JPH07103218B2 - Resin composition for optical modeling - Google Patents

Description

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

[Problems to be Solved by Prior Art and Invention]

Generally, the model corresponding to the product shape required at the time of mold making, or the model for the copying control of cutting or the electrode for die-sinking electric discharge machining is manufactured by hand or by NC cutting using an NC milling machine etc. It was done by processing. However, there is a problem that it requires a lot of labor and skill in the case of manual machining, and in the case of NC cutting,
There is also a problem that it is necessary to create a complicated machining program that takes into consideration replacement and wear for changing the shape of the cutting edge, and it may be necessary to further finish machining in order to remove the step generated on the machining surface. is there. Recently, technical development is expected to solve the problems of these conventional technologies and to create a new model for creating complicated models for mold making, copying, and die-sinking electrical discharge machining and various shaped objects by optical modeling method. Has been done.

This optical molding resin has excellent curing sensitivity with energy rays, good resolution of curing with energy rays, good ultraviolet transmittance after curing, low viscosity, and large γ characteristic. Various properties are required, such as a low volumetric shrinkage ratio during curing, excellent mechanical strength of the cured product, good self-adhesiveness, and good curing properties in an oxygen atmosphere.

On the other hand, in JP-A-62-235318, 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 are disclosed. An invention is described which is characterized in that and are simultaneously photocured. However, since the synthesis method of the present invention is not particularly aimed at obtaining a resin for optical modeling, even if the resin thus obtained is used as a resin for optical modeling, it is most suitable for an optical modeling system. It wasn't something.

[Means for Solving the Problems]

The present invention has been found as a result of extensive studies on a photosensitive resin having various characteristics required as such an optical molding resin.

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

The resin composition for optical modeling of the present invention, as an essential component,
(A) Energy ray curable cationically polymerizable organic substance,
(B) Energy ray-sensitive cationic polymerization initiator, (c)
It is characterized by containing an energy ray-curable radically polymerizable organic substance, (d) an energy ray-sensitive radical polymerization initiator, and (e) a hydroxyl group-containing polyester.

The energy ray-curable cationically polymerizable organic substance (a), which is a constituent of the present invention, is a cationically polymerizable organic matter which undergoes polymerization or crosslinking reaction by irradiation with energy rays in the presence of an energy ray-sensitive cationic polymerization initiator (b). The compound is, for example, one kind or a mixture of two or more kinds such as an epoxy compound, a cyclic ether compound, a cyclic lactone compound, a cyclic acetal compound, a cyclic thioether compound, a spiro orthoester compound and a vinyl compound. Among such cationically polymerizable compounds, compounds having at least two epoxy groups in one molecule are preferable, and examples thereof include conventionally known aromatic epoxy resins, alicyclic epoxy resins, and aliphatic epoxy resins. To be

The preferred aromatic epoxy resin is a polyglycidyl ether of a polyhydric phenol having at least one aromatic nucleus or an alkylene oxide adduct thereof, such as bisphenol A or bisphenol F or an alkylene oxide adduct thereof and epichlorohydrin. Examples thereof include glycidyl ether and epoxy novolac resin produced by reaction with.

Further, as preferable alicyclic epoxy resin, polyglycidyl ether of polyhydric alcohol having at least one alicyclic ring or cyclohexene, or cyclopentene ring-containing compound, hydrogen peroxide, peracid, etc.,
Mention may be made of cyclohexene oxide- or cyclopentene oxide-containing compounds obtained by epoxidation with a suitable oxidizing agent. Typical examples of the alicyclic epoxy resin include hydrogenated bisphenol A diglycidyl ether, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 2- (3,4-epoxycyclohexyl-5,5- Spiro-3,4-epoxy)
Cyclohexane-meta-dioxane, bis (3,4-epoxycyclohexylmethyl) adipate, vinylcyclohexenedioxide, 4-vinylepoxycyclohexane, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, 3,4-epoxy -6-methylcyclohexyl-3,4-epoxy-6-methylcyclohexanecarboxylate, methylenebis (3,4-epoxycyclohexane), dicyclopentadiene diepoxide, di (3,4-epoxycyclohexylmethyl) ether of ethylene glycol, Examples thereof include ethylene bis (3,4-epoxycyclohexanecarboxylate), dioctyl epoxyhexahydrophthalate, and di-2-ethylhexyl epoxyhexahydrophthalate.

