JPH11199647A - Resin composition for optical molding - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition having high curing sensitivity with active energy light and capable of producing moldings in good productivity in shortened active energy light irradiation times by adding an oxetane monoalcohol to a specific resin composition for optical moldings. SOLUTION: This resin composition comprises (A) a cationically polymerizable organic compound, (B) a radical-polymerizable organic compound, (C) an active energy light-sensitive cation polymerization initiator, (D) an active energy light-sensitive radical polymerization initiator, and (E) an oxetane monoalcohol, preferably at least one of compounds of the formula [R<1> is an alkyl, an aryl or an aralkyl; (n) is 1-6]. The component E is preferably contained in an amount of 1-30 wt.% based on the weight of the component A, and the component A preferably comprises at least one of epoxy compounds.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an optical three-dimensional object having high curing sensitivity with active energy rays, reduced molding time, excellent molding accuracy, dimensional accuracy, water resistance, moisture resistance, and mechanical properties. The present invention relates to a resin composition for optical shaping that can be produced smoothly with high productivity.

[0002]

2. Description of the Related Art In recent years, a method of three-dimensionally optically forming a liquid photocurable resin composition based on data input to a three-dimensional CAD has been proposed. Has been widely adopted since it can be manufactured with good dimensional accuracy.
No. 78 discloses a method of obtaining a three-dimensional object by supplying a required amount of light energy to a photocurable resin, and a basic practical method is proposed in Japanese Patent Application Laid-Open No. 60-247515. Thereafter, a similar technique or an improved technique is disclosed in JP-A-62-35966, JP-A-1-204915, JP-A-2-113925, JP-A-2-145616, and JP-A-2-15.
No. 3722, JP-A-3-15520, JP-A-3-21432, JP-A-3-41126 and the like.

A typical example of the optical three-dimensional molding method is as follows.
The liquid surface of the liquid photocurable resin placed in the container is selectively irradiated with an ultraviolet laser controlled by a computer so that a desired pattern is obtained, and is cured to a predetermined thickness, and then one layer is formed on the cured layer. In this case, a liquid resin is supplied, irradiated with an ultraviolet laser, and cured in the same manner as described above, and a stacking operation for obtaining a continuous cured layer is repeated, thereby finally obtaining a three-dimensional structure. This optical three-dimensional shaping method has recently attracted particular attention because it can easily and relatively quickly obtain a shaped object having a considerably complicated shape.

A resin or a resin composition used for optical shaping has a high curing sensitivity with active energy rays, a high resolution of the shaped article and an excellent shaping accuracy,
Low volume shrinkage during curing, excellent mechanical properties of cured product, good self-adhesiveness, good curing characteristics under oxygen atmosphere, low viscosity, water resistance and moisture resistance It is required to have various properties such as excellent properties, low absorption of water and moisture over time, and excellent dimensional stability. Conventionally, as a resin composition for optical shaping,
Acrylate-based photocurable resin compositions, urethane acrylate-based photocurable resin compositions, epoxy-based photocurable resin compositions, epoxyacrylate-based photocurable resin compositions, and vinyl ether-based photocurable resin compositions have been proposed and used. I have been. Among these, epoxy-based photocurable resin compositions have recently received particular attention because of the good dimensional accuracy of the shaped articles obtained therefrom.

However, it has been pointed out that the reaction of the epoxy-based photocurable resin composition is accelerated by cations generated by light irradiation, so that the reaction speed is low and the molding takes too much time. Therefore, in order to increase the reaction rate, it has been proposed to add a low molecular polyol compound such as ethylene glycol or propylene glycol to the epoxy-based photocurable resin composition. In addition, for the purpose of shortening the molding time by improving the reaction rate, etc., for optical molding in which a polyester polyol compound is added to a photocurable resin composition containing a cationically polymerizable organic compound such as an epoxy compound and a radically polymerizable organic compound. A resin composition has been proposed (JP-B-7-103218). However, in any case, since the curing speed at the time of photocuring is low, it takes a long time to perform optical molding, and the obtained molded article is not sufficiently cured and has insufficient mechanical properties. In addition, the dimensional accuracy of the obtained molded article is low, and there is a problem in terms of water resistance and moisture resistance.

[0006]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a molded article having a high sensitivity to curing by active energy rays, a high productivity of molded articles in a shortened irradiation time of active energy rays, and a resolution and modeling. It is excellent in accuracy and can obtain a shaped article having the desired dimensions, and furthermore, has a small volume shrinkage rate during curing, high dimensional accuracy, excellent water resistance and moisture resistance, An object of the present invention is to provide a resin composition for optical modeling capable of producing a molded article having little moisture absorption, excellent dimensional stability, and excellent mechanical properties.

[0007]

The present inventors have intensively studied to solve the above-mentioned problems. As a result, a resin composition for optical shaping was prepared using a cationically polymerizable organic compound, a radically polymerizable organic compound, an active energy ray-sensitive cationic polymerization initiator and an active energy ray-sensitive radical polymerization initiator, and further, the above-mentioned optical composition was prepared. When the oxetane monoalcohol compound is contained in the optical molding resin composition, when optical molding is performed using the optical molding resin composition obtained thereby, it is excellent in water resistance and moisture resistance, and furthermore, in dimensions. It has been found that a molded article having excellent accuracy, dimensional stability, and mechanical properties can be produced with high productivity at a high reaction rate and a high molding rate and with a reduced irradiation time of active energy rays. Furthermore, the present inventors further include a compound having two or more oxetane groups in one molecule in the above-mentioned optical molding resin composition containing an oxetane monoalcohol compound, and obtains the compound using the compound. It has been found that the dimensional accuracy of the optically formed object obtained is further improved, and the present invention has been completed based on those findings.

