JP2590215B2 - Optical molding resin composition - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to an active energy ray-curable resin composition for optical shaping.

[Problems to be solved by conventional technology and invention]

Generally, a model corresponding to the product shape required at the time of mold production, or a model for contouring control of a cutting process or a model for an electric discharge machining electrode is manufactured manually or by an NC.
It was performed by NC cutting using a milling machine or the like.
However, manual machining has the problem of requiring a lot of labor and skill.In the case of NC machining, it is necessary to create a complicated machining program that takes into account replacement and wear for changing the shape of the blade edge. In addition to the above, there is a problem that further finishing may be required in order to remove a step generated on the processing surface. In recent years, technology development has been expected to solve these problems of the conventional technology and create new techniques for creating complex models and various fixed objects for mold making, copying, and sculpting EDM using optical modeling. Have been.

As the resin for optical shaping, curing sensitivity by energy rays is excellent, resolution of curing by energy rays is good, ultraviolet transmittance after curing is good,
Low viscosity, large γ characteristics, low volumetric shrinkage during curing, excellent mechanical strength of cured product, good self-adhesiveness, good curing characteristics under oxygen atmosphere For example, various characteristics are required.

On the other hand, JP-A-62-235318 discloses an epoxy compound having two or more epoxy groups in a molecule and a vinyl compound having two or more vinyl groups in a molecule using a triarylsulfonium salt catalyst. And photocuring at the same time. However,
Since the synthesis method of the present invention is not specifically aimed at obtaining an optical molding resin, even if the resin obtained thereby is used as an optical molding resin, it is not optimal for an optical molding system. Did not.

[Means for solving the problem]

The present invention is a result of intensive studies on photosensitive resins having various characteristics required as such optical molding resin,
It has been found.

An object of the present invention is to provide a resin composition most suitable for an optical molding system using active energy rays.

The resin composition for optical shaping of the present invention comprises, as essential components, (a) an energy ray-curable cationic polymerizable organic substance, (b) an energy ray-sensitive cationic polymerization initiator,
(C) an energy ray-curable radically polymerizable organic substance,
(D) An energy ray-sensitive radical polymerization initiator is contained.

The energy ray-curable cationic polymerizable organic substance (a) which is a constituent element of the present invention is a cationic polymerizable polymer that undergoes polymerization or cross-linking reaction by irradiation with energy rays in the presence of an energy ray-sensitive cationic polymerization initiator (b). Compound, 1
A compound containing 40% by weight or more of an alicyclic epoxy resin having at least two or more epoxy groups in a molecule. Compounds other than the alicyclic epoxy resin include, for example, an epoxy compound, a cyclic ether compound, a cyclic lactone compound, One or more of a cyclic acetal compound, a cyclic thioether compound, a spiroorthoester compound, a vinyl compound and the like may be contained. Among such cationically polymerizable compounds, an alicyclic epoxy resin having at least two epoxy groups in one molecule alone or a mixture with a conventionally known aromatic epoxy resin or aliphatic epoxy resin is preferable.

Preferred as the aromatic epoxy resin are polyphenols having at least one aromatic nucleus or polyglycidyl ethers of alkylene oxide adducts thereof, such as bisphenol A and bisphenol F.
Or a glycidyl ether produced by reacting an alkylene oxide adduct thereof with epichlorohydrin, or
Epoxy novolak resins.

Further, as a preferable alicyclic epoxy resin, a polyglycidyl ether or cyclohexene of a polyhydric alcohol having at least one alicyclic ring, or a cyclopentene ring-containing compound, such as hydrogen peroxide, peracid,
Cyclohexene oxide or cyclopentene oxide-containing compounds obtained by epoxidation with a suitable oxidizing agent. Representative examples of alicyclic epoxy resins 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, vinylcyclohexene dioxide, 4-vinylepoxycyclohexane, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, 3,4-epoxy -6-methylcyclohexyl-3,4-epoxy-6-methylcyclohexanecarboxylate, methylenebis (3,4-epoxycyclohexane), dicyclopentadiene diepoxide, di (3,4-epoxycyclohexylmethyl) ether of ethylene glycol, Examples include ethylenebis (3,4-epoxycyclohexanecarboxylate), dioctyl epoxyhexahydrophthalate, and di-2-ethylhexyl epoxyhexahydrophthalate.

