JP2725136B2 - Optical three-dimensional molding method and three-dimensional molded object - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an optical three-dimensional object forming method and a three-dimensional object obtained by the method. The NC cutting method has been used to produce various models and fixed objects such as mold working models, copying machining models, sculpture electric discharge machining models, and the like. Attention has been paid to a method of irradiating an energy ray to a composition for photostereolithography (photopolymerizable composition) to cure the composition into a predetermined shape. The present invention, among such optical three-dimensional molding methods, after forming an initial cured layer by irradiating an energy-cured layer of the uncured optical three-dimensional molding composition, and then newly on the cured layer A method of supplying a layer of an uncured optical three-dimensional structure composition, irradiating the layer with an energy beam to form a next cured layer, and forming a three-dimensional structure having a predetermined shape (hereinafter, referred to as “ Such an optical three-dimensional molding method is referred to as a lamination curing method). In the composition for optical three-dimensional molding provided for optical three-dimensional molding, good photopolymerization reactivity and excellent thermal physical properties of the obtained three-dimensional molded object are simultaneously obtained. The present invention relates to a method that can be applied and a three-dimensional structure obtained by the method.

[0002]

2. Description of the Related Art Heretofore, as a composition for optical stereolithography to be subjected to an optical stereolithography method, a composition containing a monomer or oligomer having an α, β-ethylenically unsaturated group and a photopolymerization initiator has been known. Have been. Examples of such a monomer or oligomer having an α, β-ethylenically unsaturated group include:
(Meth) acrylic esters such as alkyl (meth) acrylate, diol di (meth) acrylate, trioltri (meth) acrylate, and tetraoltetra (meth) acrylate (JP-A-3-15520); polyether polyols and polyester polyols Polyurethane poly (meth) acrylates obtained from a polyol compound, a diisocyanate compound and a hydroxyalkyl (meth) acrylate, and polyurethane poly (meth) acrylates obtained from the above polyol compound, a diisocyanate compound and a triol di (meth) acrylate ( JP-A-2-145616, JP-A-1-20
4915).

However, in the above-mentioned lamination curing method, among the above-mentioned conventional optical three-dimensional molding compositions, those using a monomer or oligomer having an acrylate group as a polymerizable group are not polymerizable groups. As compared with those using a monomer or oligomer having a methacrylate group, the photopolymerization reactivity is good, but there is a drawback that the obtained three-dimensionally formed product has poor thermal properties, especially low heat deformation temperature. In order to improve the thermal properties, to increase the crosslink density of the three-dimensional object obtained by photopolymerization,
Attempts have been made to increase the concentration of ethylenic double bonds in the composition for optical stereolithography. However, such a method is disadvantageous because reaction shrinkage during curing by photopolymerization increases. Further, among the conventional optical stereolithography compositions as described above, those using a monomer or oligomer having a methacrylate group as a polymerizable group,
Compared to those using a monomer or oligomer having an acrylate group as a polymerizable group, the obtained three-dimensionally formed product has good thermal properties, but has a disadvantage of poor photopolymerization reactivity. When a composition for optical stereolithography containing a known monomer or oligomer having an α, β-ethylenically unsaturated group is subjected to a lamination curing method, its photopolymerization reactivity is poor.
Alternatively, the thermal properties of the resulting three-dimensional object are poor.

[0004]

The problem to be solved by the present invention is that when a conventional optical three-dimensional molding composition is subjected to a lamination curing method, its photopolymerization reactivity is poor or the three-dimensional This is a point that the thermal properties of the formed object are poor.

[0005]

Means for Solving the Problems Thus, the present inventors have
As a result of studying to solve the above-mentioned problems, in the lamination curing method, a specific unsaturated urethane, a specific vinyl monomer, a specific filler and / or a specific shrinkage reducing agent are each contained at a predetermined ratio. It has been found that it is correct and suitable to use the composition for optical stereolithography contained therein.

