JPH0275618A - Resin composition for optical molding - Google Patents

Abstract

PURPOSE:To obtain the title compsn. providing a cured product with excellent mechanical strength, hardness, etc., by incorporating a radiation-curable cationicallypolymerizable org. substance and a radiation-curable radicalpolymerizable org. substance as well as a radiation-sensitive cationic polymn. initiator, a radiation-sensitive radical polymn. initiator and a polyester contg. hydroxyl groups as essential components. CONSTITUTION:A radiation-curable cationically polymerizable org. substance contg. 40wt.% or more alicyclic epoxy resin contg. pref. 2 or more epoxy groups in its molecule (e.g., 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate), a radiation-sensitive cationic polymn. initiator (e.g., an arom. onium salt), a radiation-curable radicalpolymerizable org. substance contg. 50wt.% or more compd. contg. pref. 3 or more unsatd. double bonds in its molecule (e.g., dipentaerythritol hexaacrylate), a radiation-sensitive radical polymn. initiator (e.g., benzophenone) and a polyester contg. hydroxyl groups (e.g., trimethylolpropane epsilon-caprolactone ester) 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; 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 resin for optical modeling has excellent curing sensitivity with energy rays, good resolution of curing with energy rays, good ultraviolet transmittance after curing, low viscosity, and large T characteristics. Various properties are required, such as 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) Energy ray-curable cationic polymerizable organic substance, (
b) an energy ray-sensitive cationic polymerization initiator, (c) an energy ray-curable radically polymerizable organic substance, (6) an energy ray-sensitive radical polymerization initiator, and (e) a hydroxyl group-containing polyester. be.

The energy ray-curable cationic polymerizable organic substance (a) that is a component of the present invention is a cationic polymerization material that undergoes polymerization or crosslinking reaction by energy ray irradiation in the presence of an energy ray-sensitive cationic polymerization initiator (b). It is a compound consisting of one or a mixture of two or more of, for example, an epoxy compound, a cyclic ether compound, a cyclic lactone compound, a cyclic acetal compound, a cyclic thioether compound, a spiro-orthoester compound, a vinyl compound, etc. Among such cationically polymerizable compounds, compounds having at least two or more epoxy groups in one molecule are preferred, such as conventionally known aromatic epoxy resins, alicyclic epoxy resins, and aliphatic epoxy resins. It will be done.

Preferred aromatic epoxy resins are polyglycidyl ethers of polyhydric phenols having at least one aromatic nucleus or their alkylene oxide adducts, such as bisphenol A, bisphenol F or their alkylene oxide adducts, and epichlorohydrin. Glycidylethenope epoxy novolac resins produced by reaction with.

In addition, as a preferable alicyclic epoxy resin, polyglycidyl ether of a polyhydric alcohol having at least one alicyclic ring or cyclohexene, or a cyclopentene ring-containing compound is mixed with a suitable solvent such as hydrogen peroxide or peracid. Examples include cyclohexene oxide or cyclopentene oxide-containing compounds obtained by epoxidation with an oxidizing agent. Typical examples of alicyclic epoxy resins include hydrogenated bisphenol A diglycidyl ether, 3,4-epoxycyclohexylmethyl-3,4-
Epoxycyclohexane carboxylate, 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, ethylene glycol di(
Examples thereof include 3,4-epoxycyclohexylmethyl) ether, ethylene bis(3,4-epoxycyclohexanecarboxylate), dioctinope epoxy hexahydrophthalate, and di-2-ethylhexyl epoxy hexahydrophthalate.

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, triclycidyl ether of glycerin, triclycidyl ether of trimethylolpropane, and tetraglycidyl ether of sorbitol. Ether, hexaglycidyl ether of dipentaerythritol, diglycidyl ether of polyethylene glycol, diglycidyl ether of polypropylene glycol, ethylene glycol, propylene glycol/lz.

Polyglycidyl ether of polyether polyol obtained by adding one or more alkylene oxides to aliphatic polyhydric alcohol such as glycerin,
Diglycidyl esters of aliphatic long chain dibasic acids are mentioned. Furthermore, monoglycidyl ethers of aliphatic higher alcohols, phenol, cresol, butylphenol, or monoglycidyl ethers of polyether alcohols obtained by adding alkylene oxide to these, glycidyl esters of higher fatty acids, epoxidized soybean oil, butyl epoxy stearate. , epoxy stearate octinope, epoxidized linseed oil, epoxidized polybutadiene, and the like.

