JP2632961B2 - Optical molding method of resin - Google Patents

Description

The present invention relates to an optical shaping method using 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. Recently, technology development is expected to solve these problems of the conventional technology and create new methods 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.

Optical molding method of the resin of the present invention, as an essential component,
(A) an energy ray-curable cationic polymerizable organic substance,
(B) bis- [4-diphenylsulfonio) phenyl] sulfide bishexafluoroantimonate as an energy ray-sensitive cationic polymerizable initiator; and (c) epoxy acrylate having two unsaturated double bonds in one molecule. An energy ray-curable radically polymerizable organic substance containing 50% by weight or more, and a resin composition containing (d) an energy ray-sensitive radical polymerization initiator are contained in a container, and the resin is irradiated with active energy rays. It is characterized in that a molded article is obtained by curing the composition.

The energy-ray-curable cationically polymerizable organic substance (a) which is a constituent element of the present invention is bis- [4- (diphenylsulfonio) phenyl] sulfide bishexafluoroantimonate (an energy-ray-sensitive cationic polymerization initiator). In the presence of b), a cationically polymerizable compound that polymerizes or undergoes a cross-linking reaction by irradiation with energy rays, such as an epoxy compound, a cyclic ether compound, a cyclic lactone compound, a cyclic acetal compound, a cyclic thioether compound,
It comprises one or a mixture of two or more spiro orthoester compounds, vinyl compounds and the like. Among these cationically polymerizable compounds, compounds having at least two or more epoxy groups in one molecule are preferable, and examples thereof include conventionally known aromatic epoxy resins, alicyclic epoxy resins, and aliphatic epoxy resins. Can be

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. There are, as typical examples, diglycidyl ether of 1,4-butanediol, diglycidyl ether of 1,6-hexanediol, triglycidyl ether of glycerin, triglycidyl ether of trimethylolpropane, tetraglycidyl ether of sorbitol, Hexaglycidyl ether of dipentaerythritol, diglycidyl ether of polyethylene glycol, diglycidyl ether of polypropylene glycol, ethylene glycol, propylene glycol Polyglycidyl ethers of polyether polyols obtained by adding one or more alkylene oxides to aliphatic polyhydric alcohols such as glycerin, and diglycidyl esters of aliphatic long-chain dibasic 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). Epoxy acrylate having two unsaturated double bonds in one molecule
It contains 50% by weight or more.

Preferred as such epoxy acrylate is bisphenol A epoxy acrylate, and other hydrogenated bisphenol A epoxy acrylate, alkylene oxide-added bisphenol A epoxy acrylate, and bisphenol F epoxy acrylate are also used.

1 such as the above bisphenol A epoxy acrylate
Epoxy acrylate having two unsaturated double bonds in the molecule has particularly good radical polymerization reactivity among acrylate resins. In the optical molding method of the resin of the present invention, by including such an epoxy acrylate as an energy ray-curable radically polymerizable organic substance, the curing speed can be increased and the molding time can be reduced.

In the present invention, other energy ray-curable radically polymerizable organic substances can be used in a proportion of less than 50% by weight.

Such a substance is, for example, one or two of an acrylate compound, a methacrylate compound, an allyl urethane compound, an unsaturated polyester compound, a polythiol compound and the like.
It consists of a mixture of more than one species. 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, preferred epoxy acrylates include conventionally known aromatic epoxy resins, alicyclic epoxy resins, and aliphatic epoxy resins other than the epoxy acrylate having two unsaturated double bonds in one molecule. When,
It is an acrylate obtained by reacting with acrylic acid. Among these epoxy acrylates, particularly preferred are acrylates of aromatic epoxy resins,
An acrylate 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,
An acrylate obtained by reacting an epoxy novolak resin with acrylic acid is exemplified.

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 polyhydrochloride group 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. Examples of the monobasic acid include formic acid, acetic acid, butylcarboxylic acid, and benzoic acid.
Examples of polybasic acids include adipic acid, terephthalic acid,
Examples include 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, isooctyl 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.