That is, the present invention is characterized by containing a cationically polymerizable organic compound, a radically polymerizable organic compound, an active energy ray-sensitive cationic polymerization initiator, an active energy ray-sensitive radical polymerization initiator, and an oxetane monoalcohol compound. It is a resin composition for optical modeling.

Further, the present invention provides an optical molding resin composition according to the present invention, wherein the oxetane compound having two or more oxetane groups in one molecule is contained in an amount of 50 to 200% by weight based on the weight of the oxetane monoalcohol compound. %.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. Cationic polymerizable organic compound used in the present invention,
When the active energy ray is irradiated in the presence of the active energy ray-sensitive cationic polymerization initiator, the polymerization reaction and / or
Or an organic compound which causes a crosslinking reaction. The term "active energy ray" as used herein refers to an energy ray such as an ultraviolet ray, an electron beam, an X-ray, a radiation, or a high frequency that can cure an optical molding resin composition.

In the present invention, as the cationically polymerizable organic compound, any compound which undergoes a polymerization reaction and / or a crosslinking reaction when irradiated with an active energy ray in the presence of an active energy ray-sensitive cationic polymerization initiator can be used. As typical examples, epoxy compounds, cyclic ether compounds, cyclic acetal compounds, cyclic lactone compounds, cyclic thioether compounds, spiroorthoester compounds,
Vinyl ether compounds and the like can be mentioned. In the present invention, one or two or more of the above-mentioned cationically polymerizable organic compounds may be used.

Specific examples of the cationically polymerizable organic compound include: (1) an epoxy compound such as an alicyclic epoxy resin, an aliphatic epoxy resin, or an aromatic epoxy resin; (2) trimethylene oxide, 3,3-dimethyloxetane , 3,3-dichloromethyloxetane, 3-methyl, 3-phenoxymethyloxetane, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl]
Oxetane compounds such as benzene, tetrahydrofuran, oxolane compounds such as 2,3-dimethyltetrahydrofuran, trioxane, 1,3-dioxolane,
Cyclic ether or cyclic acetal compounds such as 1,3,6-trioxanecyclooctane; (3) cyclic lactone compounds such as β-propiolactone and ε-caprolactone; (4) ethylene sulfide and thioepichlorohydrin (5) Thietane compounds such as 1,3-propyne sulfide and 3,3-dimethylthiethane; (6) 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; (7) spiroorthoester compounds obtained by reacting epoxy compounds with lactones; (8) ethylenically unsaturated compounds such as vinylcyclohexane, isobutylene and polybutadiene. be able to.

Among the above, in the present invention, an epoxy compound is preferably used as the cationically polymerizable organic compound, and a polyepoxy compound having two or more epoxy groups in one molecule is more preferably used. In particular, the cationic polymerizable organic compound contains an alicyclic polyepoxy compound having two or more epoxy groups in one molecule, and the content of the alicyclic polyepoxy compound is based on the total weight of the epoxy compound. 30% by weight or more, more preferably 5%
When an epoxy compound (a mixture of epoxy compounds) of 0% by weight or more is used, the rate of cationic polymerization, thick film curability,
Resolution, ultraviolet transmittance and the like are further improved, and the viscosity of the optical molding resin composition is reduced so that the molding is performed smoothly, and the volume shrinkage of the obtained optical molded article is further reduced. Become.

The above-mentioned alicyclic epoxy resin includes a polyglycidyl ether of a polyhydric alcohol having at least one alicyclic ring, or a compound containing a cyclohexene or cyclopentene ring, which is suitably oxidized with hydrogen peroxide, peracid or the like. Cyclohexene oxide or cyclopentene oxide-containing compounds obtained by epoxidation with an agent. More specifically, as alicyclic epoxy resins, for example, 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, vinylcyclohexene dioxide,
4-vinylepoxycyclohexane, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, 3,4-epoxy-6-methylcyclohexyl-
3,4-epoxy-6-methylcyclohexanecarboxylate, methylene bis (3,4-epoxycyclohexane), dicyclopentadiene diepoxide, di (3,4-epoxycyclohexylmethyl) ether of ethylene glycol, ethylene bis (3,4 -Epoxycyclohexanecarboxylate), dioctyl epoxyhexahydrophthalate, di-2-ethylhexyl epoxyhexahydrophthalate, and the like.

Examples of the above-mentioned aliphatic epoxy resin include polyglycidyl ethers of aliphatic polyhydric alcohols or alkylene oxide adducts thereof, polyglycidyl esters of aliphatic long-chain polybasic acids, and homopolymers of glycidyl acrylate and glycidyl methacrylate. Examples thereof include polymers and copolymers. More specifically, for example, diglycidyl ether of 1,4-butanediol, diglycidyl ether of 1,6-hexanediol, triglycidyl ether of glycerin, triglycidyl ether of trimethylolpropane, tetraglycidyl ether of sorbitol, Adding one or more alkylene oxides to aliphatic polyhydric alcohols such as hexaglycidyl ether of dipentaerythritol, diglycidyl ether of polyethylene glycol, diglycidyl ether of polypropylene glycol, ethylene glycol, propylene glycol, and glycerin. And polyglycidyl ethers of aliphatic long-chain dibasic acids. Further, in addition to the above epoxy compounds, for example, monoglycidyl ethers of higher aliphatic alcohols, glycidyl esters of higher fatty acids, epoxidized soybean oil, butyl epoxystearate, octyl epoxystearate, epoxidized linseed oil, epoxidized polybutadiene And the like.

