JPH0280423A - Resin composition for optical molding - Google Patents

Abstract

PURPOSE:To obtain the title compsn. providing a cured product with excellent mechanical strengths, hardness, etc., by incorporating a specified radiation- curable cationically polymerizable org. substance and a radiation-curable radical polymerizable org. substance as well as a radiation-sensitive cationic polymn. initiator and a radiation-sensitive radical polymn. initiator as essential components. CONSTITUTION:A radiation-curable cationically polymerizable org. substance contg. 40wt.% or more alicyclic epoxy resin contg. 2 or more epoxy groups in the molecule (e.g., 3,4-epoxycyclohexylmethyl-3,4- epoxycyclohexanecarboxylate), and 30wt.% or more vinyl ether resin contg. 2 or more vinyl groups in the molecule (e.g., bisphenol A divinyl ether), a radiation sensitive cationic polymn. initiator (e.g., an arom. onium salt), a radiation- curable radical-polymerizable org. substance contg. 50wt.% or more compd. having 3 or more unsatd. double bonds in the molecule (e.g., dipentaerythritol hexaacrylate) and a radiation-sensitive radical polymn. initiator (e.g., benzophenone) are incorporated as essential components.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to an active energy ray-curable resin composition for optical modeling.

[Problems to be solved by the prior art and the invention] In general, a model corresponding to the product shape required when manufacturing a mold,
Alternatively, models for tracing control in cutting or for die-sinking electrical discharge machining electrodes have been manufactured by hand or by NC cutting using an NC milling machine or the like. However, when using manual processing, there is a problem in that it requires a lot of time and skill, while when using NC cutting,
It is necessary to create a complex machining program that takes into account replacement and wear to change the shape of the cutting edge, and there is also the problem that additional finishing machining may be required to remove steps that occur on the machined surface. be. Recently, there are expectations for the development of new methods for solving the problems of these conventional technologies and creating complex models and various shaped objects for mold making, copying, and die-sinking electrical discharge machining using optical modeling methods. has been done.

This tit resin for optical modeling has excellent curing sensitivity with energy rays, good resolution of curing with energy rays, good UV transmittance after curing, low viscosity, and T characteristics. Various properties are required, such as large size, low volumetric shrinkage during curing, excellent mechanical strength of the cured product, good self-adhesion, and good curing characteristics in an oxygen atmosphere. .

On the other hand, JP-A No. 62-235318 discloses that an epoxy compound having two or more epoxy groups in the molecule and a vinyl compound having two or more vinyl groups in the molecule are prepared using a triarylsulfonium salt catalyst. The invention is characterized in that both are photocured at the same time. However, the synthesis method of this invention is not particularly aimed at obtaining a resin for optical modeling, so even if the resin obtained by this method is used as a resin for optical modeling, it is not suitable for an optical modeling system. It wasn't something.

[Means to solve the problem]

The present invention was discovered as a result of extensive research into photosensitive resins having various properties required for optical modeling resins.

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

The optical modeling resin composition of the present invention has as essential components:
(a) Contains 40% by weight or more of a ring group epoxy resin having at least two or more epoxy groups in one molecule, and contains 30% by weight or more of a vinyl ether resin having at least two or more vinyl groups in one molecule. (b) an energy ray-sensitive cationic polymerization initiator; (c) an energy ray-curable radically polymerizable organic substance; and (d) an energy ray-sensitive radical polymerization initiator. Features.

Typical examples of the alicyclic epoxy resin containing at least two or more epoxy groups in one molecule included in the essential component (a) of the resin composition for optical modeling of the present invention include hydrogenated bisphenol A diglycidyl Etenope 3.4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 2-(3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy)cyclohexane-meth-dioxane, Bis(3,4-epoxycyclohexylmethyl)adipate, vinylcyclohexene dioxide, 4-vinylethoxycyclohexane, bis(3,4-epoxy-6-methylcyclohexylmethyl)adipate), 3,4-epoxy-6-methylcyclo Hexyl-3,4-epoxy-6-methylcyclohexane carboxylate, methylene bis(3,4-epoxycyclohexane), dicyclopenk diene dieboxide, di(3,4-epoxycyclohexylmethyl) ether of ethylene glycol, Ethylene bis(3,
4-epoxycyclohexanecarboxylate), dioctyl epoxy hexahydrophthalate, di-2-ethylhexyl epoxy hexahydrophthalate, and the like.