That is, according to the present invention, after an uncured optical three-dimensional structure forming layer is irradiated with energy rays to form a first cured layer, a new uncured optical three-dimensional structure is formed on the cured layer. In a method of forming a three-dimensional structure by repeatedly supplying a layer of the molding composition and irradiating the layer with an energy ray to form a next cured layer (lamination curing method), an optical three-dimensional molding As a composition for use, an unsaturated urethane represented by the following formula 1, a (meth) acrylate as a vinyl monomer copolymerizable with the unsaturated urethane, and an inorganic solid having an average particle diameter of 0.1 to 50 μm. One or more kinds of fillers selected from fine particles and inorganic fiber whiskers having an average fiber length of 1 to 70 μm, and / or an organic polymer as a shrinkage reducing agent and a photopolymerization initiator, and the unsaturated urethane / Bi Nyl monomer = 10 / 90-90 /
10 (weight ratio), the filler is 300 parts by weight or less per 100 parts by weight of the total amount of the unsaturated urethane and the vinyl monomer, and the shrinkage reducing agent is 100 parts by weight of the total amount of the unsaturated urethane and the vinyl monomer. The present invention relates to a method characterized by using a composition for optical three-dimensional modeling containing 100 parts by weight or less per part by weight and a three-dimensional molded article obtained by this method.

[0007]

(Equation 1)

In the formula 1, X ² : a residue obtained by removing an isocyanate group from a diisocyanate Y ³ : a residue obtained by removing a hydroxyl group from a triol Y ⁴ : a residue R ⁵ , R ⁶ , R ^{7 obtained} by removing a hydroxyl group from a diol : H or CH ₃ not simultaneously the same]

The unsaturated urethane represented by the formula (1) includes 1)
Triol diacrylate / diol monomethacrylate / diisocyanate = 1/1/1 (molar ratio) reactant, 2) triol dimethacrylate / diol monoacrylate / diisocyanate = 1/1/1 (molar ratio) reactant, 3) Triacrylate monoacrylate / monomethacrylate / diol monoacrylate or diol monomethacrylate / diisocyanate = 1/1
/ 1 (molar ratio) reactants.

For convenience, diols, dimethacrylates and monoacrylates / monomethacrylates of triols are hereinafter generally referred to as di (meth) acrylates of triols. The di (meth) acrylates of triols include 1) glycerin and trimethylolpropane. , 5-
Methyl-1,2,4-heptanetriol, 1,2,6
-Di (meth) of trihydric alcohol such as hexanetriol
Acrylates and 2) di (meth) acrylates of (poly) ether triols such as ethylene glycol monoglyceryl ether, (poly) ethoxylated trimethylolpropane, (poly) ethoxylated glycerin and the like.
Among such triol di (meth) acrylates,
As di (meth) acrylates of trihydric alcohol, glycerin diacrylate, glycerin dimethacrylate, glycerin monoacrylate / monomethacrylate can be advantageously used, and (poly) ether in di (meth) acrylates of (poly) ether triol Triols having a molecular weight of 100 or less per hydroxyl group contained in the molecule can be advantageously used.

Similarly, for convenience, monoacrylates and monomethacrylates of diols are hereinafter collectively referred to as mono (meth) acrylates of diols. The mono (meth) acrylates of diols include 1) 2-hydroxyethyl (meth) acrylate, C2 to C6 alkanediol mono (meth) acrylates, such as hydroxypropyl (meth) acrylate and 1,6-hexanediol mono (meth) acrylate; 2) diethylene glycol mono (meth) acrylate; tripropylene glycol mono Mono (meth) polyalkylene glycol having 2 or 3 carbon atoms in the alkylene group, such as (meth) acrylate
There are acrylates. Mono (meta) of such diol
Among acrylates, 2-hydroxyethyl acrylate and methacrylate can be advantageously used as the mono (meth) acrylate of alkanediol, and the number of oxyalkylene groups in the mono (meth) acrylate of polyalkylene glycol is 5 or less.