Examples of the aromatic epoxy resin include mono- or polyglycidyl ethers of a monohydric or polyhydric phenol having at least one aromatic nucleus or an alkylene oxide adduct thereof. For example, glycidyl ether obtained by the reaction of bisphenol A or bisphenol F or an alkylene oxide adduct thereof with epichlorohydrin, epoxy novolak resin, phenol, cresol, butylphenol or a polyether alcohol obtained by adding an alkylene oxide thereto. Monoglycidyl ether and the like can be mentioned.

In the present invention, one of the above epoxy compounds
As the cation polymerizable organic compound, an epoxy compound containing at least 30% by weight of a polyepoxy compound having two or more epoxy groups in one molecule can be used as described above. It is preferably used.

In the present invention, a radically polymerizable organic compound is used together with the above-mentioned cationically polymerizable organic compound. The radically polymerizable organic compound used in the present invention is an organic compound that polymerizes and / or crosslinks when irradiated with ultraviolet rays or other active energy rays in the presence of an active energy ray-sensitive radical polymerization initiator. In the present invention, as the radically polymerizable organic compound, any compound which undergoes a polymerization reaction and / or a crosslinking reaction when irradiated with an active energy ray in the presence of an active energy ray-sensitive radical polymerization initiator can be used. as,
Examples thereof include (meth) acrylate compounds, unsaturated polyester compounds, allyl urethane compounds, and polythiol compounds, and one or more of the above-described radically polymerizable organic compounds can be used. Among them, a compound having at least one (meth) acryl group in one molecule is preferably used. Specific examples thereof include a reaction product of an epoxy compound and (meth) acrylic acid, and a (meth) acrylic alcohol. Acid esters, urethane (meth) acrylate, polyester (meth) acrylate, polyether (meth) acrylate and the like can be mentioned.

The reaction product of the above epoxy compound and (meth) acrylic acid includes an aromatic epoxy compound,
(Meth) acrylate-based reaction products obtained by reacting an alicyclic epoxy compound and / or an aliphatic epoxy compound with (meth) acrylic acid can be exemplified. Among the (meth) acrylate-based reaction products described above, a (meth) acrylate-based reaction product obtained by reacting an aromatic epoxy compound with (meth) acrylic acid is preferably used. As a specific example, bisphenol A (Meth) acrylate and epoxy novolak resin obtained by reacting glycidyl ether obtained by reacting a bisphenol compound such as bisphenol S or an alkylene oxide adduct thereof with an epoxidizing agent such as epichlorohydrin with (meth) acrylic acid (Meth) acrylate-based reaction products obtained by reacting (meth) acrylic acid can be exemplified.

The above-mentioned (meth) acrylates of alcohols include aromatic alcohols, aliphatic alcohols, alicyclic alcohols and / or alkylene oxide adducts thereof having at least one hydroxyl group in the molecule. And (meth) acrylate obtained by a reaction with (meth) acrylic acid. More specifically, for example, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, isooctyl (meth) Acrylate, tetrahydrofurfuryl (meth) acrylate, isobornyl (meth) acrylate, benzyl (meth) acrylate, 1,4-butanediol di (meth) acrylate,
1,6-hexanediol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) A) alkylene oxide adducts of polyhydric alcohols such as acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the aforementioned diols, triols, tetraols, and hexaols (Meth) acrylate and the like. Among them, as the (meth) acrylate of alcohols, (meth) acrylate having two or more (meth) acryl groups in one molecule obtained by reacting a polyhydric alcohol with (meth) acrylic acid is preferably used. Can be In addition, the above (meta)
Among acrylate compounds, acrylate compounds are preferably used from the viewpoint of polymerization rate, compared to methacrylate compounds.

The urethane (meth) acrylate includes, for example, (meth) acrylate obtained by reacting a hydroxyl group-containing (meth) acrylate with an isocyanate compound. Examples of the hydroxyl group-containing (meth) acrylate include aliphatic 2
A hydroxyl group-containing (meth) acrylate obtained by an esterification reaction between a polyhydric alcohol and (meth) acrylic acid is preferable, and specific examples thereof include 2-hydroxyethyl (meth) acrylate. The isocyanate compound is preferably a polyisocyanate compound having two or more isocyanate groups in one molecule, such as tolylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate and the like.

Further, examples of the above-mentioned polyester (meth) acrylate include polyester (meth) acrylate obtained by reacting a hydroxyl group-containing polyester with (meth) acrylic acid. Examples of the above polyether (meth) acrylate include polyether acrylate obtained by reacting a hydroxyl group-containing polyether with acrylic acid.