Similarly, the vinyl ether resins having at least two vinyl groups in one molecule included in the essential component (a) include ethylene glycol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, alkyl vinyl ether, 3.
4-dihydrobyran-2-methyl (3,4-dihydrobyran-2-carboxylate), dipropylene glycol divinyl ether, triethylene glycol divinyl ether, butanediol divinyl ether, divinyl ether of ethylene oxide-added butanediol, bisphenol A , divinyl ether to hydrogenated bisphenol A1 side chain type bisphenol, and the like.

By using a predetermined amount or more of an alicyclic epoxy resin having at least two or more epoxy groups in one molecule as the energy ray-curable cationically polymerizable organic material of the present invention, it is possible to improve cationic polymerization reactivity, reduce viscosity, and improve ultraviolet rays. Shows good properties in terms of transparency, thick film curability, volume shrinkage, resolution, etc. Further, by using a predetermined amount or more of a vinyl ether resin having at least two or more vinyl groups in one molecule, cationic polymerization reactivity is significantly promoted.

The energy ray-curable cationic polymerizable organic substance (a), which is a component of the present invention, is polymerized or crosslinked by energy ray irradiation in the presence of an energy ray-sensitive cationic polymerization initiator (b) in addition to the above-mentioned essential compounds. Cationic polymerizable compounds to react, such as epoxy compounds, cyclic ether compounds, cyclic lactone compounds, cyclic acetal compounds, cyclic thioether compounds, spiro-orthoester compounds,
One type or a mixture of two or more types of vinyl compounds can be added. Examples of such compounds include conventionally known aromatic epoxy resins, alicyclic epoxy resins, and aliphatic epoxy resins.

Preferable aromatic epoxy resins are polyglycidyl ethers of polyhydric phenols or their alkylene oxide adducts having a small number (at least one aromatic nucleus), such as bisphenol A, bisphenol F, or their alkylene oxide adducts. Examples include glycidyl ether and epoxy novolak resin produced by reaction with epichlorohydrin.

Further preferred aliphatic epoxy resins include aliphatic polyhydric alcohols or their alkylene oxide adducts, polyglycidyl ethers, polyglycidyl esters of aliphatic long-chain polybasic acids, and homopolymers and copolymers of glycidyl acrylate and glycidyl methacrylate. Typical examples include diglycidyl ether of 1,4-butanediol, diglycidyl ether of 1,6-hexanediol, triglycidyl ether of peglycerin, triglycidyl ether of trimethylolpropane, and diglycidyl ether of polyethylene glycol. Ether, diglycidyl ether of polypropylene glycol, ethylene glycone, polyglycidyl ether of polyether polyol obtained by adding one or more alkylene oxides to an aliphatic polyhydric alcohol such as glycerin, Diglycidyl esters of aliphatic long chain dibasic acids are mentioned. Furthermore, monoglycidyl ethers of aliphatic higher alcohols, phenols, and cresols6. Butyl phenol or monoglycidyl ether of polyether alcohol obtained by adding alkylene oxide to these, glycidyl ester of higher fatty acids, epoxidized soybean oil, butyl epoxy stearate, octyl epoxy stearate, epoxidized linseed oil, epoxidized polybutadiene etc.

Examples of cationically polymerizable organic substances other than epoxy compounds include oxetane compounds such as trimethylene oxide, 3,3-dimethyloxetane, and 3,3-dichloromethyloxetane; and oxolane compounds such as tetrahydrofuran and 2,3-dimethyltetrahydrofuran. ; cyclic acetal compounds such as trioxane, 1,3-dioxolane, l, 3,6-drioxanecyclooctane; β
- cyclic lactone compounds such as propiolactone, ε-caprolactone; thiirane compounds such as ethylene sulfide, thioevichlorohydrin; thiecunes compounds such as 1,3-propyne sulfide, 3,3-dimethylthietane; Spiroorthoester compounds obtained by reaction of an epoxy compound and a lactone; ethylenically unsaturated compounds such as vinylcyclohexane, imbutylene, polybutadiene, and derivatives of the above compounds.

The energy a-sensitive cationic polymerization initiator (b) used in the present invention is a compound capable of releasing a substance that initiates cationic polymerization by energy ray irradiation,
Particularly preferred are the group of double salts that are onium salts that release Lewis acids upon irradiation. Typical examples of such compounds include -amount % formula %] [wherein the cation is onium, Z is S, Se.

