JP3410799B2 - Optical three-dimensional molding resin composition - Google Patents

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. ]

[0010] Epoxy compounds, e Po carboxymethyl acrylate compounds, ester acrylate compound, at least one compound selected from the group consisting of acrylate compounds 40 wt% to 90 wt%, photoinitiator 0.1 against + 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, 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 = CH
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 = 15,
R ₁ = H; n = 15, R ₁ = CH ₃ ; other n = 6-1
5 is also preferable because the effect of the present invention can be obtained. The component indicated by is basically the epoxy compound indicated by
Things, et Po carboxymethyl acrylate compound, an aid existence improving main agent, such as ester acrylate compound in the composition ratio of the components is shown in the main agent the apparatus having to exceed 60% by weight is a component of performance (toughness etc. Cannot be used because the rigidity, mechanical properties, etc.) are not exhibited. In other words, the composition ratio effective for the present invention is limited to the range of 10 to 60% by weight.

[0016] component of, in the shown of the compositions used in the present invention, an epoxy compound, or e Po carboxymethyl acrylate compounds, ester acrylate compound, selected from the group consisting of vinylic unsaturated compounds acrylate compound At least one compound. Typical epoxy compounds include hydrogenated bisphenol A diglycidyl ether, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, and 2- (3,4-epoxycyclohexyl-5,5.
-Spiro-3,4-epoxy) cyclohexane-meta-
Dioxane, bis (3,4-epoxycyclohexylmethyl) adipate and the like can be mentioned. Also et Po carboxymethyl acrylate compounds, ester acrylate compounds may be used either so-called monomers, oligomers.

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.

[0018] d Po carboxymethyl acrylate compounds, bisphenol A obtained by reacting glycidyl ether with acrylic acid, phenol novolak type, each compound alicyclic like can be mentioned as a typical example. The ester acrylate compound, phthalic anhydride, propylene oxide diol, a compound consisting of acrylic acid,
Typical examples thereof include adipic acid, 1,6-hexanediol, a compound of acrylic acid, trimellitic acid, diethylene glycol, and a compound of acrylic acid. Such components can be used in the form of a mixture of one or more monofunctional and / or polyfunctional compounds. The components represented by may be used alone or in combination of two or more. 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 2-hydroxyoxyethyl acrylate and oligoester consisting of neopentyl glycol and adipic acid, and adduct consisting of isophorone. Acrylate, EO-modified bisphenol A diacrylate, PO-modified pentaerythritol tetraacrylate (PO: abbreviation for propion oxide) and 2,2-
A composition of dimethoxy-2-phenylacetophenone, an alicyclic epoxy celloxite 2021P (manufactured by Daicel Chemical Industries, Ltd.), EO-modified bisphenol A diacrylate, propion oxide-modified pentaerythritol tetraacrylate cation catalyst UVI-9670 (Tomo Kogyo ( 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.

Reference Example 1 [Synthesis of Urethane Acrylate Oligomer] IPDI terpolymer (manufactured by Sumitomo Bayer Co., Ltd .; a product of Sumitomo Bayer Co., Ltd.) in which isophorone diisocyanate was trimerized in a 5-liter three-necked flask equipped with a stirrer, a cooling tube and a dropping funnel with a side tube. Module Z-4372) 1023
g and 0.076 g of dibutyltin laurate are charged, and the internal temperature is adjusted to 65 ° C. in an oil bath. Polyneopenthylene adipate (manufactured by Asahi Denka; Adeka New Ace Y9-10) 420.
Charge 1g. The entire system is depressurized and the operation of returning to normal pressure with nitrogen gas is repeated to degas and replace nitrogen. The entire system is set to normal pressure and the temperature of the flask contents is set to 65 in a nitrogen atmosphere.
While maintaining the temperature at 0 ° C., the content is stirred and the polyneopentylene adipate is added dropwise from the dropping funnel over 1 hour. After the dropping, the contents are kept at 65 ° C. for another hour and the reaction is continued with stirring. After cooling the temperature of the flask contents to 50 ° C., 2-hydroxyethyl acrylate 254.
A solution prepared by homogeneously dissolving and mixing 0.90 g of methylhydroquinone in 5 g is charged, and the solution is rapidly added dropwise within a range in which the temperature of the contents of the flask does not exceed 55 ° C., and then the reaction is continued for 2 hours with stirring. 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]

Reference 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 Reference Example 1 and EO-modified bisphenol A diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., NK ester AB)
PE-4 is n = 2 in the present invention, R ₁ = H] 1680 g,
PO-modified trimethylolpropane triacrylate [NK ester A-TMPT-3PO manufactured by Shin-Nakamura Chemical Co., Ltd.]
720 g was charged and degassed with nitrogen was replaced with nitrogen. 2,2-dimethoxy-2-phenylacetophenone (Ciba Geigy; Irgacure 651) 12 under UV-protected environment
Optical composition was prepared by adding 0 g and mixing until completely dissolved.