In the present invention, the active energy ray-sensitive cationic polymerization initiator (hereinafter, may be simply referred to as “cationic polymerization initiator”) is used for the cationic polymerization of the cationically polymerizable organic compound when irradiated with active energy rays. Any of the initiators that can be initiated can be used. Among them, as the cationic polymerization initiator, an onium salt which releases a Lewis acid when irradiated with active energy rays is preferably used. Examples of such onium salts include aromatic sulfonium salts of Group VIIa elements described in JP-B-52-14277, JP-B-52-14277.
The aromatic onium salts of Group VIa elements described in JP-A-14278, the aromatic onium salts of Group Va elements described in JP-B No. 52-14279, and the like can be mentioned. More specifically, for example, triphenylphenacylphosphonium tetrafluoroborate, triphenylsulfonium hexafluoroantimonate, bis- [4- (diphenylsulfonio) phenyl] sulfidebisdihexafluoroantimonate, bis- [ 4
-(Di4'-hydroxyethoxyphenylsulfonio) phenyl] sulfide bisdihexafluoroantimonate, bis- [4- (diphenylsulfonio) phenyl] sulfide bisdihexafluorophosphate, diphenyliodonium tetrafluoroborate And the like. In the present invention, one or more of the above-mentioned cationic polymerization initiators can be used. Among them, an aromatic sulfonium salt is more preferably used in the present invention. In the present invention, for the purpose of improving the reaction rate, a photosensitizer such as benzophenone, benzoin alkyl ether, or thioxanthone may be used together with the cationic polymerization initiator, if necessary.

In the present invention, as an active energy ray-sensitive radical polymerization initiator (hereinafter sometimes simply referred to as a "radical polymerization initiator"), radical polymerization of a radical polymerizable organic compound is initiated when irradiated with an active energy ray. Any of the obtained polymerization initiators can be used, and examples thereof include benzyl or its dialkyl acetal compound, acetophenone compound, benzoin or its alkyl ether compound, benzophenone compound, and thioxanthone compound.

Specifically, examples of benzyl or a dialkyl acetal compound thereof include benzyl dimethyl ketal, benzyl-β-methoxyethyl acetal, 1-hydroxycyclohexyl phenyl ketone and the like. Examples of the acetophenone-based compound include, for example, diethoxyacetophenone, 2-hydroxymethyl-1-phenylpropan-1-one,
4'-isopropyl-2-hydroxy-2-methyl-propiophenone, 2-hydroxy-2-methyl-propiophenone, p-dimethylaminoacetophenone, p-
tert-butyldichloroacetophenone, p-ter
Examples thereof include t-butyltrichloroacetophenone, p-azidobenzalacetophenone and the like. Examples of the benzoin-based compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin normal butyl ether, and benzoin isobutyl ether. Examples of the benzophenone compound include benzophenone, methyl o-benzoylbenzoate, Michler's ketone, 4,4'-bisdiethylaminobenzophenone, and 4,4'-dichlorobenzophenone. Examples of the thioxanthone-based compound include thioxanthone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, and 2-isopropylthioxanthone. In the present invention,
One or more radical polymerization initiators can be blended and used according to the desired performance.

The resin composition for optical shaping of the present invention may contain an oxetane monoalcohol compound together with the above-mentioned cationically polymerizable organic compound, radically polymerizable organic compound, cationic polymerization initiator and radical polymerization initiator. is necessary. Since the optical molding resin composition contains an oxetane monoalcohol compound, a molded article having high dimensional accuracy, which is excellent in water resistance, moisture resistance and mechanical properties, has a high reaction rate and a molding rate, and is excellent. It can be manufactured with high modeling accuracy and high productivity.

As the oxetane monoalcohol compound, any compound having at least one oxetane group and one alcoholic hydroxyl group in one molecule can be used. Among them, particularly, the following general formula: (1);

[0028]

Embedded image (Wherein, R ¹ represents an alkyl group, an aryl group, or an aralkyl group, and n represents an integer of 1 to 6).

In the above formula (1), examples of R ¹ include an alkyl group having 1 to 10 carbon atoms such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, phenyl, Aryl groups such as tolyl, naphthyl, methylphenyl, naphthyl,
And aralkyl groups such as benzyl and β-phenylethyl groups. Among them, R ¹ is methyl,
It is preferably a lower alkyl group such as ethyl, propyl and butyl. In the general formula (1),
n is an integer of 1 to 6, and is preferably an integer of 1 to 4.

Specific examples of the oxetane monoalcohol compound represented by the general formula (1) include 3-hydroxymethyl-3-methyloxetane, 3-hydroxymethyl-3-ethyloxetane, and 3-hydroxymethyl-3.
-Propyloxetane, 3-hydroxymethyl-3-normalbutyloxetane, 3-hydroxymethyl-3-
Phenyloxetane, 3-hydroxymethyl-3-benzyloxetane, 3-hydroxyethyl-3-methyloxetane, 3-hydroxyethyl-3-ethyloxetane, 3-hydroxyethyl-3-propyloxetane,
3-hydroxyethyl-3-phenyloxetane, 3-
Examples include hydroxypropyl-3-methyloxetane, 3-hydroxypropyl-3-ethyloxetane, 3-hydroxypropyl-3-propyloxetane, 3-hydroxypropyl-3-phenyloxetane, and 3-hydroxybutyl-3-methyloxetane. be able to. In the present invention, one or more of oxetane monoalcohol compounds can be used. Among them, 3-hydroxymethyl-3-methyloxetane and 3-hydroxymethyl-3-ethyloxetane are preferably used as oxetane monoalcohol compounds from the viewpoint of availability.

The resin composition for optical shaping of the present invention can be used in combination with the above-mentioned cationically polymerizable organic compound in view of the viscosity of the composition, the reaction speed, the shaping speed, the dimensional accuracy of the obtained shaped article, the mechanical properties and the like. The radical polymerizable organic compound preferably contains the cationic polymerizable organic compound: the radical polymerizable organic compound in a weight ratio of 90:10 to 30:70, and a ratio of 80:20 to 40:60. More preferably, it is contained.