Te, P, As, Sb, Bi, O, halogen (e.g. I, Or.

CI), 11-N, and R', R2, R3, and R' are organic groups which may be the same or different. a,
b.

c and d are each integers from 0 to 3, and a+b+C+d
is equal to the valence of Z. M is a metal or metalloid that is the central atom of the halide complex, and is B, P, As, Sb, Fe, Sn.

Bi, ^I, Ca, In, Ti
, 2n, Sc, V, Cr,
Mn, C.

etc. X is halogen, m is the net charge of the halide complex ion, and n is the number of atoms in the halide complex ion. ].

Above - large amount of anions! , IX, ..., as specific examples of tetrafluoroborate (BF4-), hexafluorophosphate (PF6-), hexafluoroantimonate (SbF6-), hexafluoroarsene (AsF6-), hexachloroantimonate (SbC1s) and the like.

Even bigger! JX, an anion represented by (OH)- can also be used. In addition, other anions include
Examples include perchlorate ion (clO2-), trifluoromethyl sulfite ion (cF3SO3-), fluorosulfonate ion (FSO, -8), luenesulfonate anion, and trinitrobenzenesulfonate anion.

Among such onium salts, it is particularly effective to use aromatic onium salts as cationic polymerization initiators;
Aromatic halonium salts described in JP-A No. 158680, etc., JP-A-50-151997, JP-A-52-30899, JP-A-56-55420, JP-A-55-12510
VIA group aromatic onium salts described in JP-A No. 5, etc., VA group aromatic onium salts described in JP-A-50-158698, etc., JP-A-56-8428, JP-A-56-149, etc.
No. 402, okinsulfoquinium salts described in JP-A-57-192429, etc., aromatic diazonium salts described in JP-B-49-17040, etc., U.S. Patent No. 41
Thiopyrylium salts and the like described in No. 39655 are preferred. Also included are iron/arene complexes, aluminum complexes/photodegradable silicon compound-based initiators, and the like.

Such a cationic polymerization initiator can also be used in combination with a photosensitizer such as benzophenone or penzoin isopropyle tenopetioxanthone.

The energy ray-curable radically polymerizable organic substance (c) used in the present invention is a radically polymerizable compound that undergoes polymerization or crosslinking reaction by energy ray irradiation 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 preferred, such as epoxy acrylate, urethane acrylate, polyester acrylate, polyether acrylate, and acrylic esters of alcohols. It will be done.

Here, preferred epoxy acrylates are acrylates obtained by reacting conventionally known aromatic epoxy resins, alicyclic epoxy resins, aliphatic epoxy resins, and the like with acrylic acid. Among these epoxy acrylates, particularly preferred are acrylates of aromatic epoxy resins, which are prepared 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 acrylate obtained is, for example, an acrylate obtained by reacting a glycidyl ether obtained by reacting bisphenol A1 or its alkylene oxide adduct with epichlorohydrin with acrylic acid, or an acrylate obtained by reacting an epoxy novolak resin with acrylic acid. Examples include acrylates obtained by

Preferred urethane acrylates include one or more hydroxyl group-containing polyesters, acrylates obtained by reacting hydroxyl group-containing polyethers with hydroxyl group-containing acrylic esters and incyanates, and hydroxyl group-containing acrylic esters and incyanates. It is an acrylate obtained by reacting the following. The hydroxyl group-containing polyester used here is preferably a hydroxyl group-containing polyester obtained by an esterification reaction between one or more aliphatic polyhydric alcohols and one or more polybasic acids. , as aliphatic polyhydric alcohol,
For example, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, triethylene glyconopeneobentyl glycol, polyethylene glycol, polypropylene glycol, trimethylolpropane, glycerin, pentaerythritol, dipentaerythritol. IJ)-ru is mentioned.