Further preferred as the aliphatic epoxy resin, aliphatic polyhydric alcohols, or polyglycidyl ether of an alkylene oxide adduct thereof, polyglycidyl esters of aliphatic long-chain polybasic acids, homopolymers of glycidyl acrylate and glycidyl methacrylate, copolymers and the like. Typical examples thereof include diglycidyl ether of 1,4-butanediol, diglycidyl ether of 1,6-hexanediol, triglycidyl ether of glycerin, triglycidyl ether of trimethylolpropane, and diglycidyl ether of polyethylene glycol. ,
Polyglycidyl ethers of polyether polyols obtained by adding one or more alkylene oxides to aliphatic polyhydric alcohols such as diglycidyl ether of polypropylene glycol, ethylene glycol, propylene glycol, and glycerin; And diglycidyl esters of basic acids. Furthermore, monoglycidyl ether of aliphatic higher alcohol, phenol, cresol, butylphenol or monoglycidyl ether of polyether alcohol obtained by adding alkylene oxide thereto, glycidyl ester of higher fatty acid, epoxidized soybean oil, butyl epoxy stearate Octyl epoxy stearate,
Epoxidized linseed oil, epoxidized polybutadiene, and the like.

Examples of cationic polymerizable organic substances other than epoxy compounds include oxetane compounds such as trimethylene oxide, 3,3-dimethyloxetane, and 3,3-dichloromethyloxetane; oxolane compounds such as tetrahydrofuran and 2,3-dimethyltetrahydrofuran Cyclic acetal compounds such as trioxane, 1,3-dioxolan, 1,3,6-trioxanecyclooctane; cyclic lactone compounds such as β-propiolactone and ε-caprolactone; ethylene sulfide, thioepichlorohydrin Such thiirane compounds; 1,3-propyne sulfide, 3,3-
Thietane compounds such as dimethylthiethane; ethylene glycol divinyl ether, alkyl vinyl ether,
Vinyl ether compounds such as 3,4-dihydropyran-2-methyl (3,4-dihydropyran-2-carboxylate) and triethylene glycol divinyl ether; spiro ortho ester compounds obtained by reacting epoxy compounds with lactones; Examples include ethylenically unsaturated compounds such as vinylcyclohexane, isobutylene, polybutadiene and derivatives of the above compounds. These cationically polymerizable compounds can be used alone or in combination of two or more kinds according to desired performance.

Particularly preferred among these cationically polymerizable organic substances are alicyclic epoxy resins having at least two or more epoxy groups in one molecule, and having cationic polymerization reactivity,
It shows good properties in terms of viscosity reduction, UV transmittance, thick film curability, volume shrinkage, resolution and the like.

The energy ray-sensitive cationic polymerization initiator (b) used in the present invention is bis- [4- (diphenylsulfonio) phenyl] sulfide bishexafluoroantimonate.

A photosensitizer such as benzophenone, benzoin isopropyl ether, or thioxanthone can be used in combination with the cationic polymerization initiator.

The energy ray-curable radical polymerizable organic substance (c) used in the present invention is a radical polymerizable compound that undergoes a polymerization or cross-linking reaction by irradiation with energy rays in the presence of an energy ray-sensitive radical polymerization initiator (d). For example, it is composed of one or a mixture of two or more of acrylate compounds, methacrylate compounds, allyl urethane compounds, unsaturated polyester compounds, polythiol compounds and the like. Among such radically polymerizable compounds, compounds having at least one acrylic group in one molecule are preferable, and examples thereof include epoxy acrylate, urethane acrylate, polyester acrylate, polyether acrylate, and acrylic acid esters of alcohols. Can be