The resin composition for optical shaping according to the present invention is characterized in that the cationic polymerization initiator is used in an amount of 1 to the total weight of the cationically polymerizable organic compound and the radically polymerizable organic compound.
-10% by weight and a radical polymerization initiator of 0.5-10
%, More preferably 2 to 6% by weight of a cationic polymerization initiator and 1 to 5% by weight of a radical polymerization initiator.

The resin composition for optical shaping of the present invention preferably contains the oxetane monoalcohol compound in the range of 1 to 30% by weight based on the weight of the cationic polymerization initiator. More preferably, it is contained in the range of -20% by weight. If the content of the oxetane monoalcohol compound is too small, the reaction of the resin composition for optical shaping becomes slow and the curing is insufficient, so that it takes a long time for molding or the mechanical properties of the molded article due to insufficient curing. , The dimensional accuracy is likely to be reduced. On the other hand, if the content of the oxetane monoalcohol compound is too large,
The reaction proceeds too much to cause a decrease in molecular weight, resulting in a decrease in mechanical properties of the obtained molded article, and furthermore, water resistance, moisture resistance,
Heat resistance and the like are likely to decrease.

The resin composition for optical shaping of the present invention may further comprise, if necessary, an oxetane compound having two or more oxetane groups in one molecule and having no alcoholic hydroxyl group (hereinafter, referred to as an oxetane compound). This may be referred to as a “polyoxetane compound”). When a polyoxetane compound is contained in the resin composition for optical shaping of the present invention, the dimensional accuracy of the obtained shaped article is further improved. When the polyoxetane compound is contained in the resin composition for optical shaping, the content thereof is 50 to 50% based on the weight of the oxetane monoalcohol compound.
Desirably, it is in the range of 200% by weight. As the polyoxetane compound, for example, the following general formula (2);

[0035]

Embedded image (Wherein, R ² represents a hydrogen atom, a fluorine atom, an alkyl group, a fluoroalkyl group, an aryl group or an aralkyl group, Z represents an oxygen atom or a sulfur atom, p represents an integer of 2 or more, and A represents 2 Which represents an organic group having a valency or higher.).

In the above formula (2), examples of R ² include a hydrogen atom, a fluorine atom, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl and the like. An alkyl group of
A fluoroalkyl group having 1 to 6 carbon atoms such as fluoromethyl, fluoroethyl, fluoropropyl, fluorobutyl, fluoropentyl, and fluorohexyl substituted with one or more fluorines, phenyl, tolyl, naphthyl, methylphenyl, Examples include an aryl group such as naphthyl, an aralkyl group such as benzyl and β-phenylethyl, and a furyl group. Among them, R ² is preferably a hydrogen atom, a lower alkyl group such as methyl, ethyl, propyl, butyl, pentyl and hexyl. Further, p is preferably an integer of 2 to 4. The valence of A is the same as the number of p. For example, an alkylene group having 1 to 12 carbon atoms, a phenylene group, a divalent arylene group such as a bisphenol residue, a diorganopolysiloxy group, a trivalent or Examples thereof include a tetravalent hydrocarbon group. Preferred examples of the compound having two or more oxetane groups in one molecule include 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene,
1,4-bis (3-ethyl-3-oxetanylmethoxy) butane and the like can be mentioned.

The optical molding resin composition of the present invention may contain, if necessary, a monooxetane compound other than an oxetane monoalcohol compound, a coloring agent such as a pigment or a dye, and a defoaming agent, as long as the effects of the present invention are not impaired. , Leveling agents, thickeners,
A suitable amount of one or more of a flame retardant, an antioxidant, a filler (silica, glass powder, ceramic powder, metal powder, etc.), a modifying resin and the like may be contained.

In carrying out optical three-dimensional modeling using the resin composition for optical modeling of the present invention, any of conventionally known optical three-dimensional modeling methods and apparatuses can be used. As a typical example of the optical three-dimensional modeling method that can be preferably adopted, the active energy ray is selectively irradiated to the liquid optical molding resin composition of the present invention so as to obtain a cured layer having a desired pattern. To form a cured layer, and then supply an uncured liquid optical modeling resin composition to the cured layer, and similarly irradiate an active energy ray to newly form a cured layer continuous with the cured layer. A method of finally obtaining a desired three-dimensional structure by repeating the laminating operation can be cited. As described above, examples of the active energy rays include ultraviolet rays, electron beams, X-rays, radiation, and high frequencies. Among them,
Ultraviolet light having a wavelength of 300 to 400 nm is preferably used from an economic viewpoint, and in this case, the light source may be an ultraviolet laser (for example, an Ar laser or a He-Cd laser), a mercury lamp, a xenon lamp, a halogen lamp, or a fluorescent lamp. Etc. can be used. Among them, a laser light source is preferably used because it can increase the energy level to shorten the molding time, and is excellent in light collecting property and can obtain high molding accuracy.

The resin composition for optical shaping of the present invention can be widely used in the field of three-dimensional optical shaping, and is not limited at all. Model for verifying the functionality, a model for checking the functionality of parts, a resin mold for producing a mold, a base model for producing a mold, and a direct mold for a prototype mold. In particular, the resin composition for optical shaping of the present invention can exert its power in creating a precise model of a part. More specifically, for example, precision components, electrical and electronic components, furniture, building structures,
Automobile parts, various containers, castings and other models, mother dies,
It can be used effectively for applications such as processing.

[0040]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited by the following examples. In the examples, "parts" means parts by weight.

