JPH07228644A - Resin composition for optically three-dimensional molding - Google Patents

Abstract

PURPOSE:To obtain a liquid resin composition which is prepared by incorporating a specific bisphenol-A derivative into a resin composition for giving three- dimensional molding, and gives molding products with high mechanical properties and dimensional accuracy because of its reduced volume shrinkage. CONSTITUTION:This liquid resin composition comprises, as essential components, (A) 10 to 60wt.% of a compound of the formula (R1 is H, a lower alkyl such as methyl, ethyl or propyl; (n) is 1 to 15); (B) 40 to 90wt.% of a compound selected from epoxy (acrylate) compounds, urethane acrylates, and (ester) acrylates and (C) 0.1 to 10wt.%, on the basis of A+B, of a photopolymerization initiator such as 2,2-dimethoxy-2-phenylacetophenone. It is preferred that this composition additionally contains a crosslinked polystyrene polymer, solid particles such as glass beads in an amount of 10 to 70wt.% based on the total amount.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an active energy ray-curable resin composition for optical three-dimensional molding, and particularly to an optical three-dimensional molding excellent in mechanical properties after curing and having small volume shrinkage and excellent dimensional accuracy. The present invention relates to a resin composition.

[0002]

2. Description of the Related Art Conventionally, an apparatus for producing a three-dimensional object using a photosensitive resin has been disclosed in Japanese Patent Application Laid-Open No. 56-144478, and the apparatus for producing a three-dimensional figure disclosed here is photocuring. A three-dimensional object is created by supplying a necessary amount of light energy to the resin. Further, in JP-A-60-247515, as a basic practical method, light energy necessary for curing is selectively supplied to a photocurable fluid substance that is cured by light to form a solid having a desired shape. Has been proposed. Thereafter, similar devices and methods or improved techniques thereof have been disclosed.

For example, JP-A-62-35966 (method and apparatus for creating a three-dimensional object), JP-A-1-204
No. 915 (Resin composition for optical three-dimensional modeling), Japanese Patent Laid-Open No. 2-113925 (three-dimensional image forming method), Japanese Patent Laid-Open No.
-145616 (optical three-dimensional resin composition), JP-A-2-153722 (optical molding method), JP-A-3-15520 (stereoscopic image forming method), JP-A-3-21432. (Stereoscopic image forming system), JP-A-3-41126 (stereoscopic image forming method)
Is disclosed in. A typical example of the optical three-dimensional modeling method is that a liquid surface of a liquid photocurable resin contained in a container is selectively irradiated with an ultraviolet laser controlled by a computer so as to obtain a desired pattern, and then predetermined. The thickness is cured, and then one layer of liquid resin is supplied onto the cured layer, and similarly cured by irradiation with an ultraviolet laser in the same manner as described above to obtain a continuous cured layer. This is a method of obtaining a three-dimensional object. This optical three-dimensional modeling method has recently attracted particular attention because it can be easily obtained in a relatively short time even if the shape of a modeled object to be manufactured is quite complicated.

Conventionally, as a photocurable resin used in the optical three-dimensional molding method, modified polyurethane (meth) acrylate, oligoester acrylate, urethane acrylate, epoxy acrylate, photosensitive polyimide, aminoalkyd, etc. are known. Recently, JP-A-1-204915 uses a monomer compound containing an ethylenically unsaturated compound having a cross-linked alicyclic hydrocarbon group and a polymer having an ethylenically unsaturated group as a curable liquid substance. It is shown that,
No. 304 publication discloses an epoxy compound, a cyclic ether compound, a cyclic lactone compound, a cyclic acetal compound, a cyclic thioether compound, a cyclic spiro orthoester compound, a vinyl compound, etc. as the energy ray-curable cationically polymerizable organic substance, Further, JP-A-2-28261 and JP-A-2-75617 disclose improved resin compositions for optical modeling containing the energy ray-curable cationically polymerizable organic substance. Further, JP-A-2-145616 discloses a resin composition for optical modeling containing a liquid curable resin and fine particles, and other JP-A-3-104626 and JP-A-3-114732.
Various improved techniques are disclosed in Japanese Laid-Open Patent Publication No. 3-114733 and the like.