Here, a preferable epoxy acrylate is an acrylate obtained by reacting a conventionally known aromatic epoxy resin, alicyclic epoxy resin, aliphatic epoxy resin or the like with acrylic acid. Among these epoxy acrylates, particularly preferred is an acrylate of an aromatic epoxy resin, which is obtained by reacting a polyglycidyl ether of a polyhydric phenol having at least one aromatic nucleus or an alkylene oxide adduct thereof with acrylic acid. The obtained acrylate, for example, bisphenol A, or an alkylene oxide adduct thereof,
Examples include acrylates obtained by reacting glycidyl ether obtained by reaction with epichlorohydrin with acrylic acid, and acrylates obtained by reacting epoxy novolak resin with acrylic acid.

Preferred urethane acrylates include one or more hydroxyl group-containing polyesters, acrylates obtained by reacting hydroxyl group-containing polyethers with hydroxyl group-containing acrylates and isocyanates, and hydroxyl group-containing acrylates and isocyanates. An acrylate obtained by the reaction. Preferred as the hydroxyl group-containing polyester used here is a hydroxyl group-containing polyester obtained by an esterification reaction of one or more aliphatic polyhydric alcohols with one or more polybasic acids. Examples of the aliphatic polyhydric alcohol include 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol,
Examples thereof include triethylene glycol, neopentyl glycol, polyethylene glycol, polypropylene glycol, trimethylolpropane, glycerin, pentaerythritol, and dipentaerythritol. Examples of the polybasic acid include adipic acid, terephthalic acid, phthalic anhydride, and trimellitic acid. Preferred as the hydroxyl group-containing polyether is a hydroxyl group-containing polyether obtained by adding one or more alkylene oxides to an aliphatic polyhydric alcohol,
Examples of the aliphatic polyhydric alcohol include 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, triethylene glycol,
Neopentyl glycol, polyethylene glycol, polypropylene glycol, trimethylolpropane, glycerin, pentaerythritol, dipentaerythritol. Examples of the alkylene oxide include ethylene oxide and propylene oxide. Preferred as a hydroxyl group-containing acrylate is an aliphatic polyhydric alcohol and a hydroxyl group-containing acrylate obtained by an esterification reaction with acrylic acid.Examples of the aliphatic polyhydric alcohol include ethylene glycol and 1 , 3-butanediol, 1,4-
Butanediol, 1,6-hexanediol, diethylene glycol, triethylene glycol, neopentyl glycol, polyethylene glycol, polypropylene glycol, trimethylolpropane, glycerin, pentaerythritol, dipentaerythritol. Among these hydroxyl group-containing acrylic esters, a hydroxyl group-containing acrylic ester obtained by an esterification reaction between an aliphatic dihydric alcohol and acrylic acid is particularly preferable, and examples thereof include 2-hydroxyethyl acrylate. As the isocyanates, compounds having at least one isocyanate group in a molecule are preferable, but compounds such as tolylene diisocyanate, hexamethylene diisocyanate and isophorone diisocyanate are preferred.
Valent isocyanate compounds are particularly preferred.

Preferred as the polyester acrylate is a polyester acrylate obtained by reacting a hydroxyl group-containing polyester with acrylic acid. Preferred as the hydroxyl group-containing polyester used here is an esterification reaction of one or more aliphatic polyhydric alcohols with one or more monobasic acids, polybasic acids, and phenols. The resulting hydroxyl group-containing polyester, as the aliphatic polyhydric alcohol, for example, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, triethylene glycol, neopentyl glycol, polyethylene Glycol, polypropylene glycol, trimethylolpropane, glycerin, pentaerythritol, dipentaerythritol. As the monobasic acid, for example,
Formic acid, acetic acid, butylcarboxylic acid, and benzoic acid. Examples of the polybasic acid include adipic acid, terephthalic acid, phthalic anhydride, and trimellitic acid. Examples of phenols include phenol and p-nonylphenol.