Further preferred aliphatic epoxy resins include aliphatic polyhydric alcohols, or polyglycidyl ethers of alkylene oxide adducts thereof, polyglycidyl esters of aliphatic long-chain polybasic acids, homopolymers of glycidyl acrylate and glycidyl methacrylate, and copolymers. There are, as typical examples thereof, diglycidyl ether of 1,4-butanediol, diglycidyl ether of 1,6-hexanediol, triglycidyl ether of glycerin, triglycidyl ether of trimethylolpropane, tetraglycidyl ether of sorbitol, Hexaglycidyl ether of dipentaerythritol, diglycidyl ether of polyethylene glycol, diglycidyl ether of polypropylene glycol, ethylene glycol, propylene glycol Le, polyglycidyl ether of polyether polyol obtained by adding one or more alkylene oxides to aliphatic polyhydric alcohols such as glycerin, and diglycidyl esters of aliphatic long-chain dibasic acids. Furthermore, monoglycidyl ethers of aliphatic higher alcohols, phenols, cresols, butylphenols or monoglycidyl ethers of polyether alcohols obtained by adding alkylene oxides to these, glycidyl esters of higher fatty acids, epoxidized soybean oil, butyl epoxystearate. , Octyl epoxy stearate, 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. Trioxane,
Cyclic acetal compounds such as 1,3-dioxolane and 1,3,6-trioxanecyclooctane; Cyclic lactone compounds such as β-propiolactone and ε-caprolactone;
Thiirane compounds such as ethylene sulfide and thioepichlorohydrin; thietane compounds such as 1,3-propyne sulfide and 3,3-dimethylthietane; ethylene glycol divinyl ether, alkyl vinyl ethers, 3,4
Vinyl ether compounds such as dihydropyran-2-methyl (3,4-dihydropyran-2-carboxylate), triethylene glycol divinyl ether; spiro orthoester compounds obtained by reaction of epoxy compounds with lactones; vinylcyclohexane, Mention may be made of ethylenically unsaturated compounds such as isobutylene, polybutadiene and derivatives of the above compounds. These cationically polymerizable compounds may be used alone or in combination of two or more, depending on the desired performance.

Among these cationically polymerizable organic substances, particularly preferable ones are alicyclic epoxy resins having at least two epoxy groups in one molecule, which have cationic polymerization reactivity, low viscosity, ultraviolet transparency and thick film curing. It shows good properties in terms of properties, volume shrinkage, resolution, and so on.

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 irradiation with energy rays,
Especially preferred are the group of double salts which are onium salts which release a Lewis acid upon irradiation. 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 onium and Z is S, Se , Te, P, As, S
b, Bi, O, halogen (for example, 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 integers of 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, Al, Ca, In, Ti, Zn, Sc, V, Cr. , Mn, C
o 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. ] Is represented.

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

Further, an anion represented by the general formula MX _n (OH) ⁻ can also be used. Examples of other anions, perchlorate ion (ClO ₄ ^-), trifluoromethyl sulfite ion (CF ₃
SO ₃ ^-), fluorosulfonic acid ion (FSO ₃ ^-), toluenesulfonate anion, trinitrobenzene sulfonic acid anion, and the like.

Among these onium salts, it is particularly effective to use an aromatic onium salt as a cationic polymerization initiator, and among them, the aromatic compounds described in JP-A-50-151996 and JP-A-50-158680. Group halonium salts, JP-A-50-151997,
JP-A-52-30899, JP-A-56-55420, JP-A-55-12510
Group VIA aromatic onium salts described in JP-A-5, JP-A-50-1
Group VA aromatic onium salts described in JP 58698 A, JP-A-5
6-8428, JP-A-56-149402, JP-A-57-192429, etc., oxosulfoxonium salts, JP-B-49-17040
Aromatic diazonium salts described in U.S. Pat.
Thiobirylium salts described in 39655 are preferred. Further, an iron / allene complex and an aluminum complex / photolytic silicon compound-based initiator may also be used.