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). 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 optical molding method of the present invention, the energy ray-curable cation polymerizable organic substance (a) and the energy ray-curable radically polymerizable organic substance (c) are used to obtain desired properties as an optical modeling resin composition. And 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).

The content of the energy ray-sensitive cationic polymerization initiator (b) in the optical shaping method 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 0.1 to 10 parts with respect to a total of 100 parts of the radical polymerizable organic substance (c),
Preferably, it can be contained in the range of 0.5 to 6 parts.
Further, the content of the energy ray-sensitive radical polymerization initiator (d) in the optical shaping method of the present invention is 0.1 to 10 parts, preferably 100 parts, based on 100 parts of the energy ray-curable organic substance.
It can be contained in the range of 0.2 to 5 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 optical shaping method of the present invention, 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 resulting composition is hardly affected by oxygen in the air at the time of the curing reaction by the active energy ray, and since the volume shrinkage at the time of curing can be reduced, the cured product is less likely to be distorted or cracked. Since the resin composition having a lower viscosity can be easily obtained, the molding time can be shortened. However, at the time of the curing reaction by the active energy ray, the polymerization reaction easily progresses from the irradiated part of the active energy to the peripheral part, so that the resolution is poor, and after the irradiation of the active energy ray, it takes several seconds until the polymerization reaction is completed. Takes time. Conversely, if the composition ratio of the energy-ray-curable cationically polymerizable organic substance (a) is too small, that is, if the composition ratio of the energy-ray-curable radically polymerizable organic substance (c) is too large, the active energy ray-irradiated portion Since the polymerization reaction hardly proceeds from the surface to the peripheral portion, the resolution is good, and almost no time is required until the polymerization reaction is completed after irradiation with active energy rays. But,
At the time of curing reaction by active energy rays, the polymerization reaction is easily inhibited by oxygen in the air, and the volume shrinkage at the time of curing is large, so that the cured product is easily deformed or cracked. Use of a viscosity-radical polymerizable resin results in great skin irritation. None of these compositions are suitable as optical molding resin compositions.

In the optical shaping method of the resin of the present invention, particularly,
When 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, it has good energy ray reactivity, It has excellent target strength and resolution, and has a shrinkage ratio of 3% or less, so that a very selected optical modeling system can be constructed.

In the optical shaping method of the resin of the present invention, a heat-sensitive cationic polymerization initiator; a coloring agent such as a pigment or a dye; a defoaming agent, a leveling agent, a thickening agent, if necessary, as long as the effects of the present invention are not impaired. Various resin additives such as agents, flame retardants, antioxidants, etc .; fillers such as silica, glass powder, ceramic powder, metal powder, etc .; As the heat-sensitive cationic polymerization initiator, for example,
The aliphatic onium salts described in JP-A-57-49613 and JP-A-58-37004 are exemplified.

The viscosity of the resin composition in the present invention is preferably 2000 cps or less at room temperature, more preferably 1000 cps.
These are: 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 resin composition in the present invention upon curing is preferably 5% or less, more preferably 3% or less.

As a specific implementation method of the present invention, JP-A-60-271515
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 resin composition of the present invention, ultraviolet rays, electron beams, X-rays, radiation, high frequency, or 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 a good light collecting property. Also, a point light source that collects ultraviolet rays from various lamps such as a mercury lamp is effective. Further, in order to selectively supply the active energy ray required for curing to the resin composition of the present invention, the resin composition has a wavelength equal to twice the wavelength suitable for curing the resin composition, and In the resin composition, two or more luminous fluxes having uniformity are irradiated so as to cross each other, and energy rays necessary for curing the resin composition are obtained by two-photon absorption. It can be done by moving. The light beams having the same phase can be obtained by, for example, a laser beam.