Preferred as the polyether acrylate is a polyether acrylate obtained by reacting a hydroxyl group-containing polyether with acrylic acid. Preferred as the hydroxyl group-containing polyether used here is a hydroxyl group-containing polyether obtained by adding one or more alkylene oxides to an aliphatic polyhydric alcohol, and as the aliphatic polyhydric alcohol, For example, 1,3-butanediol, 1,4-butanediol, 1,6-
Examples include hexanediol, diethylene glycol, triethylene glycol, neopentyl glycol, polyethylene glycol, polypropylene glycol, trimethylolpropane, glycerin, pentaerythritol, and dipentaerythritol. Examples of the alkylene oxide include ethylene oxide and propylene oxide.

Preferred as acrylates of alcohols are aromatics having at least one hydroxyl group in the molecule,
Or an aliphatic alcohol, and an acrylate obtained by reacting an alkylene oxide adduct thereof with acrylic acid, for example, 2-ethylhexyl acrylate,
2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, isoamyl acrylate, lauryl acrylate, stearyl acrylate, isooketyl acrylate, tetrahydrofurfuryl acrylate, isobornyl acrylate, benzyl acrylate, 1,3-butanediol diacrylate, 1,4 -Butanediol diacrylate, 1,6-hexanediol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, neopentyl glycol diacrylate, polyethylene glycol diacrylate, polypropylene glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate Acrylate, dipentaerythritol hexaacrylate It is.

Among these acrylates, polyacrylates of polyhydric alcohols are particularly preferred.

These radically polymerizable organic substances can be used alone or
More than one kind can be compounded and used according to the desired performance.

Among the above (c) energy ray-curable radically polymerizable organic substances, particularly preferred are compounds having at least three or more unsaturated double bonds in one molecule.

The energy ray-sensitive radical polymerization initiator (d) used in the present invention is a compound capable of releasing a substance that initiates radical polymerization by irradiation with energy rays,
Ketones such as acetophenone compounds, benzoin ether compounds, benzyl compounds, benzophenone compounds and thioxanthone compounds are preferred. Examples of the acetophenone-based compound include diethoxyacetophenone, 2-hydroxymethyl-1-phenylpropan-1-one, 4'-isopropyl-2-hydroxy-2
-Methyl-propiophenone, 2-hydroxy-2-methyl-propiophenone, p-dimethylaminoacetophenone, p-tert-butyldichloroacetophenone, p
-Tert-butyltrichloroacetophenone and p-azidobenzalacetophenone. Examples of the benzoin ether compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin normal butyl ether, and benzoin isobutyl ether. Examples of the benzyl compound include benzyl, benzyldimethyl ketal, benzyl-β-methoxyethyl acetal, and 1-hydroxycyclohexylphenyl ketone. Examples of the benzophenone-based compound include benzophenone, methyl o-benzoylbenzoate, Michler's ketone, 4,4'-bisdiethylaminobenzophenone, and 4,4'-dichlorobenzophenone.
Thioxanthone compounds include thioxanthone, 2
-Methylthioxanthone, 2-ethylthioxanthone,
2-chlorothioxanthone and 2-isopropylthioxanthone are exemplified.

These energy ray-sensitive radical polymerization initiators (d) can be used alone or in combination of two or more kinds according to desired performance.

Next, (a) an energy ray-curable cationically polymerizable organic substance, (b) an energy ray-sensitive cationic polymerization initiator, (c) an energy ray-curable radically polymerizable organic substance, and (d) an energy ray-sensitive radical according to the present invention. The composition ratio of the polymerization initiator will be described. The composition ratio will be described in parts (parts by weight).

That is, in the present invention, the composition ratio of the energy ray-curable cationic polymerizable organic substance (a) and the energy ray-curable radical polymerizable organic substance (c) is determined by comparing the energy ray-curable cationic polymerizable organic substance (a) with the energy Assuming that the total of the radiation-curable radically polymerizable organic substance (c) is 100 parts, the energy-ray-curable cationically polymerizable organic substance (a)
40 to 95 parts, that is, 5 to 60 parts of the energy ray-curable radically polymerizable organic substance (c), more preferably 50 to 90 parts of the energy ray-curable cationic polymerizable organic substance (a). Parts, that is, those containing 10 to 50 parts of the energy ray-curable radically polymerizable organic substance (c) have particularly excellent properties as a resin composition for optical shaping.