Example 1 (1) 3,4-epoxycyclohexylmethyl-3,
4-epoxycyclohexanecarboxylate 120
Parts, 1,4-butanediol diglycidyl ether 30
Part, bis- [4- (diphenylsulfonio) phenyl]
Sulfide bisdihexafluoroantimonate 4.5
Parts, 40 parts of dicyclopentanyl diacrylate, 60 parts of dipentaerythritol hexaacrylate, 3 parts of 1-hydroxy-cyclohexyl-phenyl ketone, 10 parts of 3-methyl-3-hydroxymethyloxetane, and a benzotriazole-based curing depth regulator 0 1 part was sufficiently mixed to prepare a resin composition for optical shaping, and this was placed in a light-shielded tank.

(2) Using the resin composition for optical shaping obtained in (1) above, a water-cooled Ar laser beam using an ultra-high-speed optical shaping system (“SOLIFORM500B” manufactured by Teijin Seiki Co., Ltd.) (Output: 500 mW; wavelength: 33
3, 351 and 364 nm) perpendicular to the surface, and under irradiation energy of 20 to 30 mJ / cm ² , at a slice pitch (lamination thickness) of 0.05 mm and an average molding time of 2 minutes per layer. After performing optical three-dimensional modeling,
A dumbbell-shaped test piece according to IS K7113 was prepared. Observation of the test piece thus obtained by visual observation revealed that the test piece had a good shape without any distortion. Further, when the cured state of the obtained test piece was examined by touching with a hand, the test piece was sufficiently hardened, and was not broken even when pulled with both hands, and had excellent mechanical strength.

(3) In order to examine the curing sensitivity (polymerization speed), the resin composition for optical shaping obtained in (1) above was used, and the ultrahigh-speed optical shaping system used in (2) above was used. Then, when the photolithography was performed with an average molding time of 2 minutes per layer while changing the irradiation energy, the minimum curing energy (critical curing energy Ec) was 15 mJ / cm ² , and the film was hardened with a low irradiation energy. A molded article having excellent mechanical properties was obtained.

(4) The same high-speed optical shaping system as used in (2) above, using the resin composition for optical shaping obtained in (1) above to check the shaping accuracy (dimensional accuracy) When a Pennsylvania part (a cube having a side of 200 mm) was manufactured by adopting the molding conditions, the dimensional accuracy of the obtained molded product was ± 0.05 mm, and the molding accuracy (dimensional accuracy) was extremely excellent. . (5) The Pennsylvania parts obtained in (4) above are allowed to stand in a temperature and humidity controlled room at a temperature of 25 ° C. and a humidity of 80% for one week, and moisture absorption is performed based on a difference in weight between before and after being placed in the room. When the percentage was determined, the moisture absorption was 0.6% by weight, and the dimensional increase after left for one week was 0.05 mm on each side. The moisture absorption was extremely low, and the moisture resistance and water resistance were excellent.

Comparative Example 1 (1) The procedure of Example 1 was repeated except that 10 parts of a polyester polyol ("TONE 0301" manufactured by Union Carbide) was used instead of 10 parts of 3-methyl-3-hydroxymethyloxetane. A resin composition for optical shaping was prepared in the same manner as in 1) and stored in a light-shielding tank. (2) Using the resin composition for optical shaping obtained in (1) above, a dumbbell-shaped test piece was produced in the same manner as in (2) of Example 1. The test specimen obtained in this way was soft and not sufficiently cured, and was broken when pulled with both hands. (3) In order to examine the curing sensitivity (polymerization rate), optical molding was performed in the same manner as (3) of Example 1 using the optical molding resin composition obtained in (1) above. , Minimum curing energy (critical curing energy Ec) is 28m
It was as high as J / cm ² , and the resulting cured product was soft and lacked in hardness.

(4) In order to examine the molding accuracy (dimensional accuracy), a Pennsylvania part was prepared using the optical molding resin composition obtained in the above (1) in the same manner as in (1) of Example 1. As a result, the dimensional accuracy of the obtained modeled product was ± 0.25 mm, and the modeling accuracy (dimensional accuracy) was much lower than that of Example 1. (5) The Pennsylvania parts obtained in (4) above are allowed to stand in a temperature and humidity controlled room at a temperature of 25 ° C. and a humidity of 80% for one week, and moisture absorption is performed based on a difference in weight between before and after being placed in the room. When the percentage was determined, the moisture absorption was 1.4% by weight, and the dimension increase after standing for one week was 0.5 mm on each side.
The moisture absorption rate was higher than that of the molded article obtained in the above, and the moisture resistance and the water resistance were poor.

Example 2 (1) 3,4-Epoxycyclohexylmethyl-3,
4-epoxycyclohexanecarboxylate 105
Parts, 1,4-butanediol diglycidyl ether 45
Part, bis- [4- (diphenylsulfonio) phenyl]
5 parts of sulfide bisdihexafluoroantimonate,
50 parts of ethylene oxide-modified bisphenol A diacrylate, 50 parts of dipentaerythritol hexaacrylate, 50 parts of dicyclopentanyl diacrylate, 1 part
-Hydroxy-cyclohexyl-phenyl ketone 5 parts,
25 parts of 3-methyl-3-hydroxymethyloxetane and 0.2 parts of a benzotriazole-based curing depth regulator were sufficiently mixed to prepare a resin composition for optical shaping, and this was placed in a light-shielding tank.

