JP2001031879A - Stabilization of resin composition for optical three- dimensional shaping - Google Patents

Abstract

PROBLEM TO BE SOLVED: To exhibit excellent workability and efficiency, suppress a rise in viscosity of a resin composition and stabilize the subject composition by bringing the resin composition for optical three-dimensional shaping into contact with a basic ceramics adsorbent. SOLUTION: (A) A resin composition for optical three-dimensional shaping comprising (i) a cationic polymerizable organic compound (preferably an aromatic epoxy compound, an alicyclic epoxy compound or the like) and (ii) an energy ray-sensitive cationic polymerization initiator (preferably a double salt, etc., which is an onium salt capable of releasing a Lewis acid by irradiation) is brought into contact with (B) a basic ceramics adsorbent to thereby stabilize the component A. The component B is preferably used in an amount of 0.05-10 pts.wt. based on 100 pts.wt. of the component (i) in the component A. SnO, MgO, MgO-Al2O3, etc., can be cited as the component B and the amount thereof used may be >=0.01 wt.% based on the component (ii).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for stabilizing a resin composition for optical stereolithography, and more particularly to a resin composition for optical stereolithography containing a cationically polymerizable organic compound and an energy ray-sensitive cationic polymerization initiator. The present invention relates to a method for stabilizing an object.

[0002]

2. Description of the Related Art Optical three-dimensional modeling is disclosed in Japanese Unexamined Patent Publication No. 60-24 / 1985.
As described in Japanese Patent No. 7515, various resins having photocurability are put in a container, and a beam of an argon laser, a helium cadmium laser, a semiconductor laser or the like is irradiated from above on an arbitrary portion of the resin, and irradiation is performed. By performing continuously, the above-mentioned beam-irradiated portion of the resin is cured, thereby creating a target plane to form a cured layer, and then, the resin having the above-described photocurability on the cured layer Is further supplied for one layer, this is cured in the same manner as described above, and a lamination operation is performed to obtain a cured layer continuous with the above-described cured layer. By repeating this operation, the desired three-dimensional object is obtained. How to get.

Conventionally, as a resin used for the above-mentioned optical three-dimensional molding, there is a radically polymerizable resin composition, for example, Japanese Patent Application Laid-Open Nos.
JP-A-279436 discloses a resin composition for three-dimensional modeling mainly of a (meth) acrylic resin. Also,
JP-A-2-145616 discloses, for the purpose of reducing deformation, a resin for optical three-dimensional modeling containing liquid particles and fine particles having an apparent specific gravity difference of less than 0.2. Furthermore, Japanese Patent Application Laid-Open No.
No. 520 discloses a composition comprising an ethylenically unsaturated monomer, a photoinitiator and an insoluble latent radiation-polarizing substance, and JP-A-3-41126 discloses a composition comprising an ethylenically unsaturated monomer, a photoinitiator and a soluble latent polarizer. There have been reports of compositions comprising radiation polarizing materials. JP-A-4-85314 discloses a resin composition containing silicone urethane acrylate, a compound having a polyfunctional ethylenically unsaturated bond, and a polymerization initiator.

As another optical three-dimensional molding resin, a cationically polymerizable resin composition is known. For example, JP-A-1-213304 describes an invention characterized by containing an energy-ray-curable cationically polymerizable organic compound and an energy-ray-sensitive cationic polymerization initiator. JP-A-2-28261 discloses a low-shrinkage, high-resolution resin in which an energy-ray-curable radically polymerizable organic compound is partially incorporated into an energy-ray-curable cationically polymerizable organic compound. Further, JP-A-2-80423 discloses a resin composition in which a vinyl ether resin, an energy ray-sensitive cationic polymerization initiator, a radical curable resin, and an energy ray-sensitive radical polymerization initiator are blended with an epoxy resin. Have been. Furthermore, JP-A-2-75618 discloses an energy ray-curable cationic polymerizable organic compound,
An optical stereolithography resin composition comprising an energy ray-sensitive cationic polymerization initiator, an energy ray-curable radical polymerizable organic compound, an energy ray-sensitive radical polymerization initiator and a hydroxyl group-containing polyester is disclosed. .