A photosensitizer such as benzophenone, benzoin isopropyl ether, or thioxanthone may 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 which is polymerized or cross-linked by energy ray irradiation in the presence of an energy ray-sensitive radical polymerization initiator (d), For example, it is composed of one kind or a mixture of two or more kinds of acrylate compound, methacrylate compound, allyl urethane compound, unsaturated polyester compound, polythiol compound 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. To be

Here, as the epoxy acrylate, preferred 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 its alkylene oxide adduct with acrylic acid. An acrylate obtained, for example, bisphenol A or an alkylene oxide adduct thereof,
Examples thereof include an acrylate obtained by reacting glycidyl ether obtained by a reaction with epichlorohydrin with acrylic acid, and an acrylate obtained by reacting an epoxy novolac resin with acrylic acid.

Preferred urethane acrylates include one or more kinds of hydroxyl group-containing polyesters, acrylates obtained by reacting hydroxyl group-containing polyethers with hydroxyl group-containing acrylate esters and isocyanates, and hydroxyl group-containing acrylate esters and isocyanates. It is an acrylate obtained by 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 kinds of aliphatic polyhydric alcohols with one or more kinds of polybasic acids, , 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,
Examples include dipentaerythritol. Examples of the polybasic acid include adipic acid, terephthalic acid, phthalic anhydride and trimellitic acid. Preferred as the hydroxyl group-containing polyether is 1 for the aliphatic polyhydric alcohol.
A hydroxyl group-containing polyether obtained by adding one or more alkylene oxides, and examples of the aliphatic polyhydric alcohol include 1,3-butanediol, 1,4-butanediol, 1,6 -Hexanediol,
Examples thereof include 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 the hydroxyl group-containing acrylic acid ester, an aliphatic polyhydric alcohol, a hydroxyl group-containing acrylic acid ester obtained by the esterification reaction of acrylic acid, as the aliphatic polyhydric alcohol, for example, ethylene glycol, 1 , 3-butanediol, 1,4-
Examples include butanediol, 1,6-hexanediol, diethylene glycol, triethylene glycol, neopentyl glycol, polyethylene glycol, polypropylene glycol, trimethylolpropane, glycerin, pentaerythritol, and dipentaerythritol. Among such hydroxyl group-containing acrylic acid esters, a hydroxyl group-containing acrylic acid ester obtained by an esterification reaction of 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 or more isocyanate groups in the molecule are preferable, but 2 such as tolylene diisocyanate, hexamethylene diisocyanate and isophorone diisocyanate are preferable.
Especially preferred are valent isocyanate compounds.

A preferable 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 kinds of aliphatic polyhydric alcohols with one or more kinds of monobasic acids, polybasic acids, and phenols. The hydroxyl group-containing polyester obtained, and 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 thereof include glycol, polypropylene glycol, trimethylolpropane, glycerin, pentaerythritol, and dipentaerythritol. As the monobasic acid, for example,
Examples 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 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-hexanediol, diethylene glycol, triethylene glycol, neopentyl glycol, polyethylene glycol, polypropylene glycol, trimethylolpropane, glycerin, pentaerythritol, dipentaerythritol Can be mentioned. Examples of the alkylene oxide include ethylene oxide and propylene oxide.

Preferred acrylic acid esters of alcohols are acrylates obtained by reacting an aromatic or aliphatic alcohol having at least one hydroxyl group in the molecule, and an alkylene oxide adduct thereof with acrylic acid, For example, 2-ethylhexyl acrylate, 2
-Hydroxyethyl acrylate, 2-hydroxypropyl acrylate, isoamyl acrylate, lauryl acrylate, stearyl acrylate, isooctyl acrylate, tetrahydrofurfuryl acrylate,
Isobornyl acrylate, benzyl acrylate, 1,
3-butanediol diacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, neopentyl glycol diacrylate, polyethylene glycol diacrylate, polypropylene glycol diacrylate , Trimethylolpropane triacrylate, pentaerythritol triacrylate, and dipentaerythritol hexaacrylate.