[0005]

Generally, as a photocurable resin used in an optical three-dimensional molding method, there are several types such as good handleability, high molding speed, and high molding accuracy. From the viewpoint, it is required that the resin viscosity is relatively low, the volume shrinkage ratio upon curing is low, and that the mechanical properties of the obtained molded article are sufficiently high. However, none of the above-mentioned liquid photocurable resins have necessarily obtained these properties, particularly mechanical properties and low volume shrinkage, and this has been a problem. In general, when the liquid resin is cured and polymerized, the volumetric contraction of the obtained three-dimensional model occurs,
When the liquid resin is used as the resin component of the resin composition for a three-dimensional optical three-dimensional object, there is a defect that the accuracy of the object is poor. In order to prevent such defects, various studies have been made on the resin composition, and attempts have been made to reduce the volumetric shrinkage rate of the shaped article.

[0006] As an attempt to reduce the volumetric shrinkage of the shaped article, a method of adding a filler, a method of foaming, a method of causing expansion layer separation, and other methods, lowering the functional group capacity per basic volume of a monomer or an oligomer. Although any of these methods can be considered, all of these methods are effective in reducing the volumetric shrinkage, but in reality, deterioration of mechanical properties cannot be avoided. That is, the reduction of volumetric shrinkage and the maintenance and improvement of mechanical properties are a trade-off phenomenon.
However, the present inventors surprisingly found that the composition for a three-dimensional optical three-dimensional structure obtained by blending a compound having a structural formula represented by the following general formula I in a fixed ratio surprisingly caused volume shrinkage. The present invention has been completed by finding a phenomenon in which the mechanical properties are improved at the same time as reducing the rate, and breaking the antinomy phenomenon. Therefore, the problem to be solved by the present invention is to provide a photo-curable liquid capable of forming an optical three-dimensional object excellent in so-called dimensional accuracy, which has sufficiently high mechanical properties and exhibits a low volume shrinkage ratio. It is to provide a resin composition.

[0007]

The problems to be solved by the invention described above are achieved by the following inventions. (1) 10% by weight to 60% by weight of a compound having the structural formula represented by the general formula [I],

[0008]

[Chemical 2]

[Where R ₁ is H, CH ₃ , C ₂ H ₅ , C
It is a lower alkyl group such as ₃ H ₇ and is an integer represented by n = 1 to 15. ]

40% by weight to 90% by weight of at least one compound selected from the group consisting of epoxy compounds, urethane acrylate compounds, epoxy acrylate compounds, ester acrylate compounds and acrylate compounds; A liquid resin composition for three-dimensional optical three-dimensional modeling, which contains 1% by weight to 10% by weight as an essential component. (2) A liquid three-dimensional optical three-dimensional modeling resin composition, wherein the liquid three-dimensional optical three-dimensional modeling resin composition according to the above-mentioned item 1 contains solid fine particles. (3) The solid fine particles contain at least one kind of organic polymer solid fine particles selected from a crosslinked polystyrene polymer, a crosslinked polymethacrylate polymer, a polyethylene polymer or a polypropylene polymer. The resin composition for liquid three-dimensional optical three-dimensional modeling described in the above item 2. (4) The liquid three-dimensional optical three-dimensional modeling resin composition according to item 2, wherein the solid fine particles contain at least one kind of inorganic solid fine particles selected from glass beads, talc fine particles, and silicon oxide fine particles. object. (5) The liquid three-dimensional optical three-dimensional modeling resin composition according to any one of items 2 to 4, wherein the content of the solid fine particles is 10% by weight to 70% by weight based on the total weight. (6) The liquid three-dimensional optical three-dimensional modeling resin composition according to any one of items 2 to 5, wherein the solid fine particles are treated with a silane coupling agent.

The present invention will be described in more detail below.
The compound used in the present invention has a structural formula represented by the following general formula [I].