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-dioxolane, 1,3,6-)rioxanecyclooctane; β-
Cyclic lactone compounds such as propiolactone and ε-caprolactone; thiirane compounds such as ethylene sulfide and thioevichlorohydrin; thiequene compounds such as 1,3-propyne sulfide and 3,3-dimethylthietane; ethylene Glycol divinyl ether, alkyl vinyl ether, 3,4-dihydropyran-2-methyl (3,4-dihydropyran-2-carboxylate),
Vinyl ether compounds such as triethylene glycol divinyl ether; spiro-orthoester compounds obtained by reaction of epoxy compounds and lactones; ethylenically unsaturated compounds such as vinylcyclohexane, imbutylene, polybutadiene, and derivatives of the above compounds. These cationic polymerizable compounds can be used alone or in combination of two or more kinds depending on the desired performance.

Particularly preferred among these cationic polymerizable organic substances are alicyclic epoxy resins having at least two or more epoxy groups in one molecule, which have excellent cationic polymerization reactivity, low viscosity, ultraviolet transparency, and thick film curing. It exhibits good characteristics in terms of flexibility, volume shrinkage, resolution, etc.

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 upon 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 the following formula: %] [In the formula, the cation is onium, and Z is S or Se.

Te, P, As, Sb, 口i, 0. Halogens (e.g. I, Br.

CI) , N--N, and R1, R2, R3, and R4 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, AI, Ca, In, Ti,
Zn, 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 - Monna's anion MX,. Specific examples include tetrafluoroborate (BF4-), hexafluoroantimonate (SbF6-), hexafluoroantimonate (ASF6), hexafluoroantimonate (SbF6-), hexafluoroantimonate (ASF6), nate (SbC1g-) and the like.

Furthermore, general holes MX+ and anions represented by (OH)- can also be used. In addition, other anions include
perchlorate ion (cIOl-), trifluoromethyl sulfite ion (cF3SO3-), fluorosulfonate ion (FSO3-),) luenesulfonate anion,
Examples include trinitrobenzenesulfonic acid 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, oxosulfoxonium salts described in JP-A-57-192429, etc., aromatic diazonium salts described in JP-A-49-17040, etc., U.S. Patent No. 41
Thiobi IJ IJ salts described in No. 39655 and the like are preferred. Also included are iron/arene complexes, aluminum complexes/photodegradable silicon compound-based initiators, and the like.

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

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 acrylic esters and isocyanates with hydroxyl group-containing polyethers, and hydroxyl group-containing acrylic esters and isocyanates. It is an acrylate obtained by reaction. 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 glycol, neopentyl glycol,
polyethylene glycol, polypropylene glycol,
Examples include trimethylolpropane, glycerin, and pentaerythritonopedipentaerythritol. Examples of polybasic acids include adipic acid, terephthalic acid,
Examples include 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
-butanediol, 1,4-butanediol, 1,6-
Examples include hexanediol, diethylene glycol, triethylene glycol, neopentyl glycol, polyethylene glycol, polypropylene glycol, trimethylolpropane, chrycerin, and pentaerythritol. 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-
Examples include butanediol, 1,4-butanediol, 1.6=hexanediol, diethyleneglyconohetriethyleneglycol, neopentylglycol, polyethyleneglycol, polypropylene glycol, trimethylolpropane, glycerin, pentaerythritol, and dipentaerythritol. . 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 isocyanate 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 aliphatic polyhydric alcohols include 1.3-butanediol, 1.4-butanediol, 1,6-hexanecyonovediethylene glycol, triethylene glycol, neopentyl glycol, Examples include polyethylene 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. Preferred hydroxyl group-containing polyethers used here are hydroxyl group-containing polyethers obtained by adding one or more alkylene oxides to aliphatic polyhydric alcohols. , e.g. 1,3-butanediol, 1,4-butanedione 1
．． Examples thereof include 6-hexanediol, diethylene glycol, triethylene glyconepeneopentyl glycol, polyethylene glyconepepolypropylene glycol, trimethylolpropane, glycerin, and pentaerythritonepenepentaerythritol. 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 alkylene oxide adducts thereof with acrylic acid. , e.g. 2-ethylhexyl acrylate, 2
-Hydroxyethyl acrylate, 2-hydroxypropyl acrylate, isoamyl acrylate, lauryl acrylate, stearyl acrylate, isooctyl acrylate, tetrahydrofurfuryl acrylate,
inbornyl acrylate, benzyl acrylate, 1
．． 3-butanediol diacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, diethylene glycol diacrylate,
Examples include triethylene glycol diacrylate, neopentyl glycol diacrylate, polyethylene glycol diacrylate, polypropylene glycol 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 (d) used in the present invention is a compound that can release a substance that initiates radical polymerization when irradiated with energy rays, and includes acetophenone compounds, benzoin ether compounds,
Ketones such as benzyl compounds, benzophenone compounds, and thioxanthone compounds are preferred. Examples of acetophenone compounds include jetoxyacetophenone, 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 and p-azidobenzalacetophenone.