In the composition of the present invention, the energy ray-curable cationically polymerizable organic substance (a) and the energy ray-curable radically polymerizable organic substance (c) are used in order to obtain desired properties as a resin composition for optical shaping. A plurality of energy ray-curable organic substances, that is, an energy ray-curable cationically polymerizable organic substance (a) and an energy ray-curable radically polymerizable organic substance (c) can be blended and used.

The content of the energy ray-sensitive cationic polymerization initiator (b) in the composition of the present invention is 100 parts of the energy ray-curable organic substance, that is, the energy ray-curable cationic polymerizable organic substance (a) and the energy ray-curable radical. It can be contained in the range of 0.1 to 10 parts, preferably 0.5 to 6 parts, based on 100 parts of the polymerizable organic substance (c) in total. The content of the energy-ray-sensitive radical polymerization initiator (d) in the composition of the present invention is determined by the energy-ray-curable organic substance.
It can be contained in the range of 0.1 to 10 parts, preferably 0.2 to 5 parts based on 100 parts. The energy ray-sensitive cationic polymerization initiator (b) and the energy ray-sensitive radical polymerization initiator (d) are used as a resin composition for optical shaping to obtain a plurality of energy ray-sensitive cationic polymerization initiators ( b) and an energy ray-sensitive radical polymerization initiator (d) can be used in combination. When these polymerization initiators are mixed with an energy ray-curable organic substance, the polymerization initiators can be used by dissolving them in an appropriate solvent.

In the composition of the present invention, the composition is obtained when the composition ratio of the energy-ray-curable cationically polymerizable organic substance (a) is too large, that is, when the composition ratio of the energy-ray-curable radically polymerizable organic substance (c) is too small. The composition is hardly affected by oxygen in the air at the time of the curing reaction by the active energy ray, and can reduce the volume shrinkage at the time of curing. Since a low-viscosity resin composition can be easily obtained, the molding time can be reduced. However, at the time of the curing reaction by the active energy ray, since the polymerization reaction easily proceeds from the irradiated part of the active energy ray to the peripheral part, the resolution is poor, and
After the irradiation with the active energy ray, it takes several seconds until the polymerization reaction is completed. Conversely, when the composition ratio of the energy ray-curable cationically polymerizable organic substance (a) is too small, that is, the energy ray-curable radically polymerizable organic substance (c)
If the composition ratio is too large, the polymerization reaction hardly proceeds from the irradiated portion of the active energy ray to the peripheral portion, so that the resolution is good, and almost no time is required until the polymerization reaction is completed after the irradiation of the active energy ray. . However, at the time of the curing reaction by the active energy ray, the polymerization reaction is easily inhibited by oxygen in the air, and the cured product is liable to be distorted and cracked due to a large volume shrinkage at the time of curing, further reducing the viscosity. Therefore, when a low-viscosity radically polymerizable resin is used, skin irritation is large. None of these compositions are suitable as optical molding resin compositions.

The resin composition for optical shaping according to the present invention, in particular, (a) the energy ray-curable cationically polymerizable organic substance contains at least 40% by weight of an alicyclic epoxy resin having at least two epoxy groups in one molecule. (C) the energy ray-curable radically polymerizable organic substance contains at least 3
When a compound having at least 50 unsaturated double bonds is contained in an amount of 50% by weight or more, the energy ray reactivity is good, the mechanical strength and the resolution are excellent, and the shrinkage ratio is 3% or less. An excellent optical shaping system can be constructed.

As long as the effects of the present invention are not impaired, the resin composition for optical shaping of the present invention may contain, if necessary, a heat-sensitive cationic polymerization initiator; a coloring agent such as a pigment or a dye; a defoaming agent, a leveling agent, and a thickening agent. Various resin additives such as agents, flame retardants and antioxidants;
Fillers such as silica, glass powder, ceramic powder, metal powder and the like; modifying resins and the like can be used in appropriate amounts. Examples of the heat-sensitive cationic polymerization initiator include aliphatic onium salts described in JP-A-57-49613 and JP-A-58-37004.