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

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

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

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 upon irradiation with energy rays, such as an acetophenone compound, a benzoin ether compound,
Ketones such as benzyl compounds, benzophenone compounds and thioxanthone compounds are preferred. Examples of the acetophenone compound include diethoxyacetophenone 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-te
Examples thereof include rt-butyltrichloroacetophenone and p-azidobenzalacetophenone. Examples of the benzoin ether-based 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, benzyl dimethyl ketal, benzyl-β-methoxyethyl acetal,
1-hydroxycyclohexyl phenyl ketone is mentioned. Examples of the benzophenone compound include benzophenone, methyl o-benzoylbenzoate, Michler's ketone, 4,4′-bisdiethylaminobenzophenone,
4,4'-dichlorobenzophenone may be mentioned. Examples of the thioxanthone compound include thioxanthone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, and 2-isopropylthioxanthone.

These energy ray-sensitive radical polymerization initiators (d)
Can be used alone or in combination of two or more 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 of one or more kinds of aliphatic polyhydric alcohols with one or more kinds of monobasic acids, polybasic acids, and phenols,
And a hydroxyl group-containing polyester obtained by an esterification reaction of one or more kinds of lactones with one or more kinds of monobasic acids, polybasic acids, and phenols, and as an aliphatic polyhydric alcohol, , For example, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, triethylene glycol,
Examples include neopentyl glycol, polyethylene glycol, polypropylene glycol, trimethylolpropane, glycerin, pentaerythritol, and dipentaerythritol. As the monobasic acid, for example, formic acid,
Examples include 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 depending on the desired performance.

Next, in the present invention, (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, (d) an energy ray-sensitive radical. The composition ratio of the polymerization initiator and the hydroxyl group-containing polyester (e) will be described. The composition ratio will be described in parts (parts by weight).

That is, the composition ratio of the energy ray-curable cationically polymerizable organic substance (a) and the energy ray-curable radically polymerizable organic substance (c) in the present invention is the same as the energy ray-curable cationically polymerizable organic substance (a) and the energy When the total of the radiation curable radically polymerizable organic substance (c) is 100 parts,
40 energy-curable cationically polymerizable organic substances (a)
To 95 parts, that is, those containing 5 to 60 parts of the energy ray-curable radically polymerizable organic substance (c), more preferably 50 to 90 parts of the energy ray-curable cationically polymerizable organic substance (a), That is, those containing 10 to 50 parts of the energy ray-curable radically polymerizable organic substance (c) have particularly excellent properties as a resin composition for optical modeling.

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 to obtain desired properties as a resin composition for optical modeling. A plurality of energy ray-curable organic substances, that is, the energy ray-curable cationically polymerizable organic substance (a) and the 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 cationically polymerizable organic substance (a) and the energy ray-curable radical. It may be contained in the range of 0.1 to 10 parts, preferably 0.5 to 6 parts, based on 100 parts of the total amount 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 such that the energy ray-curable organic substance 10
It can be contained in the range of 0.1 to 10 parts, preferably 0.2 to 5 parts, relative to 0 parts. The energy ray-sensitive cationic polymerization initiator (b) and the energy ray-sensitive radical polymerization initiator (d) are a plurality of energy ray-sensitive cationic polymerization initiators (in order to obtain desired characteristics) as a resin composition for optical modeling. b) and the energy ray sensitive radical polymerization initiator (d) can be blended and used. Further, when these polymerization initiators are mixed with the energy ray-curable organic substance, the polymerization initiators may be used by dissolving them in a suitable solvent.