Examples of the diisocyanate to be reacted with the triol di (meth) acrylate and the diol mono (meth) acrylate as described above include 1) various tolylene diisocyanates, methylene-bis- (4-phenyl isocyanate) and the like. Aromatic diisocyanates, 2) Aliphatic diisocyanates or alicyclic diisocyanates such as hexamethylene diisocyanate, methylene bis (4-cyclohexyl isocyanate), 3)
Aliphatic and alicyclic diisocyanates such as 4-isocyanatomethyl-1-isocyanato-1-methyl-cyclohexane, 5-isocyanatomethyl-1-isocyanato-1,1-dimethyl-5-methyl-cyclohexane (isophorone diisocyanate) There is kind.

The unsaturated urethane represented by the formula (1) is an asymmetric unsaturated urethane in which R ^{5 to} R ⁷ in the formula (1) are not simultaneously a hydrogen atom or a methyl group. As the diisocyanate used for synthesizing such an asymmetric unsaturated urethane, a diisocyanate having an isocyanate group affected by a sterically hindered substituent and an isocyanate group not affected by a sterically hindered substituent, or an aliphatic hydrocarbon It is preferable to use diisocyanates having isocyanate groups having mutually different reactive groups, such as those having an isocyanate group bonded to a group and an isocyanate group bonded to an aromatic hydrocarbon group.
4-tolylene diisocyanate, isophorone diisocyanate, 4-isocyanatomethyl-1-isocyanato-
1-methyl-cyclohexane and the like.

The present invention does not particularly limit the method for synthesizing the unsaturated urethane. For the synthesis, a known method, for example, a method described in JP-A-4-53809 can be applied. In the synthesis of the asymmetric unsaturated urethane shown in the following, 1 mole of di (meth) acrylate of triol and 1 mole of diisocyanate having an isocyanate group having different reactivity are reacted in advance to obtain unsaturated urethane monoisocyanate. A method of reacting a mono (meth) acrylate of a diol different from the above is preferable.

The unsaturated urethane represented by the formula (1) has both an acryloyl group and a methacryloyl group as polymerizable groups. Having such two different polymerizable groups is extremely effective in improving the photopolymerization reactivity and the thermal physical properties of a three-dimensional structure obtained by photopolymerizing an optical three-dimensional structure composition containing the same. is there. Among the unsaturated urethanes represented by the formula 1, those containing two acryloyl groups among the three polymerizable groups contained therein are preferable.
The relationship between the number of the polymerizable groups contained in one molecule of the unsaturated urethane and the molecular weight of the unsaturated urethane per one polymerizable group also affects the improvement of the photopolymerization reactivity and the thermal properties. Unsaturated urethanes which are preferable for obtaining photopolymerization reactivity and thermal properties suitable for practical use have a molecular weight of 100 to 6 per polymerizable group.
The unsaturated urethane having a molecular weight of 00, more preferably an unsaturated urethane having a molecular weight of 150 to 500 per one polymerizable group.

In the present invention, a (meth) acrylate, ie, an acrylate and / or a methacrylate, is used as a vinyl monomer copolymerizable with the unsaturated urethane represented by the formula (1). This includes, for example, 1) alkyl acrylates such as butyl acrylate and 2-ethylhexyl acrylate, 2) alkyl methacrylates such as methyl methacrylate, ethyl methacrylate, and isobutyl methacrylate; 3) ethylene glycol diacrylate; 4-
Dihydric alcohol diacrylates such as butanediol diacrylate; 4) dihydric alcohol dimethacrylates such as 1,2-propylene glycol dimethacrylate and 1,6-hexanediol dimethacrylate; 5)
Trihydric alcohol triacrylates such as glycerin triacrylate and trimethylolpropane triacrylate; 6) trihydric alcohol trimethacrylates such as glycerin trimethacrylate and trimethylolethane trimethacrylate; 7) trimethylolpropane diacrylate / monomethacrylate Mixed (meth) acrylates of trihydric alcohols such as glycerin monoacrylate and dimethacrylate; 8) tetraesters of tetrahydric alcohols such as pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate and pentaerythritol diacrylate dimethacrylate;
9) Ester of polyether polyol obtained from polyether polyol obtained by adding alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide, etc. to the above-mentioned dihydric alcohol and acrylic acid, methacrylic acid, or a mixed acid thereof; 10) Polyester polyols obtained by adding a polyester polyol obtained by adding an aliphatic lactone such as caprolactone or butyrolactone to the above-mentioned dihydric alcohol and acrylic acid, methacrylic acid, or a mixed acid thereof, and the like.