Examples of polybasic acids include adipic acid, terephthalic acid, phthalic anhydride, and trimellitic acid. Preferred hydroxyl group-containing polyethers are hydroxyl group-containing polyethers obtained by adding one or more alkylene oxides to aliphatic polyhydric alcohols. ,
3-bucundiol, 1.4-butanediol, 1.6
-hexanediol, diethyleneglyconohetriethyleneglycol, neopentylglycol, polyethyleneglycol, polypropylene glycol, trimethylolpropane, chrycerin, pentaerythritol, dipentaerythritol. Examples of the alkylene oxide include ethylene oxide and propylene oxide. Preferred hydroxyl group-containing acrylic esters are aliphatic polyhydric alcohols,
A hydroxyl group-containing acrylic ester obtained by an esterification reaction with acrylic acid, and examples of the aliphatic polyhydric alcohol include ethylene glycol, 1,3-butanediol, 1,4-butanediol, and 1,6-butanediol. Examples include hexanediol, diethylene glycol, triethylene glycol, neopentyl glycol, polyethylene glycol, polypropylene glycol, trimethylolpropane, glycerin, and pentaerythritonopedipentaerythritol. Among such hydroxyl group-containing acrylic esters, hydroxyl group-containing acrylic esters obtained by an esterification reaction between an aliphatic dihydric alcohol and acrylic acid are particularly preferred, and examples thereof include 2-hydroxyethyl acrylate. As incyanates, compounds having at least one isocyanate group in the molecule are preferred, and divalent incyanate compounds such as tolylene diisocyanate, hexamethylene diisocyanate, and inphorone diisocyanate are particularly preferred.

Preferred polyester acrylates are polyester acrylates obtained by reacting hydroxyl group-containing polyesters with acrylic acid. Preferred hydroxyl group-containing polyesters used here are those produced by an esterification reaction between one or more aliphatic polyhydric alcohols and one or more monobasic acids, polybasic acids, and phenols. In the resulting hydroxyl group-containing polyester, examples of the aliphatic polyhydric alcohol include 1.3-butanediol, 1.4-butanediol, 1,6-hexanediol, diethylene glycol, triethylene glycol, neopentyl glycol, and polyethylene. Examples include glycol, polypropylene glycol, trimethylolpropane, glycerin, pentaerythritol, and dipentaerythritol.

Examples of monobasic acids include formic acid, acetic acid, butylcarboxylic acid, and benzoic acid. Examples of polybasic acids include adipic acid, terephthalic acid, phthalic anhydride, and trimellitic acid.

Examples of phenols include phenol and p-nonylphenol.

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

Preferred acrylic esters of alcohols are acrylates obtained by reacting aromatic or aliphatic alcohols having at least one hydroxyl group in the molecule, and their alkylene oxide adducts with acrylic acid; Example: 2-ethylhexyl acrylate,
2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, inamyl acrylate, lauryl acrylate, stearyl acrylate, inoctyl 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 Examples include diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, and dipentaerythritol hexaacrylate.

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

These radically polymerizable organic substances can be used alone or in combination of two or more kinds depending on the desired performance.

Among the energy ray-curable radically polymerizable organic substances (c) above, particularly preferred are at least 3 in one molecule.
It is a compound that has two or more unsaturated double bonds.

The energy ray-sensitive radical polymerization initiator (cl) used in the present invention is a compound that can release a substance that initiates radical polymerization when irradiated with energy rays.
Ketones such as acetophenone compounds, benzoin ether compounds, benzyl compounds, benzophenone compounds, and thioxanthone compounds are preferred. Examples of acetophenone compounds include jetoxyacetophenone and 2-hydroxymethyl-1-phenylpropane.
1-one, 4”-isopropyl-2-hydroxy-2-
Methyl-propiophenone, 2-hydroxy-2-methyl-propiophenone, p-dimethylaminoacetophenone, p-tert-butyldichloroacetophenone,
p-tert--butyltrichloroacetophenone, p
-azidobenzalacetophenone.

Examples of benzoin ether compounds include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropylether, benzoin normal phthyl ether, and benzoin isobutyl ether. Examples of benzyl compounds include benzyl, benzyl dimethyl ketal, benzyl-β-methoxyethyl acetal, and 1-hydroxycyclohexylphenyl ketone. Examples of benzophenone compounds include benzophenone, methyl 0-benzoylbenzoate, Michler's ketone, 4,4'-bisdiethylaminobenzophenone, and 4,4'-dichlorobenzophenone. Examples include thioxanthone-based compounds, thioxanthone, 2-ethylthioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, and 2-isopropylthioxanthone.

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

Next, 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 radically polymerizable organic substance, and (d) an energy ray-sensitive radical. The composition ratio of the polymerization initiator will be explained. Regarding the composition ratio,
The explanation is given in parts (parts by weight).