The curing of the resin composition of the present invention proceeds by a cationic polymerization reaction and a radical polymerization reaction using active energy rays. Therefore, depending on the types of the cationically polymerizable organic substance (a) and the radically polymerizable organic substance (c) used, At the time of irradiation with energy rays, the resin composition is heated to about 30 to 100 ° C., so that the cross-linking and curing reaction can be effectively promoted. By performing a heat treatment at a temperature of 40 to 100 ° C. or a UV irradiation treatment with a mercury lamp or the like, a molded article having more excellent mechanical strength can be obtained.

The optical molding method of the resin of the present invention is very excellent for creating a three-dimensional three-dimensional model by stacking layered products, and the model can be formed without using a mold, and free-form surfaces can be formed. The industrial value is extremely large, as CAD / CAM and docking can create any shape with high precision. For example, as an application field of the optical shaping method of the present invention, a model for examining an external design during design, a model for checking inconvenience of combination of parts, a wooden mold for manufacturing a mold, For example, a method of forming a model for copying processing for manufacturing a mold, etc.
Can be used for a wide range of applications.

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 (a) As an energy ray-curable cationic polymerizable organic substance, 65 parts of 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 20 parts of 1,4-butanediol diglycidyl ether, (b) ) As an energy ray-sensitive cationic polymerization initiator, bis- [4-
(Diphenylsulfonio) phenyl] sulfide bishexafluoroantimonate (3 parts), (c) energy ray-curable radical polymerizable organic substance, bisphenol A epoxy acrylate (15 parts), (d) energy ray-sensitive radical polymerization initiator, benzophenone One part was sufficiently mixed to obtain an optical molding resin composition. A three-dimensional NC (numerical control) table with a container for holding the resin composition, a helium / cadmium laser (wavelength 325 nm),
Using a stereolithography experimental system consisting of an optical system and a control unit having a personal computer as the main unit, the bottom of the resin composition was 12 mm in diameter, 15 mm in height, and 0.5 mm in thickness.
Shaped cone. This molded article had no distortion, extremely high modeling accuracy, and excellent mechanical strength.

The time required for molding was measured to compare the polymerization rates by laser, and it was as short as 30 minutes. Also,
In order to measure the modeling accuracy, the diameter of the bottom surface of the conical shaped object was arbitrarily measured at 10 places, and the variation was measured.
1.8% average error from the average value (hereinafter referred to as modeling accuracy)
And was highly accurate.

Comparative Example 1 (a) As an energy ray-curable cationic polymerizable organic substance, 50 parts of 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 20 parts of 1,4-butanediol diglycidyl ether, (b) 3) triphenylsulfonium hexafluoroantimonate (3 parts) as an energy ray-sensitive cationic polymerization initiator;
Optically mix 20 parts of bisphenol A epoxy acrylate and 10 parts of trimethylolpropane triacrylate as energy ray-curable radical polymerizable organic substances and 1 part of benzyldimethyl ketal as an energy ray-sensitive radical polymerization initiator. Thus, a resin composition for modeling was obtained. Using the laser optical modeling experimental system shown in Example 1, the composition was heated to 60 ° C. to form a bridge-like shaped product. The shaped product had no distortion and extremely high modeling accuracy. And high mechanical strength. In addition, the resin composition is easy to handle with low viscosity,
It was excellent in curability by laser light.

In order to measure polymerization speed and modeling accuracy by laser,
When a conical shaped article similar to that of Example 1 was made, the shaping time was 30 minutes and the shaping accuracy was 1.5%. The molding time without heating was 65 minutes.

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

According to the laser, the same conical shaped product as in Example 1 was prepared to measure the polymerization rate and the modeling accuracy.
The reaction speed was fast because of heating, and the molding time was as short as 20 minutes. The modeling accuracy was 1.9%. The molding time without heating was 55 minutes.