As the vinyl monomer exemplified above, it is preferable to use a mixture of an acrylic ester and a methacrylic ester, and to use a mixed unsaturated acid ester obtained from a polyol and acrylic acid and methacrylic acid. Is more preferred. In this case, the ratio of the acryl group to the methacryl group is such that the acryl group / methacryl group = 9/1 to 1 in both the mixture and the mixed unsaturated acid ester.
/ 9 (molar ratio), preferably 8/2
More preferably, it is set to be 5/5 (molar ratio).

In the composition for stereolithography used in the present invention, the ratio of unsaturated urethane and a vinyl monomer copolymerizable with the unsaturated urethane is such that the ratio of the unsaturated urethane / the vinyl monomer = It is 10 / 90-90 / 10 (weight ratio), preferably 30 / 70-70 / 30 (weight ratio). If the ratio of both is less than 10/90 (weight ratio), the physical properties of the three-dimensional structure obtained by photopolymerization are inferior, and conversely, 90/1
If it exceeds 0 (weight ratio), the viscosity of the composition becomes too high.

The composition for stereolithography used in the present invention contains a photopolymerization initiator. In the present invention, the type of the photopolymerization initiator to be used is not particularly limited. Examples of the photopolymerization initiator include: 1) benzoin, α-methylbenzoin, anthraquinone, chloranthraquinone,
There are carbonyl compounds such as acetophenone, 2) sulfur compounds such as diphenyl sulfide, diphenyl disulfide and dithiocarbamate, and 3) polycyclic aromatic compounds such as α-chloromethylnaphthalene and anthracene. The content of these photopolymerization initiators in the composition for optical three-dimensional modeling is usually 0.1 to 10 parts by weight, based on 100 parts by weight of the total amount of the unsaturated urethane and the vinyl monomer, Preferably, the amount is 1 to 5 parts by weight. Along with the photopolymerization initiator, a photosensitizer such as n-butylamine, triethanolamine, N, N-dimethylaminobenzenesulfonic acid diallylamide, and N, N-dimethylaminoethyl methacrylate can be used.

The composition for optical three-dimensional modeling used in the present invention is composed of inorganic solid fine particles having an average particle diameter of 0.1 to 50 μm and an average fiber length of 0.1 to 50 μm for the purpose of reducing the reaction shrinkage due to curing during photopolymerization of the composition. It contains a filler and / or a shrinkage reducing agent selected from inorganic fiber whiskers of 1 to 70 μm. When inorganic solid fine particles are used as such a filler, the average particle diameter is preferably 1 μm or less, more preferably 0.3 μm or less. Such fillers include 1) silica, alumina, clay,
There are inorganic solid fine particles such as calcium carbonate, 2) inorganic solid fine particles composed of metal fine particles such as aluminum and iron, and 3) inorganic fiber whiskers such as potassium titanate fiber, magnesium sulfate fiber and carbon fiber. When these fillers are contained, the amount is usually 300 parts by weight or less, preferably 1 to 100 parts by weight, based on 100 parts by weight of the total amount of the unsaturated urethane and the vinyl monomer. These fillers can be used alone or in combination of two or more.