That is, the composition ratio of the energy beam-curable cationic polymerizable organic substance (a) and the energy beam-curable radical polymerizable organic substance (c) in the present invention is such that the energy beam-curable cationically polymerizable organic substance (a) and the energy beam-curable cationically polymerizable organic substance (a) When the total amount of the radiation-curable radically polymerizable organic substance (c) is 100 parts, the energy-beam-curable cationic polymerizable organic substance (a) is 40 to 95 parts, that is, the energy-beam curable radically polymerizable organic substance (c). ), and more preferably 50 to 90 parts of the energy beam curable cationic polymerizable organic substance (a), that is, 10 to 90 parts of the energy beam curable radically polymerizable organic substance (c). A resin composition containing 50 parts has particularly excellent properties as a resin composition for optical modeling.

In the composition of the present invention, the energy beam-curable cationically polymerizable organic substance (a) and the energy beam-curable radically polymerizable organic substance (c) are selected from the following in order to obtain desired characteristics as a resin composition for optical modeling: A plurality of energy ray curable organic substances, ie, an energy ray curable cationic polymerizable organic substance (a) and an energy ray curable radically polymerizable organic substance (c) can be used in combination.

The content of the energy beam-sensitive cationic polymerization initiator etc. in the composition of the present invention is 100 parts of the energy beam-curable organic substance, that is, the energy-beam-curable cationically polymerizable organic substance (a) and the energy beam-curable radical polymerization 0.1 to 10 parts per 100 parts in total of the organic substance (c),
It can be contained preferably in a range of 0.5 to 6 parts. Further, the content of the energy ray sensitive radical polymerization initiator (6) used in the composition of the present invention is 0.1 to 10 parts, preferably 0.2 to 5 parts, based on 100 parts of the energy ray curable organic substance. It can be contained within a range of 100%.

The energy ray sensitive cationic polymerization initiator (b) and the energy ray sensitive radical polymerization initiator (a) are combined with a plurality of energy ray sensitive cationic polymerization initiators ( b) and an energy ray-sensitive radical polymerization initiator (d) can be used in combination. Furthermore, when these polymerization initiators are mixed with an energy beam-curable organic substance, the polymerization initiators can be dissolved in a suitable solvent.

In the composition of the present invention, when the composition ratio of the energy beam-curable cationic polymerizable organic substance (a) is too large, that is, when the composition ratio of the energy beam-curable radically polymerizable organic substance (c) is too small, the obtained The composition is less susceptible to the effects of oxygen in the air during the curing reaction with active energy rays, and volumetric shrinkage during curing can be reduced, so the cured product is less prone to distortion or cracking. Since a low viscosity resin composition can be easily obtained, the molding time can be shortened. However, during the curing reaction with active energy rays, the polymerization reaction tends to proceed from the area irradiated with the active energy rays to the surrounding area, resulting in poor resolution, and it takes several seconds for the polymerization reaction to complete after irradiation with the active energy rays. It takes time. Conversely, if the composition ratio of the energy beam-curable cationic polymerizable organic substance (a) is too low, that is, if the composition ratio of the energy beam-curable radically polymerizable organic substance (c) is too high, the active energy ray irradiation area The resolution is good because the polymerization reaction is difficult to proceed from the surface to the surrounding areas, and it takes almost no time for the polymerization reaction to complete after irradiation with active energy rays. However, during the curing reaction with active energy rays, the polymerization reaction is likely to be inhibited by oxygen in the air, and the volume shrinkage during curing is large, which tends to cause distortions and cracks in the cured product. Therefore, the use of low-viscosity radical polymerizable resins causes significant skin irritation. None of such compositions is suitable as a resin composition for optical modeling.

In particular, in the optical modeling resin composition of the present invention, (a) the energy beam-curable cationic polymerizable organic substance contains 40% by weight or more of an alicyclic epoxy resin having at least two or more epoxy groups in one molecule. 3 vinyl ether resins containing at least two or more vinyl groups in one molecule.
0% by weight or more, and (c) the energy ray curable radically polymerizable organic substance contains a compound having at least 3 or more unsaturated double bonds in one molecule in a ratio of 50:! When configured to contain i% or more, the energy ray reactivity is good (,
It has excellent mechanical strength and resolution, and has a shrinkage rate of less than 3%.
An extremely excellent optical modeling system can be constructed.