[0012]

[Chemical 3]

[Wherein R ₁ is H, CH ₃ , C ₂ H ₅ , C
It is a lower alkyl group such as ₃ H ₇ and is an integer represented by n = 1 to 15. ]

Of these compounds, n is in the range of 1 to 15,
The range is preferably 2 to 10, more preferably 2 to 5. When the number of n exceeds 15, the mechanical strength is lowered and the effect of the present invention is not sufficiently exhibited, so that it cannot be used. In the composition used in the present invention, the composition ratio of the component represented by is 10 to 60% by weight, preferably 15 to 50% by weight, and more preferably 20 to 40% by weight. The composition ratio of the component shown by is 10% by weight.
If it is less than the above range, the effect of the present invention, that is, the mechanical properties are inferior and the volumetric shrinkage increases, which is not preferable.

The component represented by is specifically n
= 1, R ₁ = H; n = 2, R ₁ = H; n = 2, R ₁ = C
H ₃ ; n = 2, R ₁ = C ₂ H ₅ ; n = 5, R ₁ = C
_{H 3; n = 5, R} 1 = H; n = 5, R 1 = C 2 H 5; n
= 10, R ₁ = H; n = 10, R ₁ = CH ₃ ; n = 1
5, R ₁ = H; n = 15, R ₁ = CH ₃ ; otherwise n = 6
Those having a number of 15 to 15 are also preferable because the effects of the present invention are exhibited.
The component represented by is basically an auxiliary agent for improving the main component such as an epoxy compound, a urethane acrylate compound, an epoxy acrylate compound, an ester acrylate compound represented by, and the composition ratio of the component represented by is 60% by weight. %, It cannot be used because the performance of the main component (rigidity, rigidity such as toughness, mechanical properties, etc.) is not exhibited. That is, the composition ratio effective in the present invention is 10 to 60% by weight.
Is limited to the range.

In the composition used in the present invention, the component represented by is selected from the group consisting of epoxy compounds, urethane acrylate compounds, epoxy acrylate compounds, ester acrylate compounds and vinyl unsaturated compounds of acrylate compounds. And at least one compound. Typical epoxy compounds include hydrogenated bisphenol A diglycidyl ether,
3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 2- (3,4-
Examples thereof include epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane-meta-dioxane and bis (3,4-epoxycyclohexylmethyl) adipate. As the urethane acrylate compound, epoxy acrylate compound, ester acrylate compound and the like, so-called monomers and oligomers can be used.

As the acrylate compound, monofunctional compounds,
Any polyfunctional monomer and / or oligomer may be used. These monofunctional and / or polyfunctional compounds are not particularly limited, and representative examples thereof include monofunctional compounds; isobornyl acrylate, isobornyl methacrylate, dicyclopentenyl acrylate, bornyl acrylate. , Bornyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, polypropylene glycol acrylate and the like. Polyfunctional compound; trimethylolpropane triacrylate, EO-modified trimethylolpropane triacrylate (EO: abbreviation of ethylene oxide), ethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, 1,4-butanediol di Acrylate,
1,6-hexanediol diacrylate, neopentyl glycol diacrylate, dicyclopentenyl diacrylate, polyester diacrylate, diallyl phthalate and the like can be mentioned.

As the urethane acrylate compound, an addition reaction product of a compound such as ester diglycol composed of neopentyl glycol and adipic acid or ε-caprolactone and a diisocyanate such as isophorone, toluene diisocyanate and hexamethylene diisocyanate. A typical example thereof is a compound consisting of and hydroxy (meth) acrylate. Representative examples of the epoxy acrylate compound include bisphenol A, a phenol novolac type compound, and an alicyclic type compound obtained by the reaction of glycidyl ether and acrylic acid. Typical ester acrylate compounds include phthalic anhydride, propylene oxide diol, acrylic acid, adipic acid, 1,6-hexanediol, acrylic acid, trimellitic acid, diethylene glycol and acrylic acid. It can be cited as an example. Such components can be used in the form of a mixture of one or more monofunctional and / or polyfunctional compounds. The component indicated by
One kind may be used alone, or two or more kinds may be mixed and used. However, when an epoxy compound is used, it is better to avoid using it together with a basic compound such as a urethane acrylate compound. This is because when an epoxy compound is adopted, a cationic polymerization catalyst described later is often used as a polymerization initiator component represented by, and therefore it cannot be used in combination with a basic compound.

