JP2590230B2 - 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-adhesion method, good curing characteristics in 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 an essential component, (a) 40% by weight or more of an alicyclic epoxy resin containing at least two or more epoxy groups in one molecule;
An energy ray-curable cationic polymerizable organic material containing at least 20% by weight of an aliphatic or aromatic epoxy resin containing at least 3 or more epoxy groups in a molecule, (b) an energy ray-sensitive cationic polymerization initiator, (c) A) / (c) containing an energy ray-curable radically polymerizable organic substance, and (d) an energy ray-sensitive radical polymerization initiator.
= 40-95 / 60-5, (b) / [(a) + (c)] = 0.1-
10/100, (d) / [(a) + (c)] = 0.2 to 5/100.

Examples of the alicyclic epoxy resin containing at least two epoxy groups in one molecule contained in the component (a) of the composition of the present invention include hydrogenated bisphenol A diglycidyl ether, 3,4-epoxy Cyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 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, ethylenebis (3,4-epoxycyclohexanecarboxylate),
Dioctyl epoxyhexahydrophthalate, di-2-ethylhexyl epoxyhexahydrophthalate, and the like.

Next, typical examples of the aliphatic or aromatic epoxy resin containing at least three or more epoxy groups in one molecule contained in the component (a) of the composition of the present invention include triglycidyl ether of glycerin and triglycidyl ether. By adding one or more alkylene oxides to aliphatic polyhydric alcohols such as triglycidyl ether of methylolpropane, tetraglycidyl ether of sorbitol, hexaglycidyl ether of dipentaerythritol, ethylene glycol, propylene glycol and glycerin. Examples of the obtained polyether polyol include polyglycidyl ether, phenol novolak epoxy resin, and the like.

In order to obtain the resin composition for optical shaping which is the object of the present invention, at least two components per molecule in the component (a) are required.
40 cycloaliphatic epoxy resins containing more than one epoxy group
20% by weight or more of an aliphatic or aromatic epoxy resin containing at least 3 epoxy groups per molecule.
It must be contained in an amount of at least% by weight, and if it is less than this, the desired composition cannot be obtained.

In addition to the energy ray-curable cationic polymerizable organic substance (a) which is a constituent element of the present invention, in the presence of an energy ray-sensitive cationic polymerization initiator (b), a polymerization or cross-linking reaction is caused by irradiation with energy rays. Cationic polymerizable compounds, such as epoxy compounds, cyclic ether compounds,
It may include a cyclic lactone compound, a cyclic acetal compound, a cyclic thioether compound, a spiroorthoester compound, a vinyl compound, and the like.

Examples of the epoxy compound include conventionally known aromatic epoxy resins, alicyclic epoxy resins, and aliphatic epoxy resins.

Examples of cationically 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, and 1,3,6-trioxanecyclooctane; cyclic lactone compounds such as β-propiolactone and ε-caprolactone; ethylene sulfide and thioepichlorohydrin Such thiirane compounds; 1,3-propyl 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.

In the cationically polymerizable organic substance (a) of the present invention, by using the above specific components, cationic polymerization reactivity, viscosity reduction, ultraviolet light transmission, thick film curability, volume shrinkage, resolution, cationic polymerization reactivity And good characteristics in terms of molding accuracy and the like.

The energy ray-sensitive cationic polymerization initiator (b) used in the present invention is a compound capable of releasing a substance that initiates cationic polymerization by irradiation with energy rays, and particularly preferably releases a Lewis acid upon irradiation. Is a group of double salts which are onium salts. A typical example of such a compound is represented by the general formula [R ¹ _a R ² _b R ³ _c R ⁴ _d Z] ^{+ m} [MX _{n + m} ] ^-m [wherein the cation is an onium, and Z is S, Se , Te, P, As, S
b, Bi, O, halogen (eg, I, Br, Cl), N≡N,
R ¹ , R ² , R ³ and R ⁴ are organic groups which may be the same or different. a, b, c, d are each an integer of 0 to 3 and a + b
+ C + d is equal to the valence of Z. M is a metal or metalloid which is a central atom of the halide complex, and B, P, As, Sb, Fe, Sn, Bi, Al, Ca, In, Ti, Zn, Sc, V, Cr , Mn, C
o etc. X is a halogen, m is the net charge of the cation, and n is the valence of M. ] Is represented.