The viscosity of the composition of the present invention is preferably 2000 at room temperature.
Cps or less, more preferably 1000 cps or less. If the viscosity is too high, the working time tends to be poor because the molding time is long.

Generally, a molding resin composition shrinks in volume during curing, and therefore, it is required that shrinkage be small in terms of accuracy. The volume shrinkage of the composition of the present invention upon curing is preferably 5% or less, more preferably 3% or less.

As a specific method of carrying out the present invention, JP-A-60-247515
As described in the publication, the optical molding resin composition of the present invention is housed in a container, a light guide is inserted into the resin composition, and the container and the light guide are relatively positioned. By selectively supplying active energy rays necessary for curing from the light guide while moving, a solid having a desired shape can be formed. As the active energy ray used for curing the composition of the present invention, ultraviolet rays, electron beams, X-rays, radiation, high frequency, and the like can be used. Among them, ultraviolet light having a wavelength of 1800 to 5000 ° is economically preferable, and as the light source, an ultraviolet laser, a mercury lamp, a xenon lamp, a sodium lamp, an alkali metal lamp and the like can be used. A particularly preferable light source is a laser light source, which can increase the energy level to shorten the molding time, and improve the molding accuracy by using good light-collecting properties. Also, a point light source that collects ultraviolet rays from various lamps such as a mercury lamp is effective. Furthermore,
In order to selectively supply the active energy ray required for curing to the present resin composition, it is necessary to have a wavelength equal to twice the wavelength suitable for curing the resin composition and having the same phase.
In the resin composition, two or more luminous fluxes are irradiated so as to cross each other, energy rays necessary for curing the resin composition are obtained by two-photon absorption, and the crossing point of the light is moved. You can also. The light beams having the same phase can be obtained by, for example, a laser beam.

The curing of the composition of the present invention proceeds by a cationic polymerization reaction and a radical polymerization reaction by an active energy ray. Therefore, depending on the type of the cationically polymerizable organic substance (a) and the radically polymerizable organic substance (c) used, the active energy ray At the time of irradiation, by heating the resin composition to about 30 to 100 ° C., the crosslinking and curing reaction can be effectively promoted.
Heat to a temperature of 40 to 100 ° C or UV with a mercury lamp
By performing the irradiation treatment, it is also possible to obtain a molded article having more excellent mechanical strength.

The resin composition for optical shaping of the present invention is a very excellent one for creating a three-dimensional solid model by stacking layered products, and can create and process a model without using a mold, and is free. The industrial value is extremely large, as all shapes such as curved surfaces can be created with high precision by CAD / CAM and docking. For example, as application fields of the present resin composition, a model for examining an external design in the middle of design, a model for checking inconvenience of mutual combination of parts, a wooden mold for manufacturing a mold, and a mold are used. It can be used for a wide range of applications, such as copying models for manufacturing.

Specific fields of application include models and processing of various curved surfaces such as automobiles, electronic / electric parts / furniture, architectural structures, toys, containers, castings, dolls, and the like.

〔Example〕

Hereinafter, representative examples of the present invention by Examples,
Although described more specifically, the present invention is not limited by the following embodiments. In the examples, "parts" means parts by weight.

Example 1 85 parts of 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate as an energy ray-curable cationic polymerizable organic substance (a) and bis- as an energy ray-sensitive cationic polymerization initiator (b) [4
-(Diphenylsulfonio) phenyl] sulfide bishexafluoroantimonate (3 parts), as an energy ray-curable radical polymerizable organic substance (c), as dipentaerythritol hexaacrylate (15 parts), as an energy ray-sensitive radical polymerization initiator (d) , Benzophenone 1
The parts were sufficiently mixed to obtain an optical molding resin composition. 3D NC (numerical control) table with container for resin composition, helium / cadmium laser (wavelength 325nm)
And, using an optical modeling experimental system composed of a control unit having an optical system and a personal computer as a main unit,
From this resin composition, the bottom diameter is 12 mm, the height is 15 mm, and the thickness is 0.
A 5mm cone was formed. The molding time was 30 minutes.
This molded article had no distortion, extremely high modeling accuracy, and excellent mechanical strength.