[0005]

However, the radically polymerizable resin and the resin composition for optical three-dimensional modeling containing the same as a main component use radical polymerization, so that any resin (composition) is used. Even in this case, the curing is inhibited by oxygen, and the shrinkage of these resins at the time of curing is large, so that it is difficult to obtain a molded article having desired dimensions.

In addition, the cation-curable optical three-dimensional modeling resin described in JP-A-1-213304, JP-A-2-28261, and JP-A-2-75618 does not inhibit curing by oxygen. Since the curing proceeds even after light is blocked by the activator in the resin, post curing treatment is not required, and it has excellent characteristics that it is less deformed. You can get things.

[0007] However, the energy ray-sensitive cationic polymerization initiator generates a strong acid upon irradiation with energy rays and initiates the polymerization of the cationically polymerizable organic compound. In addition, strong acid is generated by scattered light, transmitted light, heat, and the like, which causes an increase in the viscosity of the resin composition during long-term use, and this increase in viscosity often makes it difficult to use the resin.

To solve this problem, US Pat.
No. 65792 discloses that 1 × 10 ^{−4 to} 0.5 g /
A method of adding a salt of a Group IA or Group IIA metal that dissolves in the range of 1 and a stabilization method using a weakly basic ion exchange resin are disclosed in JP-A-8-259614.

[0009] However, if the resin is IA group or II
The method of adding a salt of a Group A metal has a drawback that the salt reaches the portion irradiated with the energy rays, thereby inhibiting the intended curing of the resin.

In the method using an ion exchange resin,
Ion exchange resin swells in long-term use,
When an ion exchange resin is used by filling it in a filter, there are drawbacks such as poor workability and efficiency such as clogging due to swelling.

Accordingly, an object of the present invention is to provide an optical three-dimensional modeling method using a resin composition for optical three-dimensional modeling based on a cationically polymerizable organic substance and an energy-ray-sensitive cationic polymerization initiator. Without inhibiting
An object of the present invention is to provide a method for stabilizing a resin composition for optical three-dimensional modeling, which has no adverse effect on workability and efficiency and suppresses an increase in viscosity of the resin composition during long-term use.

[0012]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have reached the present invention. That is, the present invention provides a resin for optical stereolithography, which comprises contacting a resin composition for optical stereolithography containing a cationic polymerizable organic compound and an energy ray-sensitive cationic polymerization initiator with a basic ceramics adsorbent. This is a method for stabilizing the composition.

The cationically polymerizable organic compound used in the present invention refers to a substance which undergoes a polymerization or a crosslinking reaction by a cationic polymerization initiator activated by irradiation with energy rays.

Such substances include, for example, epoxy compounds, oxetane compounds, cyclic lactone compounds, cyclic acetal compounds, cyclic thioether compounds, spiro orthoester compounds, vinyl compounds (styrene, vinyl ether, etc.). Species or two or more can be used. Among them, epoxy compounds which are easy to obtain and convenient to handle are suitable.
As the epoxy compound, an aromatic epoxy compound, an alicyclic epoxy compound, an aliphatic epoxy compound and the like are suitable.

Specific examples of the alicyclic epoxy compound are obtained by epoxidizing a polyglycidyl ether of a polyhydric alcohol having at least one alicyclic ring or a compound containing cyclohexene or cyclopentene ring with an oxidizing agent. Compounds containing a cyclohexene oxide structure or a cyclopentene oxide structure are exemplified. For example, hydrogenated bisphenol A diglycidyl ether, 3,4-epoxycyclohexylmethyl-3,4-
Epoxycyclohexanecarboxylate, 3,4-epoxy-1-methylcyclohexyl-3,4-epoxy-1-methylhexanecarboxylate, 6-methyl-
3,4-epoxycyclohexylmethyl-6-methyl-
3,4-epoxycyclohexanecarboxylate,
3,4-epoxy-3-methylcyclohexylmethyl-
3,4-epoxy-3-methylcyclohexanecarboxylate, 3,4-epoxy-5-methylcyclohexylmethyl-3,4-epoxy-5-methylcyclohexanecarboxylate, 2- (3,4-epoxycyclohexyl-5, 5-spiro-3,4-epoxy) cyclohexane-metadioxane, bis (3,4-epoxycyclohexylmethyl) adipate, 3,4-epoxy-6
-Methylcyclohexylcarboxylate, methylenebis (3,4-epoxycyclohexane), dicyclopentadienediepoxide, ethylenebis (3,4-epoxycyclohexanecarboxylate), dioctyl epoxyhexahydrophthalate, di-2 epoxyhexahydrophthalate -Ethylhexyl and the like.