The content of the (e) hydroxyl group-containing polyester in the composition of the present invention is 5 based on 100 parts in total of (a) the energy ray-curable cationically polymerizable organic substance and (c) the energy ray-curable radically polymerizable organic substance. It is preferable that the resin composition contains 40 to 40 parts, more preferably 10 to 30 parts, as the resin composition for optical modeling, particularly excellent properties.

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

Thus, in the composition of the present invention, (e) a hydroxyl group-containing polyester is added to 100 parts by weight of (a) an energy ray-curable cationically polymerizable organic substance and (c) an energy ray-curable radically polymerizable organic substance. If contained in an amount of 5 to 40 parts by weight, curing is promoted and excellent properties can be provided as a resin composition for optical modeling. In particular, the content of the (e) hydroxyl group-containing polyester should be 10 to 30 parts per 100 parts of the total of (a) the energy ray-curable cationically polymerizable organic substance and (c) the energy ray-curable radically polymerizable organic substance. When configured in this way, a very excellent optical modeling system can be obtained.

In the composition of the present invention, when the composition ratio of the energy ray-curable cationically polymerizable organic substance (a) is too large, that is, when the composition ratio of the energy ray-curable radically polymerizable organic substance (c) is too small, it is obtained. The composition is less susceptible to the influence of oxygen in the air during the curing reaction with active energy rays, and can reduce the volume shrinkage during curing, so that the cured product is distorted, cracked, and the like. Since a resin composition having a low viscosity can be easily obtained, the molding time can be shortened. However, during the curing reaction by the active energy ray, the polymerization reaction is likely to proceed from the portion irradiated with the active energy ray to the peripheral portion, so that the resolution is poor, and after the irradiation with the active energy ray, the polymerization reaction is completed for several seconds. Takes time. On the contrary, when the composition ratio of the energy ray-curable cationically polymerizable organic substance (a) is too small, that is, the energy ray-curable radically polymerizable organic substance (c).
When the composition ratio of is too large, the resolution is good because the polymerization reaction is difficult to proceed from the active energy ray irradiation area to the peripheral area, and it takes almost no time until the polymerization reaction is completed after the active energy ray irradiation. . However, during the curing reaction with active energy rays, the polymerization reaction is easily inhibited by oxygen in the air, and since the volume shrinkage during curing is large, the cured product is likely to be distorted or cracked, and the viscosity is further reduced. Therefore, when a low-viscosity radically polymerizable resin is used, skin irritation is great. None of such compositions is suitable as a resin composition for optical modeling.

The optical composition resin composition of the present invention, particularly (a) 40% by weight or more of an alicyclic epoxy resin in which the energy ray-curable cationically polymerizable organic substance has at least two or more epoxy groups in one molecule. When the energy-curable radical-polymerizable organic substance (c) contains 50% by weight or more of a compound having at least three unsaturated double bonds in one molecule, the energy-ray reaction It has excellent properties, excellent mechanical strength and resolution, and has a shrinkage ratio of 3% or less, so that a very excellent optical modeling system can be constructed.

The resin composition for optical modeling of the present invention is, unless necessary to impair the effects of the present invention, a heat-sensitive cationic polymerization initiator; a colorant such as a pigment or a dye; an antifoaming agent, a leveling agent, if necessary.
Various resin additives such as thickeners, flame retardants and antioxidants; fillers such as silica, glass powder, ceramics powder and metal powders; modifying resins and the like can be used in appropriate amounts. Examples of the heat-sensitive cationic polymerization initiator include, for example, JP-A-57
-49613 and the aliphatic onium salts described in JP-A-58-37004.

The viscosity of the composition of the present invention is preferably 2000 cp at room temperature.
s or less, more preferably 1000 cps or less. If the viscosity is too high, the time required for modeling becomes long, and the workability tends to deteriorate.

Generally, the resin composition for molding undergoes volume shrinkage upon curing, and therefore it is desired that the shrinkage is small in terms of accuracy. The volumetric shrinkage of the composition of the present invention during curing is preferably 5
% Or less, more preferably 3% or less.