The composition for optical stereolithography used in the present invention is an organic polymer used as a shrinkage reducing agent together with or instead of a filler for the purpose of reducing the reaction shrinkage accompanying curing during photopolymerization of the composition. Can be contained. Such an organic polymer is obtained by polymerizing a monomer containing a vinyl aromatic hydrocarbon as its monomer component, such as 1) polystyrene, styrene-divinylbenzene copolymer, styrene-butadiene copolymer and the like. Polymer, 2)
Polyalkyl (meth) acrylates such as polymethyl methacrylate and polyisobutyl acrylate; 3) vinyl polymers such as polyvinyl acetate, polyvinyl benzoate and polyvinyl chloride; 4) poly ε-caprolactone;
Aliphatic polyesters such as polypropylene adipate and polyneopentyl adipate; 5) linear polyorganosiloxanes; and polyorganosiloxane derivatives such as polyorganosiloxane-polyvinyl graft copolymers.

Among the above-mentioned organic polymers, a thermoplastic polymer that dissolves in a mixed solution of unsaturated urethane and a vinyl monomer to be used is preferable, and a polymer that stably dissolves at room temperature is more preferable. Such a thermoplastic polymer can be appropriately selected from the above-mentioned aliphatic polyesters and polyalkyl (meth) acrylates. Among them, those having a melting point of 30 to 100 ° C and a glass transition temperature of 70 ° C or less are particularly preferred. Is preferable, and the glass transition temperature is 50 ° C.
The following are more preferred. When these thermoplastic polymers are contained, the total amount of unsaturated urethane and vinyl monomer is 100 parts by weight, so that it is 100 parts by weight or less, preferably 10 to 50 parts by weight. .

When a composition for optical stereolithography containing a thermoplastic polymer dissolved in a mixed solution of unsaturated urethane and a vinyl monomer is photopolymerized, a crosslinked structure is formed by polymerization. The dissolved thermoplastic polymer undergoes phase separation and is dispersed as solid fine particles. The rate at which the thermoplastic polymer undergoes phase separation in the photopolymerization system and the particle size of the solid fine particles formed are mainly affected by the type of the thermoplastic polymer and the unsaturated urethane used and the photopolymerization rate,
In the photopolymerization system, the thermoplastic polymer is phase-separated and dispersed as solid fine particles, whereby the effect of reducing the reaction shrinkage accompanying the curing by the photopolymerization is exerted. In the present invention, the particle diameter of the solid fine particles formed from the thermoplastic polymer can be arbitrarily controlled, but the particle diameter is preferably 0.1 to 100 μm, preferably 1 to 10 μm.
m is more preferable. In this case, it is particularly preferable to use the above-mentioned filler in combination for the purpose of promoting the preferable formation of solid fine particles of a thermoplastic polymer.

The optical three-dimensional molding method of the present invention using the optical three-dimensional molding composition as described above is a lamination curing method as described above, and the lamination curing method is an uncured optical three-dimensional molding composition. After the first cured layer is formed by irradiating the material layer with an energy ray, a new uncured composition for optical three-dimensional modeling is supplied on the cured layer, and the composition is irradiated with an energy ray to form a next composition. This is a method of forming a three-dimensionally shaped object having a predetermined shape by repeatedly performing the operation of forming a cured layer of the above, and further post-curing as necessary (Japanese Patent Laid-Open No. 56-1).
44478, JP-A-60-247515, JP-A-1-2
04915, JP-A-3-41126). Examples of the energy beam used include visible light, ultraviolet light, and electron beam, and ultraviolet light is preferable.

[0025]

EXAMPLES Test section 1 (Preliminary synthesis) 72 parts (1.0 mol, parts by weight, hereinafter the same) of acrylic acid and 1 part of triethylamine as a catalyst were placed in a reaction vessel and stirred at 60 ° C. while adding glycidyl. 142 parts (1.0 mol) of methacrylate were added dropwise over 30 minutes. Then, the reaction system was maintained at 70 ° C. for 5 hours to complete the synthesis. The oxirane oxygen content of the reaction was quantified but not detected. The product obtained here was glycerin monoacrylate / monomethacrylate, having an acid value of 1.8, a hydroxyl value of 263, and a saponification value of 522.