Specific examples of the anion MX _{n + m in} the above general formula include tetrafluoroborate (BF ₄ ⁻ ), hexafluorophosphate (PF ₆ ⁻ ), and hexafluoroantimonate (Sb
F ₆ ⁻ ), hexafluoroarsenate (AsF ₆ ⁻ ), hexachloroantimonate (SbCl ₆ ⁻ ) and the like.

Further general formula MX _n (OH) ^- can also be used anion represented by. Other anions include perchlorate ion (ClO ₄ ⁻ ), trifluoromethyl sulfite ion (CF ₃ SO ₃ ⁻ ), fluorosulfonate ion (FSO ₃ ⁻ ),
Examples include a toluenesulfonic acid anion and a trinitrobenzenesulfonic acid anion.

Among these onium salts, it is particularly effective to use an aromatic onium salt as a cationic polymerization initiator, and particularly, the aromatic onium salts described in JP-A-50-151996, JP-A-50-158680 and the like are used. Halonium salts, JP-A-50-151997
No., JP-A-52-30899, JP-A-56-55420, JP-A-55-55420
VIA group aromatic onium salts described in -125105, etc., VA group aromatic onium salts described in JP-A-50-1558698 and the like, JP-A-56-8428, JP-A-56-149402. , JP 57
Oxosulfoxonium salts described in -192429 and the like,
Aromatic diazonium salts described in JP-B-49-17040 and the like, and thiobrillium salts described in U.S. Pat. No. 4,139,655 are preferred. Further, an iron / allene complex or an aluminum complex / photolytic silicon compound-based initiator may, for example, be mentioned.

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, isooctyl acrylate, tetrahydrofurfuryl acrylate, isobornyl acrylate, benzine 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), and preferably the energy ray-curable cationically polymerizable organic substance (a).
Containing 50 to 90 parts, that is, 10 to 50 parts of the energy ray-curable radically polymerizable organic substance (c) has particularly excellent characteristics 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 is contained in an amount of 0.1 to 10 parts, preferably 0.5 to 6 parts, based on a total of 100 parts of the polymerizable organic substance (c). Further, the energy ray-sensitive radical polymerization initiator (d) in the composition of the present invention
Is contained in the range of 0.2 to 5 parts with respect to 100 parts of the energy ray-curable organic substance. 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 rays, and since the volume shrinkage at the time of curing can be reduced, the cured product is hardly distorted or cracked.
Furthermore, 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,
Further, after irradiation with the active energy ray, it takes several seconds until the polymerization reaction is completed. 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. 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 deformed or cracked due to a large volume shrinkage at the time of curing. When using a low viscosity radical polymerizable resin,
Great skin irritation. None of these compositions are suitable as optical molding resin compositions.

The resin composition for optical shaping according to the present invention, in particular, (c) a compound in which the energy ray-curable radically polymerizable organic substance has at least three or more unsaturated double bonds in one molecule.
When it is configured to contain 50% by weight or more, the energy beam reactivity is good, the mechanical strength and resolution are excellent, the shrinkage ratio is 3% or less, and a very excellent optical modeling system can be configured. .

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 (a) Energy ray-curable cationic polymerizable organic substance: 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate 65 parts, sorbitol tetraglycidyl ether 20 parts, (b) energy ray-sensitive cation Bis- [4- (diphenylsulfonio) phenyl] sulfide bishexafluoroantimonate (3 parts) as a polymerization initiator; (c) dipentaerythritol hexaacrylate (15 parts) as an energy ray-curable radical polymerizable organic substance; 1) Benzophenone (1 part) was sufficiently mixed as an energy ray-sensitive radical polymerization initiator to obtain an optical modeling resin composition. 3D NC (numerical control) table with a container for resin composition,
Using a helium / cadmium laser (wavelength: 325 nm) and a stereolithography experiment system composed of a control unit having an optical system and a personal computer as a main unit, a bottom diameter of 12 mm, a height of 15 mm, and a thickness of 0.5 were obtained from this resin composition. mm cone was shaped. 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 35 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.
Average error from the average value (hereinafter referred to as modeling accuracy) is 1.7%
And was highly accurate.