Comparative Example 1 As an energy ray-curable cationic polymerizable organic substance (a), 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate 50 parts, 1,4-butanediol diglycidyl ether 20 parts, energy ray 3 parts of triphenylsulfonium hexafluoroantimonate as a sensitive cationic polymerization initiator (b), 20 parts of dipentaerythritol hexaacrylate, 10 parts of trimethylolpropane triacrylate as an energy ray-curable radically polymerizable organic substance (c), One part of benzyldimethyl ketal was sufficiently mixed as an energy ray-sensitive radical polymerization initiator (d) to obtain a resin composition for optical shaping. Using the laser optical modeling experimental system shown in Example 1 to create a bridge-shaped molded article,
This shaped article had no distortion, extremely high modeling accuracy, and excellent mechanical strength. The resin composition was low in viscosity and easy to handle and excellent in curability by laser light, but the molding time was 60 minutes.

Comparative Example 2 As an energy ray-curable cationic polymerizable organic substance (a), bisphenol A diglycidyl ether 20 parts, 3, 3
30 parts of 4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 10 parts of vinylcyclohexene oxide, 2 parts of triphenylsulfonium hexafluoroantimonate as an energy ray-sensitive cationic polymerization initiator (b), energy ray-curable radical As a polymerizable organic substance (c), 15 parts of bisphenol A epoxy acrylate, 25 parts of pentaerythritol triacrylate, and 2 parts of 2,2-diethoxyacetophenone as an energy ray-sensitive radical polymerization initiator (d) are sufficiently mixed, An optical molding resin composition was obtained. Using the laser optical modeling experimental system shown in Example 1 to heat the composition to 60 ° C. to form a cup-shaped molded product, a product having no distortion and excellent molding accuracy was obtained. The molding time was 65 minutes.

Example 2 As an energy ray-curable cationic polymerizable organic substance (a), 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate 50 parts, 1,4-butanediol diglycidyl ether 10 parts, triethylene 20 parts of glycol divinyl ether, 20 parts of dipentaerythritol hexaacrylate as an energy ray-curable radical polymerizable organic substance (c), and bis- [4- (diphenylsulfonio) phenyl as an energy ray-sensitive cationic polymerization initiator (b) A stereolithography resin composition comprising 2 parts of sulfide bishexafluoroantimonate and 1 part of benzophenone as the energy ray-curable radical polymerization initiator (d) was obtained. Using this composition, a bridge-shaped object was produced by the laser optical modeling experimental system shown in Example 1, and there was no distortion, mechanical strength,
A product excellent in molding accuracy and surface smoothness was obtained. The modeling time was 35 minutes.

Comparative Example 3 3,4-Epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate 60 parts, bisphenol A diglycidyl ether 20 parts, 1,4-butanediol diglycidyl ether 20 parts, triphenylsulfonium hexafluoroantimonate 3 Parts were sufficiently mixed to obtain an energy ray-curable cationically polymerizable resin composition. Using this composition, a conical shaped article similar to that of Example 1 was produced using the laser optical modeling experimental system shown in Example 1. Although the resin composition had excellent strength, the resin composition had poor resolution when cured by laser light, so that the surface of the molded article was rough and had poor molding accuracy. In addition, it was necessary to wait several seconds from the time of laser irradiation until the polymerization reaction was completed, and the required molding time was 150 minutes.

Comparative Example 4 70 parts of bisphenol A epoxy acrylate, 30 parts of trimethylolpropane triacrylate, and 3 parts of benzyldimethyl ketal were sufficiently mixed to obtain an energy ray-curable radically polymerizable resin composition. Using this composition, a conical shaped article similar to that of Example 1 was produced using the laser optical modeling experimental system shown in Example 1. As a result, the molded article suffered large strain due to large curing shrinkage. However, the molding accuracy was poor. The molding time was 30 minutes.