As a specific method for carrying out the present invention, as described in JP-A-60-247515, the resin composition for optical modeling of the present invention is housed in a container, and light is guided into the resin composition. Forming a solid having a desired shape by inserting a body and selectively supplying active energy rays required for curing from the light guide while moving the container and the light guide relative to each other. You can As the active energy ray used for curing the composition of the present invention, ultraviolet rays, electron beams, X-rays, radiation, high frequency waves or the like can be used. Among these, ultraviolet rays having a wavelength of 1800 to 5000 Å are economically preferable, and as a light source thereof, an ultraviolet laser, a mercury lamp, a xenon lamp, a sodium lamp, an alkali metal lamp or the like can be used. A particularly preferable light source is a laser light source, which can increase the energy level to shorten the modeling time and improve the modeling accuracy by utilizing good light condensing property. A point light source that collects ultraviolet rays from various lamps such as a mercury lamp is also effective. Furthermore,
In order to selectively supply the active energy ray necessary for curing to the present resin composition, the resin composition has a wavelength equal to twice the wavelength suitable for curing the resin composition, and has 2 in-phase.
By irradiating two or more light fluxes in the resin composition so as to cross each other, two-photon absorption is performed to obtain an energy ray necessary for curing the resin composition, and the crossing point of the light is moved. You can also The light flux having the same phase can be obtained by, for example, laser light.

Since the composition of the present invention is cured by a cationic polymerization reaction and a radical polymerization reaction by an active energy ray, an active energy ray may be added depending on the types of the cationically polymerizable organic substance (a) and the radically polymerizable organic substance (c) used. At the time of irradiation, by heating the resin composition to about 30 to 100 ° C., it is possible to effectively accelerate the crosslinking and curing reaction, and further, to irradiate with energy rays, the obtained molded article is heated to 40 ° C.
It is also possible to obtain a molded article having more excellent mechanical strength by performing heat treatment at a temperature of -100 ° C or UV irradiation treatment with a mercury lamp or the like.

INDUSTRIAL APPLICABILITY The resin composition for optical modeling of the present invention is a very excellent one for creating a three-dimensional three-dimensional model by stacking layered products, and it is possible to perform model creation processing without using a mold, and to freely Its industrial value is extremely large, such as the ability to create highly accurate shapes such as curved surfaces by CAD / CAM and docking. For example, as the application fields of the resin composition, there are a model for judging the appearance design in the middle of design, a model for checking inconvenience of mutual combination of parts, a wooden mold for making a mold, and a mold. It can be used for a wide range of purposes, such as a copying model for manufacturing.

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

〔Example〕

Hereinafter, representative examples of the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples. In the examples, “part” means part by weight.

Example 1 (a) 65 parts of 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 20 parts of 1,4-butanediol diglycidyl ether as an energy ray-curable cationically polymerizable organic substance, (b) ) 3 parts of bis- [4- (diphenylsulfonio) phenyl] sulfide bisdihexafluoroantimonate as an energy ray sensitive cationic polymerization initiator, and (c) dipentaerythritol hexa as an energy ray curable radically polymerizable organic substance. 15 parts of acrylate, (d) 1 part of benzophenone as an energy ray sensitive radical polymerization initiator,
(E) As the 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 experimental system consisting of a three-dimensional NC (numerical control) table, a helium / cadmium laser (wavelength: 325 nm), on which a container containing a resin composition is placed, and an optical system and a control unit having a personal computer as a main unit. From this resin composition, a cone having a bottom diameter of 12 mm, a height of 15 mm, and a thickness of 0.5 mm was formed. This molded article had no distortion, had extremely high modeling accuracy, and had excellent mechanical strength.

When the time required for modeling was measured in order to compare the polymerization rate with a laser, it was as short as 35 minutes. In addition, in order to measure the molding accuracy, the diameter of the bottom surface of the conical shaped object was arbitrarily measured at 10 points, and the variation was measured. The average error from the average value (hereinafter referred to as the modeling accuracy) was 1.3%, which was high accuracy. Met.