(2) Using the resin composition for optical shaping obtained in (1) above, a dumbbell-shaped test piece was prepared in the same manner as in (2) of Example 1. Observation of the test piece thus obtained by visual observation revealed that the test piece had a good shape without any distortion. In addition, when the cured state of the obtained test piece was examined by hand, it was found that the test piece was sufficiently hardened, did not break even when pulled with both hands, and had excellent mechanical strength. (3) In order to examine the curing sensitivity (polymerization rate), optical molding was performed in the same manner as (3) of Example 1 using the optical molding resin composition obtained in (1) above. , Minimum curing energy (critical curing energy Ec) is 12m
It was J / cm ² , and a molded article excellent in mechanical properties, hardened with low irradiation energy, was obtained. (4) In order to examine the molding accuracy (dimensional accuracy), a Pennsylvania part was produced in the same manner as in (4) of Example 1 using the optical molding resin composition obtained in (1) above. The dimensional accuracy of the obtained model is ± 0.06
mm, and the molding accuracy (dimensional accuracy) was extremely excellent.

Example 3 (1) Bisphenol A diglycidyl ether 10
Part, 3,4-epoxycyclohexylmethyl-3,4-
50 parts of epoxycyclohexanecarboxylate, triphenylsulfonium hexafluoroantimonate 2
Parts, bisphenol A epoxy acrylate 15 parts, pentaerythritol triacrylate 25 parts, 2,2-
Diethoxyacetophenone (2 parts), 3-ethyl-3-hydroxymethyloxetane (5 parts) and a benzotriazole-based curing depth regulator (0.05 part) were sufficiently mixed to prepare an optical molding resin composition, which was used as a light-shielding agent. Housed in a tank.

(2) Using the resin composition for optical shaping obtained in (1) above, a dumbbell-shaped test piece was prepared in the same manner as in (2) of Example 1. Observation of the test piece thus obtained by visual observation revealed that the test piece had a good shape without any distortion. In addition, when the cured state of the obtained test piece was examined by hand, it was found that the test piece was sufficiently hardened, did not break even when pulled with both hands, and had excellent mechanical strength. (3) In order to examine the curing sensitivity (polymerization rate), optical molding was performed in the same manner as (3) of Example 1 using the optical molding resin composition obtained in (1) above. The minimum curing energy (critical curing energy Ec) at which a hardened molded product was obtained was 17 mJ / cm ² , and a molded product excellent in mechanical properties hardened with low irradiation energy was obtained. (4) In order to examine the molding accuracy (dimensional accuracy), the Pennsylvania part (1) was used in the same manner as (4) of Example 1 using the optical molding resin composition obtained in (1) above.
When a cube having a side of 200 mm) was manufactured, the dimensional accuracy of the obtained modeled product was ± 0.04 mm, which was extremely excellent in the modeling accuracy (dimensional accuracy).

Example 4 (1) 3,4-Epoxycyclohexylmethyl-3,
4-epoxycyclohexanecarboxylate 150
Parts, ethylene oxide-modified bisphenol A diacrylate 90 parts, dicyclopentanyl diacrylate 30
Parts, ethylene oxide-modified trimethylolpropane triacrylate 30 parts, bis- [4- (diphenylsulfonio) phenyl] sulfide bisdihexafluoroantimonate 4.5 parts, 1-hydroxy-cyclohexyl-phenyl ketone 6 parts, 3- A resin composition for optical shaping was prepared by sufficiently mixing 25 parts of methyl-3-hydroxymethyloxetane and 1.5 parts of a benzotriazole-based curing depth regulator, and this was placed in a light-shielding tank.

(2) Using the resin composition for optical shaping obtained in (1) above, a dumbbell-shaped test piece was prepared in the same manner as in (2) of Example 1. Observation of the test piece thus obtained by visual observation revealed that the test piece had a good shape without any distortion. In addition, when the cured state of the obtained test piece was examined by hand, it was found that the test piece was sufficiently hardened, did not break even when pulled with both hands, and had excellent mechanical strength. (3) In order to examine the curing sensitivity (polymerization rate), optical molding was performed in the same manner as (3) of Example 1 using the optical molding resin composition obtained in (1) above. , Minimum curing energy (critical curing energy Ec) is 19m
It was J / cm ² , and a molded article excellent in mechanical properties, hardened with low irradiation energy, was obtained.

(4) In order to examine the molding accuracy (dimensional accuracy), a Pennsylvania part was prepared by using the optical molding resin composition obtained in the above (1) in the same manner as in (1) of Example 1. Upon fabrication, the dimensional accuracy of the obtained modeled product was ± 0.05 mm, which was extremely excellent in the modeling accuracy (dimensional accuracy). (5) The Pennsylvania parts obtained in (4) above are allowed to stand in a temperature and humidity controlled room at a temperature of 25 ° C. and a humidity of 80% for one week, and moisture absorption is performed based on a difference in weight between before and after being placed in the room. When the percentage was determined, the moisture absorption was 0.35% by weight, the dimensional increase after standing for one week was 0.05 mm on each side, the moisture absorption was low, and the moisture resistance and water resistance were excellent.

Comparative Example 2 (1) Optical molding was performed in the same manner as in (1) of Example 4, except that 25 parts of ethylene glycol was used instead of 25 parts of 3-methyl-3-hydroxymethyloxetane. A resin composition was prepared and stored in a light-shielding tank. (2) Using the resin composition for optical shaping obtained in (1) above, a dumbbell-shaped test piece was produced in the same manner as in (2) of Example 1. The test specimen obtained in this way was soft and not sufficiently cured, and was broken when pulled with both hands. (3) In order to examine the curing sensitivity (polymerization rate), optical molding was performed in the same manner as (3) of Example 1 using the optical molding resin composition obtained in (1) above. , Minimum curing energy (critical curing energy Ec) is 28m
J / cm ² , and the resulting cured product was soft.