Example 2 (a) 40 parts of 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate, 15 parts of 1,4-butanediol diglycidyl ether, 15 parts of trimethylol as energy ray-curable cationic polymerizable organic substances 15 parts of propane triglycidyl ether, (b) 3 parts of triphenylsulfonium hexafluoroantimonate as an energy ray-sensitive cationic polymerization initiator, (c)
20 parts of dipentaerythritol hexaacrylate, 10 parts of trimethylolpropane triacrylate as an energy ray-curable radical polymerizable organic substance, and 1 part of benzyldimethyl ketal as an energy ray-sensitive radical polymerization initiator were sufficiently mixed. An optical molding resin composition was obtained. 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, easy to handle, and 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 produced, the molding time was 35 minutes, and the modeling accuracy was 1.9%.

Example 3 (a) Bisphenol A diglycidyl ether 10 parts, 3, 3
4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate 25 parts, vinylcyclohexene oxide 10 parts, phenol novolak epoxy resin
15 parts, (b) 2 parts of triphenylsulfonium hexafluoroantimonate as an energy ray-sensitive cationic polymerization initiator, (c) 15 parts of bisphenol A epoxy acrylate as an energy ray-curable radical polymerizable organic substance, pentaerythritol triacrylate twenty five
Parts, (d) 2 parts of 2,2-diethoxyacetophenone as an energy ray-sensitive radical polymerization initiator were sufficiently mixed to obtain a resin composition for optical shaping. Using the laser stereolithography experimental system shown in Example 1, this composition was
When a cup-shaped molded article was produced while heating to ° C., a molded article having no distortion and excellent molding accuracy was obtained.

A conical shaped article similar to that of Example 1 was prepared to measure the polymerization rate and the modeling accuracy by laser. The reaction rate was high because of heating to 60 ° C, and the modeling time was extremely short, 25 minutes. Met. The modeling accuracy was 1.9%.

Example 4 (a) As an energy ray-curable cationic polymerizable organic substance, 35 parts of 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 10 parts of 1,4-butanediol diglycidyl ether, triethylene 15 parts of glycol divinyl ether, 20 parts of sorbitol tetraglycidyl ether, (c) 20 parts of an energy ray-curable radically polymerizable organic substance, 20 parts of dipentaerythritol hexaacrylate, and (b) bis- [ 4- (diphenylsulfonio) phenyl] sulfide bishexafluoroantimonate (2 parts) and (d) 1 part of benzophenone as an energy-ray-sensitive radical polymerization initiator were obtained as a resin composition for optical shaping. Example 1 using this composition
When a bridge-shaped object was produced by the laser optical modeling experiment system shown in (1), a product having no distortion and excellent in mechanical strength, molding accuracy, and surface smoothness was obtained.

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 35 minutes and the shaping accuracy was 1.3%.

Comparative Example 1 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 2 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 3 65 parts of 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 20 parts of 1,4-butanediol diglycidyl ether, bis- [4- (diphenylsulfonio) phenyl] sulfide bishexafluoro Three parts of antimonate, 15 parts of dipentaerythritol hexaacrylate, 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 is 50 minutes,
The modeling accuracy was 3.0%, and as a resin composition for optical shaping, it reached a certain level, but since it does not contain any epoxy resin having at least three or more epoxy groups in one molecule, Both the molding time and the molding accuracy were clearly inferior.

〔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. Are less likely to occur, the cured product has excellent strength, and the low-viscosity resin composition is easy, so that the molding time can be shortened. 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, during the curing reaction by active energy rays,
Advantageously, the polymerization reaction hardly progresses from the active energy ray irradiation part to the peripheral part, so that the resolution is good, and almost no time is required after the active energy ray irradiation until the polymerization reaction is completed. 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 in a specific ratio, 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, 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.

Claims (1)

(57) [Claims] (1) As essential components, (a) at least 40% by weight of an alicyclic epoxy resin containing at least two epoxy groups in one molecule, and at least three or more epoxy groups in one molecule. An energy ray-curable cationically polymerizable organic substance containing at least 20% by weight of an aliphatic or aromatic epoxy resin, (b) an energy ray-sensitive cationic polymerization initiator, (c) an energy ray-curable radically polymerizable organic substance, (D) containing an energy ray-sensitive radical polymerization initiator, (a) / (c) = 40-95 / 60-5, (b) /
[(A) + (c)] = 0.1 to 10/100, (d) / [(a)
+ (C)] = 0.2 to 5/100.