As the polymerization initiator component used in the present invention, 2,2-dimethoxy-2- as a photopolymerization initiator is used.
Phenylacetophenone, 1-hydroxycyclohexyl phenyl ketone, acetophenone, benzophenone,
Typical examples include xanthone, fluorenone, benzaldehyde, fluorene, anthraquinone, triphenylamine, carbazole, 3-methylacetophenone and Michler's ketone, but the initiator is not limited to these and the initiators are not limited to these. It is also possible to use one type or a combination of two or more types. Further, if necessary, a sensitizer such as an amine compound may be used in combination. Further, as the thermal polymerization initiator, benzoyl peroxide, t-butyl peroxybenzoate, dicumyl peroxide, diisopropyl peroxydicarbonate, t-butyl peroxide, azobisisobutyronitrile and the like are mentioned as typical ones. be able to. When an epoxy compound is used, an energy-active cationic polymerization catalyst such as triphenylsulfonium hexafluoroantimonate is used. The amount of the polymerization initiator component used in the present invention is 0.1 to 10% by weight, preferably 1 to 5% by weight, based on component + component.

The combination of the component + component + component of the present invention is preferably a combination of an oligoester consisting of neopentyl glycol and adipic acid and an adduct consisting of isophorone, and a urethane acrylate consisting of 2-hydroxyethyl acrylate, and EO-modified. Bisphenol A
Composition of diacrylate, pentaerythritol tetraacrylate and 2,2-dimethoxy-2-phenylacetophenone; urethane consisting of oligoester consisting of neopentyl glycol and adipic acid and adduct of isophorone and 2-hydroxyethyl acrylate. Acrylate, EO-modified bisphenol A diacrylate, PO-modified pentaerythritol tetraacrylate (PO: abbreviation for propion oxide) and 2,2-
Composition of dimethoxy-2-phenylacetophenone, alicyclic epoxy celloxite 2021P (manufactured by Daicel Chemical Industries, Ltd.), EO-modified bisphenol A diacrylate, propion oxide-modified pentaerythritol tetraacrylate cation catalyst UVI-9670 Ltd.), 2,2-dimethoxy-2-phenylacetophenone composition, and the like.

In the resin composition of the present invention, if necessary,
A leveling agent, a surfactant, an organic polymer compound, an organic plasticizer, organic polymer solid fine particles, inorganic solid fine particles and the like may be added. In the present invention, mechanical strength or volume shrinkage can be improved by adding solid fine particles such as organic polymer solid fine particles and inorganic solid fine particles to the resin composition. The solid fine particles preferably have an average particle diameter of 3 μm to 70 μm, and more preferably 1
0 μm to 60 μm, more preferably 15 μm to 50 μm
Is. Further, as these solid fine particles, those having a particle diameter within these ranges can be arbitrarily mixed and used, but those having a similar particle diameter are preferably used. Typical examples of the organic polymer solid fine particles include crosslinked polystyrene-based polymers, crosslinked polymethacrylate-based polymers, polyethylene-based polymers, polypropylene-based polymers and the like. Further, as the inorganic solid fine particles, glass beads, talc fine particles, silicon oxide fine particles and the like can be mentioned as typical ones, but the organic polymer solid fine particles and the inorganic solid fine particles are not limited to these, and any of them can be used. Can be used.