Comparative Example 5 Bisphenol A diglycidyl ether 60 parts, bis-
[4- (Diphenylsulfonio) phenyl] sulfide bishexafluoroantimonate (3 parts), bisphenol A epoxy acrylate (15 parts), dipentaerythritol hexaacrylate (25 parts), 2,2-diethoxyacetophenone (2 parts) are sufficiently mixed, and energy rays A curable resin composition was obtained.

When a conical shaped article similar to that of Example 1 was created using the laser optical modeling experimental system shown in Example 1, the shaped article had no distortion and was excellent in mechanical strength.
The curability was poor, and the molding time was 75 minutes.

〔The invention's effect〕

Since the resin composition for optical shaping of the present invention is a mixed composition of an energy ray-curable cationically polymerizable organic substance and an energy ray-curable radically polymerizable organic substance, the properties of the energy ray-curable cationically polymerizable organic substance And a resin composition having both advantages of the properties of an energy ray-curable radically polymerizable organic substance. The cationically polymerizable resin composition is not affected by oxygen in the air at the time of the curing reaction by the active energy ray, and can reduce the volume shrinkage at the time of curing. Hardly occurs, the strength of the cured product is excellent, the molding time can be reduced because the low-viscosity tree composition is easy,
There are advantages such as. However, during the curing reaction by the active energy ray, the polymerization reaction easily progresses from the irradiated part of the active energy ray to the peripheral part, so that the resolution is poor.After the irradiation of the active energy ray, the time of several seconds until the polymerization reaction is completed. , Etc. are required. On the other hand, the radical polymerizable resin composition has a good resolution because the polymerization reaction hardly proceeds from a portion irradiated with the active energy beam to a peripheral portion at the time of the curing reaction by the active energy beam. It has the advantage that it takes almost no time to finish. However, the polymerization reaction is inhibited by oxygen in the air, the shrinkage upon curing is large, the mechanical strength of the cured product is poor, and the low-viscosity resin has disadvantages such as high skin irritation and strong odor. .

In the present invention, (a) an energy ray-curable cationic polymerizable organic substance, (b) an energy ray-sensitive cationic polymerization initiator, (c) an energy ray-curable radical polymerizable organic substance, and (d) an energy ray-sensitive radical polymerization start By mixing the agents, a resin composition for optical shaping having the following characteristics could be obtained. That is, it is hardly affected by oxygen in the air. Since the volume shrinkage at the time of curing can be reduced, distortion, cracks, and the like hardly occur in the cured product. Since the low-viscosity resin composition is easy, the molding time can be reduced. At the time of active energy ray irradiation, from the active energy ray irradiation part to the peripheral part,
Good resolution because polymerization reaction does not proceed easily. After the irradiation with the active energy ray, it takes almost no time until the polymerization reaction is completed. The cured product has excellent mechanical strength and hardness.

Continuation of front page (56) References JP-A-62-187722 (JP, A) JP-A-62-112619 (JP, A) JP-A-59-152922 (JP, A) JP-A-62-36755 (JP, A) JP-A-62-192724 (JP, A) JP-A-62-288844 (JP, A) JP-A-62-101408 (JP, A) JP-A-60-247515 (JP, A)

Claims (2)

(57) [Claims] 1. An energy ray-curable cationically polymerizable organic material containing, as essential components, (a) at least 40% by weight of an alicyclic epoxy resin having at least two epoxy groups in one molecule, (b) As an energy ray-sensitive cationic polymerization initiator, bis- [4- (diphenylsulfonio)
Phenyl] sulfide bishexafluoroantimonate, (c) an energy ray-curable radically polymerizable organic substance, and (d) an energy ray-sensitive radical polymerization initiator. 2. The method according to claim 1, wherein (c) the energy ray-curable radically polymerizable organic substance contains at least 50% by weight of a compound having at least three unsaturated double bonds in one molecule. 2. The resin composition for optical shaping according to 1.