Example 2 (a) 50 parts of 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 20 parts of 1,4-butanediol diglycidyl ether as an energy ray-curable cationically polymerizable organic substance, (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, (D) 1 part of benzyl dimethyl ketal as the energy ray-sensitive radical polymerization initiator, and (e) 10 parts of ε-caprolactone ester of glycerin as the hydroxyl group-containing polyester were sufficiently mixed to obtain a resin composition for optical modeling. . Example 1
When a hanging-shaped shaped object was created using the laser light modeling system shown in Fig. 3, the shaped object was free from distortion, had extremely high modeling accuracy, and had excellent mechanical strength. The resin composition had low viscosity, was easy to handle, and had excellent curability by laser light.

When a conical shaped article similar to that of Example 1 was prepared in order to measure the polymerization rate and modeling accuracy with a laser, the modeling time was 35 minutes and the modeling accuracy was 1.2%.

Example 3 (a) 10 parts of bisphenol A diglycidyl ether as an energy ray-curable cationically polymerizable organic substance, 3,4
-Epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate 40 parts, vinylcyclohexene oxide 10 parts, (b) energy ray sensitive cationic polymerization initiator, triphenylsulfonium hexafluoroantimonate 2 parts, (c) energy ray curing 15 parts of bisphenol A epoxy acrylate, 25 parts of pentaerythritol triacrylate as the organic radical-polymerizable organic substance, (d) 2 parts of 2,2-diethoxyacetophenone as the energy ray-sensitive radical polymerization initiator,
(E) As the hydroxyl group-containing polyester, 10 parts of ε-caprolactone ester of triethylene glycol was thoroughly mixed to obtain a resin composition for optical modeling. Using the laser stereolithography experimental system shown in Example 1, this composition was
When making a cup-shaped molded object while heating to 60 ° C,
A product with no distortion and excellent modeling accuracy was obtained.

When the same conical shaped article as in Example 1 was prepared to measure the polymerization rate and modeling accuracy with a laser, the reaction rate was fast because it was heated to 60 ° C, and the modeling time was a very short 25 minutes. Met. The molding accuracy was 1.6%.

Example 4 (a) 55 parts of 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 10 parts of 1,4-butanediol diglycidyl ether, triethylene as an energy ray-curable cationically polymerizable organic substance 10 parts of glycol divinyl ether, (b) 2 parts of bis- [4- (diphenylsulfonio) phenyl] sulfide bisdihexafluoroantimonate as an energy ray-sensitive cationic polymerization initiator, (c) energy ray-curable radical-polymerizable 20 parts of dipentaerythritol hexaacrylate as an organic substance, (d) 1 part of benzophenone as an energy ray sensitive radical polymerization initiator, (e)
As a hydroxyl group-containing polyester, 30 parts of adipic acid ester of 1,4-butanediol was sufficiently mixed to obtain a resin composition for optical modeling. Using this composition, a hanging-shaped shaped article was produced by the laser light shaping experimental system shown in Example 1, and as a result, there was obtained no distortion and excellent mechanical strength, shaping accuracy, and surface smoothness. Was given.

When a conical shaped article similar to that of Example 1 was prepared in order to measure the polymerization rate and the shaping accuracy by a laser, the shaping time was 30 minutes and the shaping accuracy was 0.5%, which was extremely high precision.

Comparative Example 1 3,4-Epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate 60 parts, bisphenol A
20 parts of diglycidyl ether, 20 parts of 1,4-butanediol diglycidyl ether and 3 parts of triphenylsulfonium hexafluoroantimonate were sufficiently mixed to obtain an energy ray-curable cationically polymerizable resin composition. Using this composition, a conical shaped object similar to that of Example 1 was created using the laser light modeling experiment system shown in Example 1. The object was free from distortion and Although the resin composition was excellent in strength, the resin composition had poor resolution when cured by a laser beam, and thus the surface of the modeled object was rough and the molding accuracy was poor. In addition, from the time of laser irradiation, it was necessary to wait for several seconds until the polymerization reaction was completed, and the time required for modeling was as long as 120 minutes. In addition, 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 benzyl dimethyl ketal were thoroughly mixed to obtain an energy ray-curable radically polymerizable resin composition. Using this composition and using the laser light modeling experiment system shown in Example 1, a conical shaped object similar to that in Example 1 was prepared. The molding time was 45 minutes. The product was distorted due to a large curing shrinkage, and the molding accuracy was 10.0%, which was very poor.