The organic polymer solid fine particles and the inorganic solid fine particles used in the present invention are used, respectively, but they may be used in combination. When these solid particles are used together, the mixing ratio of the organic polymer solid particles and the inorganic solid particles is 5: the ratio of the inorganic solid particles to the organic polymer solid particles is 5.
% By volume to 70% by volume, preferably 10% by volume
55% by volume. The predetermined organic polymer solid fine particles and / or inorganic solid fine particles used in the present invention are preferably treated with a silane coupling agent such as aminosilane, epoxysilane and acrylsilane.
When organic polymer solid fine particles or inorganic solid fine particles treated with such a silane coupling agent are used, particularly favorable results are obtained in mechanical strength. However, the effect of the type of silane coupling agent depends on the photocurable resin used. When a vinyl unsaturated compound is used as a photo-curable resin, an acrylic silane-based treatment agent is most preferable, and when an epoxy-based compound is used as a photo-curable resin, an epoxy silane-based treatment agent is most effective. I found it.

When polyethylene-based polymer solid fine particles or polypropylene-based polymer solid fine particles are used, at least 1 to 10% by weight is required to treat the silane coupling agent.
It is preferable to use a copolymer of the acrylic acid type compound of 1. The resin composition of the present invention is prepared by mixing the above-mentioned components and or, if necessary, mixing other components, but the mixing method of each component is not particularly limited. The light used for optical three-dimensional modeling using the resin composition of the present invention may be ultraviolet light, visible light, infrared light, laser light or the like depending on the purpose. From the viewpoint of curing efficiency, laser light or ultraviolet light is particularly preferable, but visible light or infrared light can also be used efficiently depending on the selection of the sensitive resin. As a typical method of the optical three-dimensional modeling method in which the resin composition of the present invention is used, the composition in a liquid state is selectively irradiated with light so that a cured layer having a desired pattern is obtained and cured. By forming a layer, then supplying the uncured liquid composition to the cured layer, and similarly irradiating with light to newly form a cured layer continuous with the above-mentioned cured layer, by repeating the laminating operation, the final purpose is obtained. Is a method of obtaining a three-dimensional molded article.

[0024]

The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples.

Example 1 [Synthesis of urethane acrylate oligomer] Stirrer,
A 5 liter three-neck flask equipped with a cooling tube and a dropping funnel with a side tube was charged with 1023 g of IPDI terpolymer (Sumitomo Bayer Co. Ltd .; Dice Module Z-4372) trimerized with isophorone diisocyanate and 0.076 g of dibutyltin laurate. , The internal temperature of the oil bath 65 ℃
To 420.1 g of polyneopentylene adipate (manufactured by Asahi Denka Co., Ltd .; ADEKA New Ace Y9-10) is charged into a dropping funnel with a side tube which is stored in advance at 50 ° C. The entire system is depressurized and the operation of returning to normal pressure with nitrogen gas is repeated to degas and replace nitrogen. The whole system is kept at normal pressure and the temperature of the flask contents is kept at 65 ° C. in a nitrogen atmosphere. While stirring the contents, polyneopentylene adipate is added dropwise over 1 hour from a dropping funnel. 6 more contents for 1 hour after dropping
The reaction is continued while stirring at 5 ° C. After cooling the temperature of the flask contents to 50 ° C, a dropping funnel was charged with a solution in which 254.5 g of 2-hydroxyethyl acrylate and 0.90 g of methylhydroquinone were homogeneously dissolved and mixed, and the temperature of the flask contents exceeded 55 ° C. Drop quickly without any
Then, the reaction is continued under stirring for 2 hours. The obtained urethane acrylate oligomer is taken out of the flask while the contents are warm. The urethane acrylate oligomer obtained here was confirmed to have the following structural formula by IR and elemental analysis.

[0026]

[Chemical 4]

Example 2 [Preparation of composition for optical modeling] In a 5 liter three-necked flask equipped with a stirrer, a cooling tube and a dropping funnel with a side tube, 1600 g of the urethane acrylate synthesized in Example 1 was added.
EO modified bisphenol A diacrylate [Shin-Nakamura Chemical Co., Ltd., NK ester A-BPE-4 is n in the present invention]
= 2, R ₁ = H] 1680 g, and PO-modified trimethylolpropane triacrylate [NK ester A-TMPT-3PO manufactured by Shin-Nakamura Chemical Co., Ltd.] 720 g were charged and degassed by nitrogen substitution. 120 g of 2,2-dimethoxy-2-phenylacetophenone (manufactured by Ciba Geigy; Irgacure 651) was added in an environment where ultraviolet rays were cut, and mixed until completely dissolved to prepare an optical modeling composition.