Reference Example 3 Focused Ar laser light (output 500 mW, wavelength 368 m) was perpendicular to the surface of the resin composition prepared in Reference Example 2 so that a dumbbell test piece conforming to JIS standard 7113 was obtained. Irradiated. The resin solution adhering to the obtained cured product was washed and removed with isopropyl alcohol, and post-cured for 10 minutes with an ultraviolet ray of 3 KW. 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 Reference Example 2, polypropylene glycol 200 diacrylate [Shin-Nakamura Chemical Co., Ltd.]
Manufactured by 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 Reference 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 The resin composition was exactly the same as in Reference Example 2 except that polypropylene glycol 700 diacrylate (NK ester APG-700 manufactured by Shin-Nakamura Chemical Co., Ltd.) was used instead of the EO-modified bisphenol A diacrylate. Prepared things. Further, a tumbler test piece was formed in the same manner as in Reference 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 Instead of the EO-modified bisphenol A diacrylate in Reference Example 2, polyethylene glycol 200 diacrylate (N manufactured by Shin-Nakamura Chemical Co., Ltd.) was used.
A resin composition was prepared in exactly the same manner except that K ester A-200) was used. Further, a tumbler test piece was formed in the same manner as in Reference 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 1 Celoxite 2021P (manufactured by Daicel Chemical Industries, Ltd., alicyclic epoxy compound) 1500
g, EO-modified bisphenol A diacrylate [NK ester A-BPE-4 manufactured by Shin-Nakamura Chemical Co., Ltd.
= 2, R ₁ = H] 750 g and 750 g of PO-modified trimethylene glycol triacrylate (NK ester A-TMPT-3PO manufactured by Shin-Nakamura Chemical Co., Ltd.) are charged and mixed with stirring. UVI-9670 under the environment where ultraviolet rays are cut.
60 g of (Catalyst catalyst manufactured by Tomoe Industry Co., Ltd.) and 120 g of 2,2-dimethoxy-2-phenylacetophenone (manufactured by Ciba-Geigy; Irgacure 651) are added, and mixed and stirred until completely dissolved. Example 3 using this resin liquid
A test piece was prepared in the same manner as in. 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 1 , polypropylene glycol 400 diacrylate (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 NK Ester APG-400 manufactured by KK was used. Further, a tumbler test piece was formed in the same manner as in Reference 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 volume shrinkage ratio are inferior to those of Example 1 .

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

Comparative Example 5 A resin composition was prepared in the same manner as in Example 1 except that polypropylene glycol 700 diacrylate (NK ester APG-700 manufactured by Shin-Nakamura Chemical Co., Ltd.) was used in place of the EO-modified bisphenol A diacrylate. I prepared it. Further, a tumbler test piece was formed in the same manner as in Reference 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 In Example 1 , polyethylene glycol 200 diacrylate (N, manufactured 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 K ester A-200) was used. Further, a tumbler test piece was formed in the same manner as in Reference 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. From the above, 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 2 Celoxite 2021P (manufactured by Daicel Chemical Industries, Ltd., alicyclic epoxy compound) 1500
g, EO-modified bisphenol A diacrylate [NK ester A-BPE-10 manufactured by Shin-Nakamura Chemical Co., Ltd., n = 5, R ₁ = H in the present invention] 750 g, PO-modified trimethylene glycol triacrylate (Shin-Nakamura Chemical Co., Ltd. 750 g of NK ester A-TMPT-3PO manufactured by Co., Ltd. was charged and mixed. UVI-9670 under the environment where ultraviolet rays are cut.
60 g of (Catalyst catalyst manufactured by Tomoe Industry Co., Ltd.) and 120 g of 2,2-dimethoxy-2-phenylacetophenone (manufactured by Ciba-Geigy; Irgacure 651) are added, and mixed and stirred until completely dissolved. Reference Example 3 using this resin liquid
A test piece was prepared in the same manner as in. 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 1 , EO-modified bisphenol A diacrylate (NK ester A-BP) was used.
E-4) instead of EO-modified bisphenol A diacrylate (NK ester A-BPE-40 n outside the present invention)
= 20) 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 Reference 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%

Reference Examples 4 to 6 Crosslinked polystyrene polymers, crosslinked polymethacrylate polymers, and glass beads were added as solid particles to the optical modeling compositions prepared in Reference Example 2, respectively. An optical modeling composition was prepared, and an optical modeling article was formed in the same manner as in Reference 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.

Reference Example 7 Glass beads GB-731C (manufactured by Toshiba Ballotini Co., Ltd., average particle size) obtained by treating the composition for optical modeling prepared in Reference Example 2 with solid fine particles treated with an acrylic silane-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 Reference 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)

(57) [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. ] Epoxy compound, e Po carboxymethyl acrylate compounds, ester acrylate compound, at least one compound selected from the group consisting of acrylate compounds 4
0% to 90% by weight, + 0.1% to 10% by weight of a photopolymerization initiator with respect to + as an essential component, a resin composition for liquid three-dimensional optical three-dimensional modeling. 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.