 hours. Post curing was carried out by heating for a period of time to prepare a test piece. Three same test pieces were prepared, and the tensile strength, the tensile elastic modulus, and the tensile elongation were measured at a tensile speed of 5 mm / sec according to JIS-K7113. Further, a toughness value (Tf) represented by tensile strength × tensile elongation was calculated. The results are shown in Table 2 as an average value of three test pieces.

3) Evaluation of thermal physical properties In the same manner as the test piece of 2), a 55 mm × 10 mm × 2 mm flat plate type test piece was prepared. The dynamic viscoelasticity of this test piece was measured, and the glass transition temperature (T
g) was determined. The results are shown in Table 2.

4) Measurement of shape Regarding the three-dimensional object obtained in 1), 2 on the XY axis plane.
The two-dimensional figure a was vertically projected, and the two-dimensional figure b was horizontally projected on arbitrary 50 planes perpendicular to the X-Y axis plane, and the following measurements were performed on these projections. The results are shown in Table 3. The two-dimensional figure a obtained here is a circle, and the two-dimensional figure b is a triangle. Two-dimensional figure a: Draw 50 arbitrary straight lines passing through the center of gravity of the projected view, measure the distance between two points intersecting the contour of the projected view,
For these measured values, the average value, maximum value, minimum value and standard deviation were calculated. Two-dimensional figure b: The area of 50 projection views was measured, and the average value, maximum value, minimum value and standard deviation were calculated for these measured values.

[0037]

[Table 2]

[0038]

[Table 3]

In Table 2 and Table 3, Comparative Example 5: ABS resin (Diapet HF-5 manufactured by Mitsubishi Rayon Co., Ltd.) Incidentally, a test piece for measuring mechanical properties and a test for measuring thermal physical properties of Comparative Example 5. Cylinder temperature 200 ℃, mold temperature 60
Injection molded at ° C. The size and shape of the injection-molded product are the same as those in the evaluation of mechanical properties in 2) and the evaluation of thermal properties in 3).

Test Category 3 (Preparation of Photocurable Composition for Optical Stereoscopic Modeling) Examples 9 to 12 and Comparative Examples 6 to 91 1) Preparation of Photocurable Composition for Optical Stereoscopic Modeling In Test Category 1 100 parts of the photocurable liquid for optical three-dimensional modeling prepared in Example 1, 3 parts of a photopolymerization initiator, 200 parts of inorganic solid fine particles and 50 parts of inorganic fiber whiskers were put into a mixing tank equipped with a biaxial stirrer, Stir and mix until uniform. The stirred mixture was filtered through a 50 μm filter to prepare a photocurable composition for optical stereolithography of Example 9. In the same manner as in Example 9, the photocurable compositions for optical stereolithography of Examples 10 to 12 and Comparative Examples 6 to 9 were prepared. These compositions are summarized in Table 4.

[0041]

[Table 4]

In Table 4, D-1: Aluminum borate whiskers (Arborex YS-4 manufactured by Shikoku Kasei Co., average fiber diameter 0.8 μm × average fiber length 20 μm) E-1: Glass beads (manufactured by Toshiba Barodini Co., Ltd. GB-
730 C, average particle size 30 μm) E-2: Aluminum hydroxide (B-1 manufactured by Nippon Light Metal Co., Ltd.)
03, average particle size 8 μm) F-1: 1-hydroxycyclohexyl phenyl ketone

Test Category 4 (Preparation and Evaluation of 3D Model) 1) Preparation of 3D Model Using the photocurable composition for optical 3D model prepared in Test Category 3, preparation of 3D model in Test Category 2 In the same way as
Design value is bottom surface diameter 200.00mm, height 20.00mm
I created a three-dimensional cone. The obtained modeled product was washed with isopropyl alcohol, heated at 98 ° C. for 2 hours and post-cured to obtain a three-dimensional modeled product.

2) Measurement of mechanical properties, thermal properties and shape Test pieces prepared separately in the same manner as in Test Category 2 and 1)
The mechanical properties, thermal properties, and shape of the three-dimensional molded object manufactured in Section 3 were measured. The results are shown in Tables 5 and 6.

[0045]

[Table 5]

[0046]

[Table 6]

In Tables 5 and 6, cracks were found on the surfaces of the three-dimensional molded articles of Comparative Examples 6 and 8.

[0048]

As is apparent from the above, the present invention described above has an effect that it is possible to obtain a three-dimensional object having excellent mechanical properties, thermal properties, and shape accuracy.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI technical display area B29K 101: 00 105: 24

Claims (6)

[Claims] 1. An unsaturated ester urethane represented by the following formula 1 and the following vinyl monomer, wherein the unsaturated ester urethane / the vinyl monomer = 100/25 to 100:
A photocurable liquid for optical three-dimensional modeling, characterized in that the ratio is / 150 (weight ratio). (Equation 1) (In Formula 1, X: a residue obtained by removing a hydroxyl group from a tetrahydric alcohol or (poly) ethertetraol R ¹ : an alkylene group having 2 to 6 carbon atoms A: an organic group represented by the following Formula 2 or Formula 3) [Formula 2] (Equation 3) (In the formula 3, R ^{2 is} an alkylene group having 2 to 6 carbon atoms) Vinyl monomer: (meth) acrylic acid morpholide or a mixture of (meth) acrylic acid morpholide and diol di (meth) acrylate 2. The unsaturated ester urethane is represented by formula A in formula 1.
The photocurable liquid for optical three-dimensional modeling according to claim 1, which is an unsaturated ester urethane in which is an organic group represented by formula 3. 3. The photocurable liquid for optical three-dimensional modeling according to claim 1 or 2, wherein the vinyl monomer contains 50% by weight or more of (meth) acrylic acid morpholide. 4. A diol di (meth) acrylate is a di (meth) acrylate of an alkanediol having 2 to 6 carbon atoms, a di (meth) acrylate of a diol having an alicyclic hydrocarbon group having 6 to 12 carbon atoms, A di (meth) acrylate of an ester diol obtained by reacting an alkanediol having 2 to 6 carbon atoms with an oxycarboxylic acid having 4 to 6 carbon atoms and a di (meth) alkoxylated bisphenol having 2 to 3 carbon atoms in an alkoxyl group. ) One or more selected from acrylates, The photocurable liquid for optical three-dimensional modeling according to claim 1, 2 or 3. 5. Solid fine particles having an average particle diameter of 0.1 to 50 μm and an average fiber length of 1 to 70 per 100 parts by weight of the photocurable liquid for optical stereolithography according to claim 1, 2, 3 or 4.
A photocurable composition for optical three-dimensional modeling, containing one or more fillers selected from inorganic fiber whiskers having a diameter of 50 μm in a proportion of 50 to 400 parts by weight. 6. Inorganic fiber whiskers 10 to 10 as a filler per 100 parts by weight of a photocurable liquid for optical three-dimensional modeling.
The photocurable composition for optical three-dimensional modeling according to claim 5, which is contained in an amount of 100 parts by weight and 40 to 300 parts by weight of inorganic solid fine particles.