Examples of benzoin ether compounds 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 pendinopebenzyl dimethyl ketanopebenzyl β-methoxyethyl acetal and 1-hydroxycyclohexylphenyl ketone. Examples of benzophenone compounds include benzophenone, methyl o-benzoylbenzoate, Michler's ketone, 4,4'-bisdiethylaminobenzophenone, and 4,4''-dichlorobenzophenone. Examples of thioxanthone compounds include thioxanthone and 2-methylthioxanthone. , 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.

The (e) hydroxyl group-containing polyester used in the present invention is
A hydroxyl group-containing polyester obtained by an esterification reaction between one or more aliphatic polyhydric alcohols and one or more monobasic acids, polybasic acids, and phenols;
and a hydroxyl group-containing polyester obtained by the esterification reaction of one or more lactones with one or more monobasic acids, polybasic acids, and phenols, and as aliphatic polyhydric alcohols. For example, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, diethylene glycone, triethylene glyconeopeneopentyl glycol, polyethylene glycol, polypropylene glycone, trimethylolpropane, glycerin. , pentaerythritonopezipentaerythritol. 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. Examples of lactones include β-propiolactone and ε-caprolactone.

These (e) hydroxyl group-containing polyesters can be used alone or in combination of two or more types 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 ratios of the polymerization initiator and (e) hydroxyl group-containing polyester will be explained. The composition ratio will be explained 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 material (c) is 100 parts, the energy-beam-curable cationic polymerizable organic material (a) is 40 to 95 parts, that is, the energy-beam-curable radically polymerizable organic material (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 (b) 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. It can be contained in a range 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 content of the energy ray sensitive radical polymerization initiator (d) 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 the range of.

Energy ray sensitive cationic polymerization initiator (b) and
- Energy ray sensitive radical polymerization initiator (d)
In order to obtain desired properties as a resin composition for optical modeling, a plurality of energy ray-sensitive cationic polymerization initiators (b) and energy ray-sensitive radical polymerization initiators (d) are used.
) can be used in combination. Also, when mixing these polymerization initiators with energy ray-curable organic substances,
A polymerization initiator can also be used by dissolving it in a suitable solvent.

The content of (e) hydroxyl group-containing polyester in the composition of the present invention is 5 parts per 100 parts in total of (a) energy beam-curable cationic polymerizable organic substance and (c) energy beam-curable radically polymerizable organic substance. A resin composition containing up to 40 parts is preferable, and a resin composition containing 10 to 30 parts more preferably has particularly excellent properties as a resin composition for optical modeling.

In the composition of the present invention, (e) the hydroxyl group-containing polyester can be used by blending a plurality of hydroxyl group-containing polyesters in order to obtain desired characteristics as a resin composition for optical modeling.

As described above, in the composition of the present invention, (e) the hydroxyl group-containing polyester is added to 100 parts in total of (a) the energy beam-curable cationic polymerizable organic substance and (c) the energy beam-curable radically polymerizable organic substance. By containing 5 to 40 parts of , curing is accelerated and excellent properties can be provided as a resin composition for optical modeling. In particular, the content of (e) hydroxyl group-containing polyester is 10 to 100 parts per 100 parts in total of (a) energy beam-curable cationically polymerizable organic material and (c) energy beam-curable radically polymerizable organic material.
When configured to have 30 parts, a very excellent optical modeling system can be obtained.