Example 3 Focused Ar laser light (output 500 mW, wavelength 368)
m 2) was irradiated perpendicular to the surface of the resin composition prepared in Example 2 so that a dumbbell test piece according to JIS standard 7113 was obtained. 3KW after removing the resin solution of the obtained cured product by washing with isopropyl alcohol
Post cure was carried out for 10 minutes with the ultraviolet rays of. The tensile properties of the obtained test piece were measured according to JIS K7113. Further, the volumetric shrinkage rate was obtained by measuring the specific gravity of the resin composition and the molded article. The results obtained are as follows, and it is clear that the shrinkage is low and the mechanical properties are excellent as compared with the volume shrinkage of 6 to 8% of the urethane acrylate resin which is generally said. Is.

[0029] Tensile strength 5.4 Kg / mm ² tensile elongation of 8% tensile modulus 243Kg / mm ² volumetric shrinkage 4.6%

Comparative Example 1 Instead of the EO-modified bisphenol A diacrylate in Example 2, polypropylene glycol 200 diacrylate [Shin-Nakamura Chemical Co., Ltd., NK ester APG-
200] was used to prepare a resin composition in exactly the same manner. Further, a tumbler test piece was formed in the same manner as in Example 3 and the physical properties and the volume shrinkage were measured in the same manner. The results are as follows, and the mechanical properties and the volumetric shrinkage ratio are inferior to those of Example 3.

Tensile strength 4.0 Kg / mm ² Tensile elongation 8% Tensile modulus 187 Kg / mm ² Volume shrinkage 7.8%

Comparative Example 2 Instead of the EO-modified bisphenol A diacrylate in Example 2, polypropylene glycol 700 diacrylate (NK ester APG-7 manufactured by Shin-Nakamura Chemical Co., Ltd.) was used.
A resin composition was prepared in exactly the same manner except that (00) was used. Further, a tumbler test piece was formed in the same manner as in Example 3 and the physical properties and the volume shrinkage were measured in the same manner. The results are shown below, and when compared with Comparative Example 1, an improvement in volume shrinkage is recognized, but a marked decrease in mechanical properties is observed.

Tensile strength 1.2 Kg / mm ² Tensile elongation 13% Tensile modulus 18 Kg / mm ² Volume shrinkage 5.9%

Comparative Example 3 Polyethylene glycol 200 diacrylate (NK Ester A-200 manufactured by Shin Nakamura Chemical Co., Ltd.) was used in place of the EO-modified bisphenol A diacrylate in Example 2.
A resin composition was prepared in exactly the same manner except that was used. Further, a tumbler test piece was formed in the same manner as in Example 3 and the physical properties and the volume shrinkage were measured in the same manner. The results are as follows. When compared with Comparative Example 1, an improvement in mechanical properties was observed, but on the other hand, the volumetric shrinkage ratio was high, and the reduction in volumetric shrinkage ratio and the improvement in mechanical properties were an antinomy phenomenon. Clearly, the effect of the invention is extremely unusual.

Tensile strength 4.5 Kg / mm ² Tensile elongation 9% Tensile modulus 203 Kg / mm ² Volume shrinkage ratio 8.0%

Example 4 1500 g of Celoxite 2021P (manufactured by Daicel Chemical Co., Ltd., alicyclic epoxy compound), EO-modified bisphenol A diacrylate [NK ester A-BPE-4 manufactured by Shin Nakamura Chemical Co., Ltd. n in the present invention] = 2, R ₁ = H] 750
g, PO-modified trimethylene glycol triacrylate (NK ester A-TMPT-3P manufactured by Shin Nakamura Chemical Co., Ltd.)
750 g of O) are charged and mixed with stirring. UVI-9670 (cation catalyst manufactured by Tomoe Kogyo Co., Ltd.) 60 g and 2,2-dimethoxy-2-phenylacetophenone (manufactured by Ciba-Geigy; Irgacure 6)
51) Add 120 g and mix and stir until completely dissolved. Using this resin solution, a test piece was prepared in the same manner as in Example 3. The obtained results were as follows, and it was a low-shrinkage shaped article excellent in mechanical properties.