Commercial products that can be suitably used as the alicyclic epoxy compound include UVR-6100 and UVR-6.
105, UVR-6110, UVR-6128, UVR
-6200 (all manufactured by Union Carbide Co., Ltd.), Celloxide 2021, Celloxide 2021P, Celloxide 2081, Celloxide 2083, Celloxide 20
85, celoxide 2000, celoxide 3000,
Cyclomer A200, Cyclomer M100, Cyclomer M101, Epolide GT-301, Epolide GT-302, Epolide GT-401, Epolide G
T-403, ETHB, Eporide HD300 (or more,
Daicel Chemical Industries, Ltd.), KRM-2110, KR
M-2199 (all manufactured by Asahi Denka Kogyo KK) and the like.

Among the alicyclic epoxy compounds, epoxy compounds having a cyclohexene oxide structure are preferable in terms of curability (curing speed).

Specific examples of the aromatic epoxy compound include a polyhydric phenol having at least one aromatic ring and a polyglycidyl ether of an alkylene oxide adduct thereof, for example, bisphenol A, bisphenol F, or an alkylene oxide. Glycidyl ether of a compound to which an oxide is added, epoxy novolak resin, and the like can be given.

Specific examples of the aliphatic epoxy compound include polyglycidyl ethers of aliphatic polyhydric alcohols or alkylene oxide adducts thereof, polyglycidyl esters of aliphatic long-chain polybasic acids, glycidyl acrylate and vinyl glycidyl methacrylate. Examples include a homopolymer synthesized by polymerization, and a copolymer synthesized by vinyl polymerization of glycidyl acrylate or glycidyl methacrylate with another vinyl monomer. Representative compounds include 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, triglycidyl ether of glycerin, triglycidyl ether of trimethylolpropane, tetraglycidyl ether of sorbitol, and dipentaerythritol. One or two or more glycidyl ethers of polyhydric alcohols such as hexaglycidyl ether, diglycidyl ether of polyethylene glycol, diglycidyl ether of polypropylene glycol, and aliphatic polyhydric alcohols such as propylene glycol, trimethylolpropane, and glycerin. Polyglycidyl ether of polyether polyol obtained by adding alkylene oxide, diglycidyl ester of aliphatic long-chain dibasic acid It is below. Furthermore, monoglycidyl ethers of aliphatic higher alcohols, phenol, cresol, butylphenol, and monoglycidyl ethers of polyether alcohols obtained by adding alkylene oxide to these, glycidyl esters of higher fatty acids, epoxidized soybean oil, Examples thereof include octyl epoxy stearate, butyl epoxy stearate, and epoxidized polybutadiene.

Commercial products that can be suitably used as the aromatic and aliphatic epoxy compounds include Epicoat 80
1, Epicoat 828 (all, manufactured by Yuka Shell Epoxy), PY-306, 0163, DY-022 (all,
Ciba-Geigy), KRM-2720, EP-410
0, EP-4000, EP-4080, EP-490
0, ED-505, ED-506 (all manufactured by Asahi Denka Kogyo KK), Epolite M-1230, Epolite EH
DG-L, Epolite 40E, Epolite 100E, Epolite 200E, Epolite 400E, Epolite 7
0P, Epolite 200P, Epolite 400P, Epolite 1500NP, Epolite 1600, Epolite 80MF, Epolite 100MF, Epolite 400
0, Epolite 3002, Epolite FR-1500
(Kyoeisha Chemical Co., Ltd.), Suntote ST000
0, YD-716, YH-300, PG-202, PG
-207, YD-172, YDPN638 (all manufactured by Toto Kasei Co., Ltd.) and the like.