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, ``active energy ray irradiation'' The resolution is good because the polymerization reaction is difficult to proceed from one area to the surrounding area, and it takes almost no time to complete the polymerization reaction 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. (c) an energy ray-curable radically polymerizable organic substance containing at least 3 per molecule;
When the composition contains 50% by weight or more of a compound having 1 or more unsaturated double bonds, it has good energy ray reactivity, excellent mechanical strength and resolution, and a shrinkage rate of 3% or less, making it extremely An 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. L-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 is economically preferable, and its light sources include ultraviolet lasers, mercury lamps, xenon lamps, sodium lamps,
Alkali metal lamps 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. A molded article with even better mechanical strength can be obtained by heat treatment at a temperature of 100° C. or UV irradiation treatment using a mercury lamp or the like.

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 fields of application of this resin composition include models for examining external designs during the design process, models for checking inconveniences in the combination of parts, and wooden molds and metal molds for producing molds. It can be used for a wide range of purposes, including copying models for manufacturing.

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
65 parts of epoxycyclohexane carboxylate, 1,
20 parts of 4-butanediol diglycidyl ether, (b
) 3 parts of bis-[4-(diphenylsulfonio)phenyl]sulfide bisdihexafluoroantimonate as an energy ray-sensitive cationic polymerization initiator, (c) dipentaerythritol as an energy ray-curable radically polymerizable organic substance. 15 parts of xacrylate, (d)
As an energy ray-sensitive radical polymerization initiator, 1 part of benzophenone, (e) as a hydroxyl group-containing polyester,
15 parts of ε-caprolactone ester of trimethylolpropane was thoroughly mixed to obtain a resin composition for optical modeling. Using a stereolithography experiment system consisting of a three-dimensional NC (numerical control) table with a container containing the resin composition, a helium cadmium laser (2 & 325 nm long), and a control section mainly consisting of an optical system and a personal computer. , the diameter of the bottom surface is 12 mm from this resin composition.
, a cone with a height of 15 mm and a thickness Q of 5 mm was modeled. This model was free from distortion, had extremely high precision, and had excellent mechanical strength.

When the time required for modeling was measured to compare the polymerization speed by laser, it was found to be as short as 35 minutes. Also,
In order to measure the modeling accuracy, we measured the diameter of the bottom of the conical model at 10 arbitrary locations and measured the variation, and found that the average error from the average value (hereinafter referred to as modeling accuracy) was 1.
The accuracy was as high as 3%.

Example 2 (a) 3,4-epoxycyclohexylmethyl-3,4- as energy ray-curable cationically polymerizable organic substance
50 parts of epoxycyclohexane carboxylate, 1,
20 parts of 4-butanediol diglycidyl ether, (b
) Triphenylsulfonium hexafluoroantisupernate 3 as an energy ray-sensitive cationic polymerization initiator
Part, (c) dipentaerythritol hexaacrylate 2 as energy ray-curable radically polymerizable organic substance
0 parts, 10 parts of trimethylolpropane triacrylate, (d) 1 part of benzyl dimethyl ketal as an energy ray-sensitive radical polymerization initiator, and (e) 10 parts of ε-caprolactone ester of glycerin as a hydroxyl group-containing polyester. , a resin composition for optical modeling was obtained. Using the laser beam modeling experimental system shown in Example 1, we created a bell-shaped object, which was found to have no distortion, extremely high modeling accuracy, and excellent mechanical strength. Met. Furthermore, the resin composition had a low viscosity, was easy to handle, and had excellent curability with laser light.

In order to measure the polymerization rate and modeling accuracy using a laser, a conical shaped article similar to that in Example 1 was created, and the modeling time was 35 minutes and the modeling accuracy was 1.2%.