(4) In order to examine the molding accuracy (dimensional accuracy), a Pennsylvania part was prepared using the optical molding resin composition obtained in (1) above in the same manner as in (1) of Example 1. As a result of the fabrication, the dimensional accuracy of the obtained modeled product was ± 0.20 mm, and the modeling accuracy (dimensional accuracy) was low. (5) The Pennsylvania parts obtained in (4) above are allowed to stand in a temperature and humidity controlled room at a temperature of 25 ° C. and a humidity of 80% for one week, and moisture absorption is performed based on a difference in weight between before and after being placed in the room. When the percentage was determined, the moisture absorption was 1.0% by weight, and the dimension increase after standing for 1 week was 1 mm on each side, indicating that the moisture absorption was high.
It was inferior in moisture resistance and water resistance.

Example 5 (1) 3,4-epoxycyclohexylmethyl-3,
4-epoxycyclohexanecarboxylate 125
Parts, ethylene oxide-modified bisphenol A diacrylate 90 parts, dicyclopentanyl diacrylate 30
Part, ethylene oxide-modified trimethylolpropane triacrylate 30 parts, bis- [4- (diphenylsulfonio) phenyl] sulfide bisdihexafluoroantimonate 4.5 parts, 1-hydroxy-cyclohexyl-phenyl ketone 6 parts, 3-part 25 parts of ethyl-3-hydroxymethyloxetane, 25 parts of 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene and 1.5 parts of a benzotriazole-based curing depth controlling agent are sufficiently mixed and optically mixed. A typical molding resin composition was prepared and stored in a light-shielding tank.

(2) Using the resin composition for optical shaping obtained in (1) above, a dumbbell-shaped test piece was prepared in the same manner as in (2) of Example 1. Observation of the test piece thus obtained by visual observation revealed that the test piece had a good shape without any distortion. In addition, when the cured state of the obtained test piece was examined by hand, it was found that the test piece was sufficiently hardened, did not break even when pulled with both hands, and had excellent mechanical strength. (3) In order to examine the curing sensitivity (polymerization rate), optical molding was performed in the same manner as (3) of Example 1 using the optical molding resin composition obtained in (1) above. , Minimum curing energy (critical curing energy Ec) is 15m
It was J / cm ² , and a molded article excellent in mechanical properties, hardened with low irradiation energy, was obtained.

(4) In order to examine the molding accuracy (dimensional accuracy), a Pennsylvania part was prepared using the optical molding resin composition obtained in (1) in the same manner as in (1) of Example 1. Upon fabrication, the dimensional accuracy of the obtained modeled product was ± 0.04 mm, and was extremely excellent in the modeling accuracy (dimensional accuracy). (5) The Pennsylvania parts obtained in (4) above are allowed to stand in a temperature and humidity controlled room at a temperature of 25 ° C. and a humidity of 80% for one week, and moisture absorption is performed based on a difference in weight between before and after being placed in the room. When the percentage was determined, the moisture absorption was 0.45% by weight, and the dimensional increase after standing for one week was 0.06 mm on each side. The moisture absorption was low, and the moisture resistance and water resistance were excellent.

[0059]

The resin composition for optical shaping of the present invention has a high curing sensitivity with active energy rays, and can produce shaped articles with a reduced irradiation time of active energy rays with high productivity. Furthermore, when performing optical three-dimensional modeling using the resin composition for optical modeling of the present invention, it is possible to smoothly obtain a high-quality modeled product having excellent resolution and modeling accuracy and dimensions as intended. And, since the optical molding resin composition of the present invention has a small volume shrinkage upon curing,
It is possible to obtain a molded article having excellent dimensional accuracy. further,
The molded article obtained by using the optical molding resin composition of the present invention has excellent water resistance and moisture resistance, has little absorption of moisture and moisture over time, has excellent dimensional stability, and has excellent mechanical properties. Excellent in mechanical properties.

Claims (7)

[Claims] 1. A cationically polymerizable organic compound, a radically polymerizable organic compound, an active energy ray-sensitive cationic polymerization initiator, an active energy ray-sensitive radical polymerization initiator,
And an oxetane monoalcohol compound. 2. An oxetane monoalcohol compound represented by the following general formula (1): (Wherein, R ¹ represents an alkyl group, an aryl group, or an aralkyl group, and n represents an integer of 1 to 6.) An oxetane monoalcohol compound represented by the following formula: -Forming resin composition. 3. The resin composition for optical shaping according to claim 1, wherein the oxetane monoalcohol compound is contained in a proportion of 1 to 30% by weight based on the weight of the cationically polymerizable organic compound. 4. The resin composition for optical shaping according to claim 1, wherein the cationically polymerizable organic compound comprises at least one kind of epoxy compound. 5. An epoxy as the cationically polymerizable organic compound, wherein the content of the alicyclic polyepoxy compound having two or more epoxy groups in one molecule is 30% by weight or more based on the total weight of the epoxy compound. The resin composition for optical shaping according to any one of claims 1 to 4, wherein a compound is used. 6. The method according to claim 1, wherein the radically polymerizable organic compound is (meth)
The resin composition for optical shaping according to any one of claims 1 to 5, comprising at least one acrylate compound. 7. The oxetane compound having two or more oxetane groups in one molecule, wherein the oxetane compound further comprises 50 to 200% by weight based on the weight of the oxetane monoalcohol compound. 2. The resin composition for optical shaping according to claim 1.