Specific examples of the oxetane compound include:
For example, the following compounds can be mentioned. 3-ethyl-3-hydroxymethyloxetane, 3- (meth) allyloxymethyl-3-ethyloxetane, (3-ethyl-3-oxetanylmethoxy) methylbenzene, 4-fluoro- [1- (3-ethyl-3) -Oxetanylmethoxy) methyl] benzene, 4-methoxy- [1- (3-ethyl-3-oxetanylmethoxy) methyl] benzene,
[1- (3-ethyl-3-oxetanylmethoxy) ethyl] phenyl ether, isobutoxymethyl (3-ethyl-3-oxetanylmethyl) ether, isobornyloxyethyl (3-ethyl-3-oxetanylmethyl)
Ether, isobornyl (3-ethyl-3-oxetanylmethyl) ether, 2-ethylhexyl (3-ethyl-3-oxetanylmethyl) ether, ethyldiethylene glycol (3-ethyl-3-oxetanylmethyl)
Ether, dicyclopentadiene (3-ethyl-3-oxetanylmethyl) ether, dicyclopentenyloxyethyl (3-ethyl-3-oxetanylmethyl) ether, dicyclopentenyl (3-ethyl-3-oxetanylmethyl) ether, tetrahydro Furfuril (3-
Ethyl-3-oxetanylmethyl) ether, tetrabromophenyl (3-ethyl-3-oxetanylmethyl)
Ether, 2-tetrabromophenoxyethyl (3-ethyl-3-oxetanylmethyl) ether, tribromophenyl (3-ethyl-3-oxetanylmethyl) ether, 2-tribromophenoxyethyl (3-ethyl-
3-oxetanylmethyl) ether, 2-hydroxyethyl (3-ethyl-3-oxetanylmethyl) ether, 2-hydroxypropyl (3-ethyl-3-oxetanylmethyl) ether, butoxyethyl (3-ethyl-3-oxetanylmethyl) ) Ether, pentachlorophenyl (3-ethyl-3-oxetanylmethyl) ether, pentabromophenyl (3-ethyl-3-oxetanylmethyl) ether, bornyl (3-ethyl-3-oxetanylmethyl) ether, 3,7-bis (3-oxetanyl) -5-oxa-nonane, 3,3 ′-(1,3
-(2-methylenyl) propanediylbis (oxymethylene)) bis- (3-ethyloxetane), 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, 1,2-bis [( 3-ethyl-3-oxetanylmethoxy) methyl] ethane, 1,3-bis [(3-ethyl-3-oxetanylmethoxy) methyl]
Propane, ethylene glycol bis (3-ethyl-3-
Oxetanylmethyl) ether, dicyclopentenylbis (3-ethyl-3-oxetanylmethyl) ether,
Triethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, tetraethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether,
Tricyclodecanediyl dimethylene (3-ethyl-3-
Oxetanylmethyl) ether, trimethylolpropane tris (3-ethyl-3-oxetanylmethyl) ether, 1,4-bis (3-ethyl-3-oxetanylmethoxy) butane, 1,6-bis (3-ethyl-3- Oxetanylmethoxy) hexane, pentaerythritol tris (3-ethyl-3-oxetanylmethyl) ether, pentaerythritol tetrakis (3-ethyl-3)
-Oxetanylmethyl) ether, polyethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol hexakis (3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol pentakis (3-ethyl-3- Oxetanylmethyl) ether, dipentaerythritol tetrakis (3-ethyl-3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol hexakis (3-ethyl-3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol pentakis (3- Ethyl-3-oxetanylmethyl) ether, ditrimethylolpropanetetrakis (3-ethyl-3-
Oxetanylmethyl) ether, EO-modified bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, PO-modified bisphenol A bis (3-ethyl-3
-Oxetanylmethyl) ether, EO-modified hydrogenated bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, PO-modified hydrogenated bisphenol A bis (3
-Ethyl-3-oxetanylmethyl) ether, EO-modified bisphenol F (3-ethyl-3-oxetanylmethyl) ether, and the like, and these can be used alone or in combination of two or more. These oxetane compounds are effective and preferable when used particularly when flexibility is required.

The energy ray-sensitive cationic polymerization initiator used in the present invention is a compound capable of releasing a substance that initiates cationic polymerization by irradiation with energy rays. Particularly preferred is a Lewis acid by irradiation. A resalt, which is an onium salt to be released, or a derivative thereof. Representative examples of such compounds include salts of cations and anions represented by the general formula [A] ^{m +} [B] ^m- .

The cation [A] ^{m +} is preferably an onium, and its structure is, for example, [(R ¹ ) _a
Q] ^{m +} .