Test Category 2 (Synthesis of Unsaturated Urethane) 184 parts (1.0 mol) of commercially available glycerin diacrylate, 222 parts (1.0 mol) of isophorone diisocyanate, 0.5 part of di-n-butyltin dilaurate and 200 parts of toluene was placed in a reaction vessel and stirred at 60 ° C. During the reaction, the contents in the reaction system were sampled, and the amount of the isocyanate residue was successively analyzed. When the amount of the isocyanate residue became 1/2 of the theoretical amount before the reaction, the reaction was stopped. Next, toluene was distilled off from the reaction mixture under reduced pressure to recover 195 parts of toluene. The product obtained here was an unsaturated urethane monoisocyanate bonded by glycerin diacrylate / isophorone diisocyanate = 1/1 (molar ratio), and the yield was 407 parts. 406 parts (1.0 mol) of the unsaturated urethane monoisocyanate obtained above, 130 parts (1.0 mol) of 2-hydroxyethyl methacrylate, 200 parts of toluene and di-n
0.2 parts of butyltin dilaurate are placed in a reaction vessel, and
The mixture was stirred at 0 ° C for 2 hours to complete the synthesis. Toluene was distilled off from the reaction product under reduced pressure to obtain 540 parts of unsaturated urethane C. Similarly to the case of the unsaturated urethane C, the unsaturated urethane D, the unsaturated urethane R-3, and the unsaturated urethane R-
4 and unsaturated urethane R-5 were obtained. Table 1 shows the amounts of the raw materials used in the synthesis. Table 2 summarizes the contents of the obtained unsaturated urethane.

[0027]

[Table 1]

In Table 1, numerical values: upper part: part, lower part: mole * 2: isophorone diisocyanate * 3: glycerin monoacrylate / monomethacrylate obtained by preliminary synthesis * 4: glycerin diacrylate * 5: glycerin dimethacrylate * 6: 2-hydroxyethyl methacrylate * 7: 2-hydroxyethyl acrylate

[0029]

[Table 2]

In Table 2, A: acryloyl group M: methacryloyl group

Test Category 3 (Examples and Comparative Examples and Evaluations) Examples 1 to 8 and Comparative Examples 1 to 50 50 parts of unsaturated urethane, 50 parts of vinyl monomer and light described in Table 3 or Table 4 5 parts of the polymerization initiator and 100 parts of the filler to be added were placed in a mixing vessel, and stirred until uniform using a paint shaker to prepare a composition for optical three-dimensional modeling. In the case of adding a thermoplastic polymer, 30 parts of the thermoplastic polymer were previously uniformly dissolved in a mixed solution composed of 50 parts of unsaturated urethane and 50 parts of a vinyl monomer. An uncured layer is formed by using an optical three-dimensional modeling apparatus mainly including a three-dimensional NC table equipped with a container filled with the optical three-dimensional modeling composition and a helium / cadmium laser beam (wavelength: 3250 Å) control system. A lamination curing method in which the mixed solution is supplied in a thickness of 0.2 mm, and the surface is irradiated with a helium-cadmium laser beam focused from a vertical direction to cure the uncured layer, thereby repeatedly performing a lamination curing method. Thus, a disk having a diameter of 150 mm and a thickness of 10 mm was formed. The time required for molding was measured for each optical three-dimensional molding composition, and the results are shown in Table 3 or Table 4. In addition, the shaped disk is 127mm long x 1 width.
The test piece was cut to 2.7 mm using a diamond cutter. About this test piece, JIS-K6919
The heat distortion temperature was measured according to. In addition to visually observing the degree of warpage of the molded disk, as an index of reaction contraction,
The average particle diameter of the solid fine particles in the disk was measured. The results are shown in Table 3 or Table 4.