Example 2 (a) As an energy ray-curable cationic polymerizable organic substance, 55 parts of 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 10 parts of 1,4-butanediol diglycidyl ether, triethylene 15 parts of glycol divinyl ether, (b) 2 parts of bis- [4- (diphenylsulfonio) phenyl] sulfide bishexafluoroantimonate as an energy ray-sensitive cationic polymerization initiator, and (c) energy ray-curable radical polymerizable organic compound 20 parts of bisphenol A epoxy acrylate as a substance and 1 part of benzophenone as an energy ray-sensitive radical polymerization initiator (d) were sufficiently mixed to obtain a resin composition for optical shaping. Using this composition, a bridge-shaped object was produced by the laser optical modeling experimental system shown in Example 1. As a result, a product having no distortion and excellent mechanical strength, molding accuracy, and surface smoothness was obtained. Was done.

In order to measure polymerization speed and modeling accuracy by laser,
When a conical shaped article similar to that of Example 1 was made, the shaping time was 30 minutes and the shaping accuracy was 1.6%.

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 as long as 120 minutes. The modeling accuracy showed a large value of 6.8%.

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, and the molding time was relatively short, 45 minutes. However, this molded article was distorted due to large curing shrinkage, and the molding accuracy was very poor at 10.0%.

Comparative Example 5 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate 65 parts, 1,4-butanediol diglycidyl ether 20 parts, bis- [4- (diphenylsulfonio) phenyl] sulfide bishexafluoro 3 parts of antimonate, 10 parts of dipentaerythritol hexaacrylate, 5 parts of bisphenol A epoxy acrylate and 1 part of benzophenone were sufficiently mixed to obtain an energy ray-curable cation / radical 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. This molded article had no distortion and excellent mechanical strength. The molding time was 50 minutes, the molding accuracy was 3.0%, and the resin composition for optical molding had reached a certain level, but the radically polymerizable organic substance contained 50% or more of bisphenol A epoxy acrylate. The molding time was clearly inferior because there was no.

〔The invention's effect〕

The resin composition for optical shaping used in the method 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 resin composition has both advantages of the properties of the organic substance and the properties of the 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.
The cured product has advantages such as hardly causing distortion, cracking, and the like, excellent strength of the cured product, and shortening of molding time due to easy production of a low-viscosity resin composition. 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, and (b) bis- [4- (diphenylsulfonio) phenyl] sulfide bishexafluoroantimonate as an energy ray-sensitive cationic polymerizable initiator; The following advantages are obtained by irradiating an active energy ray to a resin composition obtained by mixing an energy ray-curable radically polymerizable organic substance and (d) an energy ray-sensitive radical polymerization initiator to obtain a molded article. Was completed. 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, the resolution is good because the polymerization reaction hardly proceeds from the active energy ray irradiated portion to the peripheral portion. 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.

 ──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-59-159820 (JP, A) JP-A-61-157520 (JP, A) JP-A-56-100817 (JP, A) JP-A 55-159820 125105 (JP, A) JP-A-2-9480 (JP, A) JP-A-2-12630 (JP, A)

Claims (3)

(57) [Claims] An essential component is (a) an energy ray-curable cationic polymerizable organic substance, and (b) bis- [4- (diphenylsulfonio) phenyl] sulfide bishexafluoroantimonate as an energy ray-sensitive cationic polymerization initiator. (C) an energy ray-curable radically polymerizable organic substance containing 50% by weight or more of an epoxy acrylate having two unsaturated double bonds in one molecule;
(D) A resin composition containing an energy ray-sensitive radical polymerization initiator is contained in a container, and the resin composition is cured by irradiating with an active energy ray to obtain a molded article. Modeling method. 2. The method according to claim 1, wherein (a) the energy ray-curable cationic polymerizable organic substance contains at least 40% by weight of an alicyclic epoxy resin having at least two epoxy groups in one molecule. Item 7. The optical shaping method according to Item 1. 3. The optical shaping method according to claim 1, wherein the active energy ray is a laser beam.