The optical modeling resin composition of the present invention may optionally contain a heat-sensitive cationic polymerization initiator; a coloring agent such as a pigment or dye; an antifoaming agent, a leveling agent, etc., as long as the effects of the present invention are not impaired.
Appropriate amounts of various resin additives such as thickeners, flame retardants, and antioxidants; fillers such as silica, glass powder, ceramic powder, and metal powder; and modifying resins may be used. As a heat-sensitive cationic polymerization initiator, for example, JP-A-5
Examples include aliphatic onium salts described in No. 7-49613 and JP-A-58-37004.

The viscosity of the composition of the present invention is preferably 200 at room temperature.
0 cps or less, more preferably 1000 cps
These are as follows. If the viscosity becomes too high, the time required for modeling becomes longer and workability tends to deteriorate.

Generally, resin compositions for modeling undergo volumetric shrinkage during curing, and therefore, from the viewpoint of accuracy, it is desired that the shrinkage be small. The volume shrinkage rate of the composition of the present invention during curing is preferably 5.
% or less, more preferably 3% or less.

As a concrete implementation method of the present invention, Japanese Patent Application Laid-Open No. 60-247
As described in Japanese Patent No. 515, the resin composition for optical modeling of the present invention is placed in a container, a light guide is inserted into the resin composition, and the container and the light guide are placed relative to each other. Specifically, 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 active energy rays used for curing the composition of the present invention, ultraviolet rays, electron beams, X-rays, radiation, high frequency waves, etc. can be used. Among these, ultraviolet light having a wavelength of 1,800 to 5,000 wavelengths is economically preferable, and as the light source, an ultraviolet laser, a mercury lamp, a xenon lamp, a sodium lamp, an alkali metal lamp, etc. can be used. A particularly preferred light source is a laser light source, which can increase the energy level to shorten the modeling time, and utilize good light focusing to improve the modeling accuracy. A point light source that condenses ultraviolet light from various lamps such as a mercury lamp is also effective.

Furthermore, in order to selectively supply the active energy rays necessary for curing to the present resin composition, it is necessary to use active energy rays that have a wavelength equal to twice the wavelength suitable for curing the resin composition and that are in phase. The resin composition is irradiated with two or more light fluxes so as to cross each other, and the energy rays necessary for curing the resin composition are obtained by two-photon absorption, and the intersection points of the lights are moved. You can also do it by The phase-aligned light beam can be obtained by, for example, a laser beam.

Since the composition of the present invention is cured by cationic polymerization reaction and radical polymerization reaction caused by active energy rays, depending on the types of cationically polymerizable organic substance (a) and radically polymerizable organic substance (c) used, active energy rays At the time of irradiation, the crosslinking curing reaction can be effectively promoted by heating the resin composition to about 30 to 100°C. By performing heat treatment at a temperature of 100° C. or UV irradiation treatment using a mercury lamp or the like, it is also possible to obtain a shaped article with even better mechanical strength.

The resin composition for optical modeling of the present invention is extremely excellent for creating three-dimensional three-dimensional models by stacking layered products, and allows creation and processing of models without using a mold, and moreover, The industrial value is extremely large, as all shapes, including curved surfaces, can be created with high precision using CAD/CAM and docking. For example, the field of application of this resin composition is the manufacture of wooden molds and metal molds for manufacturing modenope molds to check for inconveniences in the combination of modenope parts to examine the external design during the design process. It can be used for a wide range of purposes, including as a model for copy processing.

Specific fields of application include automobiles, electronic/electrical parts,
Examples include models and processing of various curved objects such as furniture, architectural structures, toys, containers, castings, and dolls.

〔Example〕

Hereinafter, typical examples of the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to the following Examples.

In the examples, "parts" means parts by weight.

Example 1 (a) 3,4-epoxycyclohexylmethyl-3,4- as an energy beam-curable cationic polymerizable organic substance
30 parts of epoxycyclohexane carboxylate 55L bisphenol A divinyl ether, (5) 3 parts of bis-C4-(diphenylsulfonio)phenyl]sulfide bisdihexafluoroantimonate as an energy ray-sensitive cationic polymerization initiator, (c) energy 15 parts of dipentaerythritol hexaacrylate as a radiation-curable radically polymerizable organic substance and 1 part of benzophenone as (d) an energy ray-sensitive radical polymerization initiator were thoroughly mixed to obtain a resin composition for optical modeling. . A three-dimensional NC (numerical control) table with a container containing the resin composition, a helium cadmium laser (wavelength 3250
m) and a stereolithography experiment system consisting of an optical system and a control unit mainly consisting of a personal computer.
A cone with a thickness of 0.5 mm and a thickness of 0.5 mm was modeled. This model was free from distortion, had extremely high precision, and had excellent mechanical strength.