Comparative Example 3 3,4-Epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate 65 parts, 1,4-butanediol diglycidyl ether 20 parts, bis [4- (diphenylsulfonio) phenyl] sulfide bisdihexafluoro 3 parts of antimonate, 15 parts of dipentaerythritol hexaacrylate and 1 part of benzophenone were thoroughly mixed to obtain an energy ray-curable cation / radical polymerizable resin composition. Using this composition, a conical shaped object similar to that in Example 1 was prepared by using the laser light modeling experiment system shown in Example 1. This shaped article had no distortion and was excellent in mechanical strength. Molding time is 50 minutes,
The molding accuracy was 3.0%, and the resin composition for optical modeling had reached a certain level, but it was clearly inferior to that containing the hydroxyl group-containing polyester.

〔The invention's effect〕

Since the resin composition for optical modeling 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, it has characteristics of the energy ray-curable cationically polymerizable organic substance. And a resin composition having the advantages of both properties of an energy ray-curable radically polymerizable organic substance. The cationically polymerizable resin composition is not affected by oxygen in the air during the curing reaction with active energy rays, and can reduce the volume shrinkage during curing. Is less likely to occur, the strength of the cured product is excellent, 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 is likely to proceed from the portion irradiated with the active energy ray to the peripheral portion, resulting in poor resolution. There are drawbacks such as requiring. On the other hand, the radically polymerizable resin composition, during the curing reaction by active energy rays,
Since the polymerization reaction does not easily proceed from the active energy ray irradiation area to the peripheral area, the resolution is good, and it takes almost no time until the polymerization reaction is completed after the active energy ray irradiation. However, the polymerization reaction is inhibited by oxygen in the air, the shrinkage rate during curing is large, the mechanical strength of the cured product is poor, and the low-viscosity resin has the drawbacks of high skin irritation and strong odor. .

In the present invention, (a) energy ray-curable cationically polymerizable organic substance, (b) energy ray-sensitive cationic polymerization initiator, (c) energy ray-curable radically polymerizable organic substance, (d) energy ray-sensitive radical polymerization initiator By mixing the agent and the (e) hydroxyl group-containing polyester,
It was possible to obtain a resin composition for optical modeling having the following features. That is, it is hardly affected by oxygen in the air. Since the volume shrinkage during curing can be reduced, the cured product is less likely to be distorted or cracked.
Since the low-viscosity resin composition is easy, the molding time can be shortened. When the active energy ray is irradiated, the resolution is good because the polymerization reaction does not easily proceed from the active energy ray irradiated area to the peripheral area. It takes almost no time until the polymerization reaction is completed after irradiation with the active energy rays. The cured product has excellent mechanical strength and hardness. The cationic polymerization rate is accelerated and the curability is excellent. That is, the curing speed is fast,
Moreover, since the curing shrinkage is low, a highly accurate resin composition for optical modeling can be obtained.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Office reference number FI technical display location G03F 7/029 7/038 503

Claims (2)

[Claims] 1. As essential components, (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) energy. A resin composition for optical modeling, comprising a line-sensitive radical polymerization initiator and (e) a hydroxyl group-containing polyester. 2. The energy ray-curable cationically polymerizable organic substance (a) contains 40% by weight or more of an alicyclic epoxy resin having at least two epoxy groups in one molecule.
(C) The energy ray curable radically polymerizable organic substance is
The resin composition for optical modeling according to claim 1, which contains 50% by weight or more of a compound having at least three unsaturated double bonds in one molecule.