[0032]

[Table 3]

[0033]

[Table 4]

In Tables 3 and 4, * 9: triethoxylated trimethylolpropane diacrylate / monomethacrylate * 10: tetraethylene glycol diacrylate * 11: tetraethylene glycol diacrylate / tetraethylene glycol dimethacrylate = (1 / * 1: 1-hydroxycyclohexylphenyl ketone (trade name: Irgacure 184, manufactured by Ciba Geigy) * 15: Methylsiloxane particles having an average particle diameter of 0.7 μm * 16: Magnesium sulfate fiber having an average fiber length of 10 μm Whisker * 17: Polyisobutyl methacrylate (average molecular weight: about 50,000) * 18: Polypropylene adipate (average molecular weight: about 55)
00)

Comparative Examples 6 to 10 (Manufacture and evaluation of three-dimensional molded articles by optical cast molding method) The compositions for optical three-dimensional molding used in Examples 7, 8 and Comparative Examples 2, 4, and 5 were prepared as follows. 10mm silicone rubber 3mm thick
Is filled into a casting tank having a space of 150 mm wide x 150 mm high x 10 mm thick sandwiched between two glass plates, and then ultraviolet rays from a distance of 20 cm using a 500 watt ultra-high pressure mercury lamp (main wavelength: 3650 angstroms). Irradiation was performed to obtain a three-dimensional structure by an optical cast molding method. A thermocouple was attached to the center of the casting tank, the heat generated by curing was measured, the time from the start of irradiation to the maximum temperature was measured, and this was used as an index of photopolymerization reactivity, and the results are shown in Table 5. Was. In addition, the obtained three-dimensional molded article was cut into a length of 127 mm × a width of 12.7 mm using a diamond cutter to prepare a test piece, which was subjected to JIS.
The heat distortion temperature was measured according to -K6919. Table 5 shows the results
It was shown to.

[0036]

[Table 5]

In Table 5, **: almost no heat generation was observed even 100 minutes after the start of irradiation.

[0038]

As is clear from the above, the present invention described above can impart good photopolymerization reactivity to the optical three-dimensional molding composition used in the method of forming a three-dimensional molded object by the lamination curing method. In addition, there is an effect that excellent thermal properties can be imparted to the three-dimensional structure obtained at the same time.

──────────────────────────────────────────────────続 き Continuation of the front page (51) Int.Cl. ⁶ Identification code Agency reference number FI Technical display location G03F 7/028 G03F 7/028 (56) References JP-A-2-3133 (JP, A) JP-A 64-948 (JP, A) JP-A-2-145616 (JP, A) JP-A 63-107954 (JP, A)

Claims (4)

(57) [Claims] An uncured optical three-dimensional structure forming composition is formed by irradiating an energy beam to an uncured layer of the optical three-dimensional structure forming composition, and then forming a new uncured optical three-dimensional structure composition on the cured layer. In a method of forming a three-dimensional object by repeatedly performing an operation of supplying a layer of the object and irradiating it with an energy ray to form a next cured layer, the composition for optical three-dimensional object is represented by the following formula: And a vinyl monomer copolymerizable with the unsaturated urethane (meth).
An acrylic acid ester, one or more fillers selected from inorganic 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, and / or an organic polymer as a shrinkage reducing agent And a photopolymerization initiator, and the unsaturated urethane / the vinyl monomer =
10/90 to 90/10 (weight ratio), the filler is 300 parts by weight or less per 100 parts by weight of the total amount of the unsaturated urethane and the vinyl monomer, and the shrinkage reducing agent is the unsaturated urethane and the vinyl monomer. 1 per 100 parts by weight of the total amount of
00 optical three-dimensional forming form how, which comprises using a stereolithography composition comprising in an amount of less parts. (Equation 1) [In the formula 1, X ² : a residue obtained by removing an isocyanate group from a diisocyanate Y ³ : a residue obtained by removing a hydroxyl group from a triol Y ⁴ : a residue obtained by removing a hydroxyl group from a diol R ⁵ , R ⁶ , R ⁷ : same at the same time H or CH ₃ ] Wherein optical three-dimensional forming form how according to claim 1 is mixed unsaturated acid esters obtained from a vinyl monomer is a polyol and acrylic acid and methacrylic acid. Wherein optical three-dimensional forming form how according to claim 1 or 2 wherein the thermoplastic polymer shrinkage reducing agent is dissolved in a mixed solution consisting of an unsaturated urethane and vinyl monomer. 4. A three-dimensional structure obtained by the method according to claim 1, 2 or 3 .