In order to compare the polymerization speed by laser, the time required for modeling was measured and found to be a short time of 30 minutes.

Example 2 (a) 3,4-epoxycyclohexylmethyl-3,4- as energy ray-curable cationically polymerizable organic substance
Epoxycyclohexane carboxylate 45L)
25 parts of diethylene glycol divinyl ether, etc. As an energy ray-sensitive cationic polymerization initiator, bis-
3 parts of 4-(diphenylsulfonio)phenyl sulfide bisdihexafluoroantimonate, (c) 20 parts of dipentaerythritol hexaacrylate, 10 parts of trimethylolpropane triacrylate as an energy ray-curable radically polymerizable organic substance, (d) One part of benzyl dimethyl ketal was sufficiently mixed as an energy ray-sensitive radical polymerization initiator to obtain a resin composition for optical modeling. When a hanging glass-shaped object was created using the laser beam modeling experimental system shown in Example 1, it was found that this object had no distortion, had extremely high modeling accuracy, and had excellent mechanical strength. Ta. In addition, this resin composition has
It has a low viscosity of 130 cps (25°C) and is easy to handle.
It had excellent curability with laser light.

In order to measure the polymerization rate by laser, a conical shaped article similar to that in Example 1 was created, and the molding time was 30 minutes.

Example 3 (a) Bisphenol Δ diglycidyl ether IO part, 3 as an energy beam-curable cationically polymerizable organic substance
．． 4-Epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate 30L 20 parts of ethylene glycol divinyl ether, (b) 2 parts of triphenylsulfonium hexafluoroantisupernate as an energy ray-sensitive cationic polymerization initiator, (c) Energy 15 parts of bisphenol A epoxy acrylate as a radiation-curable radically polymerizable organic substance, 25L of pentaerythritol triacrylate (d) and 2 parts of 2,2-jetoxyacetophenone as an energy ray-sensitive radical polymerization initiator were thoroughly mixed, and optically A resin composition for modeling was obtained. Using the laser beam modeling experimental system shown in Example 1, a pot-shaped object was created while heating this composition to 60°C, and the object was found to have no distortion.
A product with excellent molding accuracy was obtained.

In order to measure the polymerization rate using the laser, we created a cone-shaped object similar to that in Example 1, and found that the reaction rate was fast due to the heating at 60°C, and the building time was very short at 20 minutes. Ta.

Example 4 (a) 3,4-epoxycyclohexylmethyl-3,4- as energy ray-curable cationic polymerizable organic substance
Epoxycyclohexane (Lupoxylene) 50L)
30 parts of dimethylolpropane trivinyl ether, etc.)
(c) 2 parts of triphenylsulfonium hexafluoroantimone as an energy ray-sensitive cationic polymerization initiator; 20 parts of dipentaerythritol hexaacrylate as (c) an energy ray-curable radically polymerizable organic substance;
(d) 2 parts of benzoin isopropyl ether as an energy ray-sensitive radical polymerization initiator were sufficiently mixed to obtain a resin composition for optical modeling. When a bell-shaped object was created using the Lehde optical modeling experiment system shown in Example 1, it was free from distortion and had excellent mechanical strength, modeling accuracy, and surface smoothness.

In order to measure the polymerization rate by laser, a conical shaped article similar to that in Example 1 was created, and the molding time was 30 minutes.

Comparative Example 1 60 parts of 3.4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 20 parts of bisphenol A diglycidyl ether, 20 parts of 1.4-butanediol diglycidyl ether, triphenylsulfonium hexafluoroanthine 3 parts of Nato were thoroughly mixed to obtain an energy ray-curable cationically polymerizable resin composition. Using this composition, a conical shaped object similar to that in Example 1 was created using the laser beam modeling experimental system shown in Example 1. Although the strength was excellent, this resin composition had poor resolution during curing with laser light, resulting in a rough surface of the modeled object and poor modeling accuracy.

In addition, it was necessary to wait several seconds from the time of laser irradiation until the polymerization reaction was completed, and the time required for modeling was as long as 120 minutes.