Tensile strength 7.1 Kg / mm ² Tensile elongation 7% Tensile modulus 335 Kg / mm ² Volume shrinkage 5.6%

Comparative Example 4 In Example 4, polypropylene glycol 400 diacrylate (NK ester APG-produced by Shin Nakamura Chemical Co., Ltd.) was used instead of the EO-modified bisphenol A diacrylate.
A resin composition was prepared in exactly the same manner except that 400) was used. Further, a tumbler test piece was formed in the same manner as in Example 3 and the physical properties and the volume shrinkage were measured in the same manner. The results are as follows, and the mechanical properties and volume shrinkage ratio are inferior to those of Example 4.

Tensile strength 3.8 Kg / mm ² Tensile elongation 8% Tensile modulus 191 Kg / mm ² Volume shrinkage 7.0%

Comparative Example 5 Instead of the EO-modified bisphenol A diacrylate in Example 4, polypropylene glycol 700 diacrylate (NK ester APG-7 manufactured by Shin-Nakamura Chemical Co., Ltd.)
A resin composition was prepared in exactly the same manner except that (00) was used. Further, a tumbler test piece was formed in the same manner as in Example 3 and the physical properties and the volume shrinkage were measured in the same manner. The results are as follows. When compared with Comparative Example 1, improvement in volume shrinkage is recognized, but deterioration in mechanical properties is observed.

Tensile strength 3.1 Kg / mm ² Tensile elongation 8% Tensile modulus 166 Kg / mm ² Volume shrinkage ratio 6.0%

Comparative Example 6 Instead of the EO-modified bisphenol A diacrylate in Example 4, polyethylene glycol 200 diacrylate (NK ester A-200 manufactured by Shin-Nakamura Chemical Co., Ltd.)
A resin composition was prepared in exactly the same manner except that was used. Further, a tumbler test piece was formed in the same manner as in Example 3 and the physical properties and the volume shrinkage were measured in the same manner. The results are as follows. When compared with Comparative Example 1, an improvement in mechanical properties was recognized, but on the other hand, the reduction in volumetric shrinkage and the improvement in mechanical properties are antinomy phenomena. Recognized by
The effect of the present invention, which achieves the improvement of mechanical properties and the reduction of volume shrinkage at the same time, is extremely unusual.

Tensile Strength 5.9 Kg / mm ² Tensile Elongation 5% Tensile Modulus 366 Kg / mm ² Volume Shrinkage 7.5%

Example 5 1500 g of Celoxite 2021P (manufactured by Daicel Chemical Co., Ltd., alicyclic epoxy compound), EO-modified bisphenol A diacrylate [NK ester A-BPE-10 manufactured by Shin Nakamura Chemical Co., Ltd. n in the present invention] = 5, R ₁ = H] 750
g, PO-modified trimethylene glycol triacrylate (NK ester A-TMPT-3P manufactured by Shin Nakamura Chemical Co., Ltd.)
750 g of O) are charged and mixed with stirring. UVI-9670 (cation catalyst manufactured by Tomoe Kogyo Co., Ltd.) 60 g and 2,2-dimethoxy-2-phenylacetophenone (manufactured by Ciba-Geigy; Irgacure 6)
51) Add 120 g and mix and stir until completely dissolved. Using this resin solution, a test piece was prepared in the same manner as in Example 3. The obtained results were as follows, and it was a low-shrinkage shaped article excellent in mechanical properties.