Example 3 (a) As an energy beam-curable cationically polymerizable organic substance, 10 parts of bisphenol A diglycidyl ether, 3
．． 4-Epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate 40L 10 parts of vinylchlorohexene oxide, (b) 2 parts of triphenylsulfonium hexafluoroantisupernate as an energy ray-sensitive cationic polymerization initiator, (c) Energy As a radiation-curable radical polymerizable organic substance, 15 parts of bisphenol A epoxy acrylate, 25 parts of pentaerythritol triacrylate, (d) as an energy ray-sensitive radical polymerization initiator, 2 parts of 2,2-jetoxyacetophenone, (e) hydroxyl group As the containing polyester, ε-caprolactone ester of triethylene glycol 1
0 parts were sufficiently mixed to obtain a resin composition for optical modeling.

When this composition was heated to 60° C. to create a pot-shaped object using the laser beam modeling experimental system shown in Example 1, it was found that there was no distortion and excellent modeling accuracy was obtained.

In order to measure the polymerization rate and modeling accuracy using the laser, we created a cone-shaped object similar to that in Example 1, and found that the reaction speed was fast due to the heating at 60°C, and the building time was very short at 25 minutes. Met.

Moreover, the modeling accuracy was 1.6%.

Example 4 (a) 3,4-epoxycyclohexylmethyl-3,4- as energy ray-curable cationic polymerizable organic substance
55 parts of epoxycyclohexane carboxylate, 1.
10 parts of 4-butanediol diglycidyl ether, 10 parts of triethylene glycol divinyl ether, (b) bis-[4
-(diphenylsulfonio)phenyl] 2 parts of sulfide bis dihexafluoroantimonate, (c) 20 parts of dipentaerythritol hexaacrylate as energy ray-curable radically polymerizable organic substance, (d) Energy ray-sensitive radical polymerization initiation As an agent, 1 part of benzophenone, (e) as a hydroxyl group-containing polyester, ■, 4
- 30 parts of adipic acid ester of butanediol were thoroughly mixed to obtain a resin composition for optical modeling. When a hanging glass-shaped object was created using this composition using the laser beam modeling experimental system shown in Example 1, it was found to have no distortion and excellent mechanical strength, modeling accuracy, and surface smoothness. It was done.

In order to measure the polymerization rate and modeling accuracy by laser, a conical shaped article similar to that in Example 1 was created, and the modeling time was 30 minutes and the modeling accuracy was 0.5%, which was very high precision.

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.

Furthermore, it took several seconds from the time of laser irradiation until the polymerization reaction was completed, resulting in a long modeling time of 120 minutes. Furthermore, the modeling accuracy showed a high value of 6.8%.

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 45 minutes. The object was distorted due to large curing shrinkage, and the printing accuracy was 10.0%.
It was very inferior.

Comparative Example 3 65 parts of 3.4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 1.4-
20 parts of butanediol diglycidyl ether, HisC4
-(diphenylsulfonio)phenyl] 3 parts of sulfide bisdihexafluoroantimonate, 15 parts of dipentaerythritol hexaacrylate, 1 part of benzophenone
The components were thoroughly mixed to obtain an energy beam-curable cation/radical polymerizable resin composition. Using this composition,
Using the laser beam shaping experiment system shown in Example 1, a conical shaped article similar to that in Example 1 was created. This model was free from distortion and had excellent mechanical strength. The modeling time was 50 minutes, and the modeling accuracy was 3.0%, which reached a certain level as a resin composition for optical modeling, but it was clearly inferior to those containing hydroxyl group-containing polyester. .

〔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 have small volumetric shrinkage during curing, resulting in distortions and cracks in the cured product. etc., 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, (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. agent and (
e) By mixing the hydroxyl group-containing polyester, 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. Cationic polymerization rate is accelerated and curability is excellent. That is, since the curing speed is fast and the curing shrinkage is low, a resin composition for optical modeling with high precision can be obtained.

Applicant's agent Kaoru Furutani

Claims (1)

[Scope of Claims] 1. As essential components: (a) an energy ray-curable cationic polymerizable organic substance, (b) an energy ray-sensitive cationic polymerization initiator, (c) an energy ray-curable radically polymerizable organic substance, (d 1.) A resin composition for optical modeling, comprising an energy ray-sensitive radical polymerization initiator and (e) a hydroxyl group-containing polyester. 2 (a) The energy beam-curable cationically 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, and (c)
Claim 1, wherein 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.
The optical modeling resin composition described above.