Comparative Example 2 70 parts of bisphenol A epoxy acrylate, 30 parts of trimethylolpropane triacrylate, and 3 parts of benzyl dimethyl ketal were sufficiently mixed to obtain an energy ray-curable radically polymerizable resin composition. When this composition was used to create a cone-shaped object similar to that in Example 1 using the laser beam modeling experimental system shown in Example 1, the molding time was relatively short at 45 minutes. However, this modeled object suffered from distortion due to large curing shrinkage, and its modeling accuracy was poor.

Comparative Example 3 75 parts of 3.4-epoxycyclohexylmethyl-3,4-epoxycyclohexane hydroxylate, triethylene glycol divinyl ether 10aE, bis[4-
3 parts of (diphenylsulfonio)phenyl sulfide bisdihexafluoroantimonate, 15 parts of dipentaerythritol hexaacrylate, and 1 part of benzophenone were thoroughly mixed to obtain an energy beam-curable cationic/radical polymerizable resin composition. . Using this composition, using the laser stereolithography experimental system shown in Example 1,
A conical shaped object similar to that in Example 1 was created. Although this model was free from distortion and had excellent mechanical strength, it took only 50 minutes to build due to the low content of vinyl ether resin, which was clearly inferior to the resin composition for optical modeling of the present invention. Ta.

〔Effect of the invention〕

Since the resin composition for optical modeling of the present invention is a mixed composition of an energy beam-curable cationic polymerizable organic substance and an energy beam-curable radically polymerizable organic substance, the characteristics of the energy beam-curable cationic polymerizable organic substance are It is a resin composition that has the advantages of both the properties of an energy beam-curable radically polymerizable organic material. Cationic polymerizable resin compositions are completely unaffected by oxygen in the air during the curing reaction with active energy rays, and can reduce volumetric shrinkage during curing, resulting in distortions and cracks in the cured product. hard to occur, the strength of the cured product is excellent, and the molding time can be shortened because it is easy to prepare a low-viscosity resin composition.
There are advantages such as However, during the curing reaction caused by active energy rays, the polymerization reaction tends to proceed from the area irradiated with the active energy rays to the surrounding areas, resulting in poor resolution and the time it takes several seconds for the polymerization reaction to complete after irradiation with the active energy rays. There are drawbacks such as the need for On the other hand, radically polymerizable resin compositions have good resolution because the polymerization reaction is difficult to proceed from the active energy ray irradiated area to the surrounding area during the curing reaction with active energy rays. It takes almost no time to finish,
There is an advantage. However, the polymerization reaction is inhibited by oxygen in the air, the shrinkage rate during curing is high, the mechanical strength of the cured product is poor, and low viscosity resins are highly irritating to the skin.
It has drawbacks such as strong odor.

In the present invention, (a) an energy ray-curable cationic polymerizable organic substance, an energy ray-sensitive cationic polymerization initiator, (c) an energy ray-curable radically polymerizable organic substance,
(d) By mixing an energy ray-sensitive radical polymerization initiator, it was possible to obtain a resin composition for optical modeling having the following characteristics. That is, it is hardly affected by oxygen in the air. Since volumetric shrinkage during curing can be reduced, distortions and cracks are less likely to occur in the cured product. Since it is easy to use a low viscosity resin composition, the molding time can be shortened.

When irradiated with active energy rays, the polymerization reaction is difficult to proceed from the area irradiated with the active energy rays to the surrounding areas, resulting in good resolution. After irradiation with active energy rays, almost no time is required until the polymerization reaction is completed. The cured product has excellent mechanical strength and hardness.

Claims (1)

[Scope of Claims] 1. As an essential component, (a) contains 40% by weight or more of an alicyclic epoxy resin having at least two or more epoxy groups in one molecule, and at least two or more epoxy groups in one molecule; An energy ray-curable cationic polymerizable organic material containing 30% by weight or more of a vinyl ether resin having a vinyl group, (b) an energy ray-sensitive cationic polymerization initiator, (c) an energy ray-curable radically polymerizable organic material, (d) A resin composition for optical modeling characterized by containing an energy ray-sensitive radical polymerization initiator. 2. The optical system according to claim 1, wherein (c) the energy beam-curable radically polymerizable organic substance contains 50% by weight or more of a compound having at least three or more unsaturated double bonds in one molecule. Resin composition for modeling.