Tensile strength 4.0 Kg / mm ² Tensile elongation 10% Tensile modulus 200 Kg / mm ² Volume shrinkage 4.9%

Comparative Example 7 In Example 4, instead of the EO-modified bisphenol A diacrylate (NK ester A-BPE-4), EO was used.
Modified bisphenol A diacrylate (NK ester A
-BPE-40 A resin composition was prepared in exactly the same manner except that n = 20 in the present invention was used. Further, a tumbler test piece was formed in the same manner as in Example 3 and the physical properties and the volume shrinkage were measured in the same manner. The results are as follows. The volume contraction rate is remarkably lowered, but the mechanical properties are remarkably lowered and cannot be used.

Tensile strength 0.6 Kg / mm ² Tensile elongation 20% Tensile modulus 3 Kg / mm ² Volume shrinkage ratio 4.0%

Examples 6 to 8 Crosslinked polystyrene type polymers, crosslinked type polymethacrylate type polymers and glass beads were added to the optical modeling composition prepared in Example 2 as solid fine particles, respectively. An optical modeling composition was prepared, and an optical modeling article was formed in the same manner as in Example 3. The results thus obtained are shown in Table 1.

[0049]

[Table 1]

As is clear from Table 1, by adding solid particles, the volume shrinkage can be reduced while maintaining the mechanical strength.

Example 9 Glass beads GB-731C (manufactured by Toshiba Ballotini Co., Ltd., average particle size) obtained by treating the composition for optical modeling prepared in Example 2 with solid fine particles treated with an acrylsilane-based treating agent. 30 μ) was added in an amount of 50% by volume to prepare an optical modeling composition, and an optical modeling article was formed in the same manner as in Example 3. The optical model thus obtained has excellent mechanical strength of 5.1 kg / mm ² and volumetric shrinkage of 2.2%.

[0052]

INDUSTRIAL APPLICABILITY According to the present invention, by adding a specific modified bisphenol A diacrylate compound as a component of a resin composition for optical three-dimensional molding, the volumetric shrinkage of the obtained optical three-dimensional molding is small, and It is also possible to obtain an excellent mechanical physical property, and to add a solid fine particle to the optical three-dimensional modeling resin composition to further improve the volume shrinkage ratio, which is a remarkably unprecedented remarkable effect. It plays.

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Claims (6)

[Claims] 1. A compound having a structural formula of general formula [I] 10% to 60% by weight, [Here, R ₁ is a lower alkyl group such as H, CH ₃ , C ₂ H ₅ , C ₃ H _{7 and the} like, and n is an integer represented by 1 to 15. ] 40% by weight to 90% by weight of at least one compound selected from the group consisting of an epoxy compound, a urethane acrylate compound, an epoxy acrylate compound, an ester acrylate compound, and an acrylate compound; A resin composition for liquid three-dimensional optical three-dimensional modeling, characterized by containing 10% by weight as an essential component. 2. A liquid three-dimensional optical three-dimensional modeling resin composition comprising the liquid three-dimensional optical three-dimensional modeling resin composition according to claim 1 containing solid fine particles. 3. The solid fine particles contain at least one kind of organic polymer solid fine particles selected from crosslinked polystyrene-based polymers, crosslinked polymethacrylate-based polymers, polyethylene-based polymers and polypropylene-based polymers. The resin composition for liquid three-dimensional optical three-dimensional modeling according to claim 2. 4. The liquid three-dimensional optical three-dimensional molding resin according to claim 2, wherein the solid fine particles contain at least one kind of inorganic solid fine particles selected from glass beads, talc fine particles, and silicon oxide fine particles. Composition. 5. The content of solid fine particles is 10% by weight of the whole.
The resin composition for liquid three-dimensional optical three-dimensional modeling according to any one of claims 2 to 4, wherein the resin composition is contained in an amount of 70 to 70% by weight. 6. The liquid three-dimensional optical three-dimensional modeling resin composition according to any one of claims 2 to 5, wherein the solid fine particles are treated with a silane coupling agent.