Here, R ¹ has ¹ to 60 carbon atoms.
And is an organic group which may contain any number of atoms other than carbon atoms. a is an integer of 1 to 5. a R
Each ¹ is independent and may be the same or different. Also,
At least one is preferably an organic group having an aromatic ring as described above. Q is S, N, Se, Te, P,
It is an atom or an atomic group selected from the group consisting of As, Sb, Bi, O, I, Br, Cl, F, and N = N. When the valence of Q in the cation [A] ^{m +} is q,
It is necessary that the relationship of m = a−q hold (however, N = N is treated as valence 0).

The anion [B] ^m- is preferably a halide complex, and its structure is, for example, [LX
_b ] ^m- .

Here, L is a metal or metalloid which is the central atom of the halide complex, and B, P, As, Sb, Fe, Sn, Bi, Al,
Ca, In, Ti, Zn, Sc, V, Cr, Mn, Co
And so on. X is a halogen atom. b is an integer of 3 to 7. Further, the valence of L in the anion [B] ^{m- is} expressed as p
In this case, it is necessary that the relationship m = bp is satisfied.

Specific examples of the anion [LX _b ] ^{m− in} the above general formula include tetrafluoroborate (BF ₄ ) ⁻ , hexafluorophosphate (PF ₆ ) ⁻ , hexafluoroantimonate (SbF ₆ ) ⁻ , Fluoroarsenate (AsF ₆ ) ^- , hexachloroantimonate (SbCl
₆₎ ^-, and the like can be given.

The anion [B] ^m- is represented by [LX
_b-1 (OH)] Those having a structure represented by ^m- can also be preferably used. L, X and b are the same as above.

Other anions that can be used
As perchlorate ion (ClO _Four)^-, Trifluoro
Methyl sulfite ion (CF_ThreeSO_Three)^-, Fluorosulfo
Acid ion (FSO_Three)^-, Toluenesulfonic acid anion
, Trinitrobenzenesulfonate anion, tetrakis
(Pentafluorophenyl) borate
Can be.

In the present invention, among such onium salts, it is particularly effective to use the following aromatic onium salts (a) to (c). Among these, one kind can be used alone, or two or more kinds can be used in combination.

(A) Aryldiazonium salts such as phenyldiazonium hexafluorophosphate, 4-methoxyphenyldiazonium hexafluoroantimonate and 4-methylphenyldiazonium hexafluorophosphate (b) diphenyliodonium hexafluoroantimonate, di (4-methylphenyl) ) Diaryliodonium salts such as iodonium hexafluorophosphate, di (4-tert-butylphenyl) iodonium hexafluorophosphate, tolylcumyliodonium tetrakis (pentafluorophenyl) borate, etc. (c) Triphenylsulfonium hexafluoroantimonate, -Methoxyphenyl) sulfonium hexafluorophosphate, diphenyl-4-thiophenoxyphene Rusulfonium hexafluoroantimonate, diphenyl-4-thiophenoxyphenylsulfonium hexafluorophosphate, 4,4'-bis (diphenylsulfonio) phenylsulfide-bis-hexafluoroantimonate, 4,4'-bis (diphenylsulfonium) Fonio) phenylsulfide-bis-hexafluorophosphate, 4,4′-bis [di (β-hydroxyethoxy) phenylsulfonio] phenylsulfide-bis-hexafluoroantimonate, 4,4′-bis [di ( β-hydroxyethoxy) phenylsulfonio] phenylsulfide-bis-hexafluorophosphate, 4- [4 ′-(benzoyl)
Phenylthio] phenyl-di- (4-fluorophenyl) sulfonium hexafluoroantimonate, 4-
[4 '-(benzoyl) phenylthio] phenyl-di-
Triarylsulfonium salts such as (4-fluorophenyl) sulfonium hexafluorophosphate are preferred.

Other preferred examples are (η
⁵ -2,4-cyclopentadiene-1-yl) [(1,
2,3,4,5,6-η)-(1-methylethyl) benzene] -iron-hexafluorophosphate and other iron-arene complexes, tris (acetylacetonato) aluminum, tris (ethylacetonatoacetate) And mixtures of aluminum complexes such as aluminum and tris (salicylaldehyde) aluminum with silanols such as triphenylsilanol. Among these, it is preferable to use an aromatic iodonium salt, an aromatic sulfonium salt, or an iron-arene complex from the viewpoint of practical use and light sensitivity.

The resin composition for optical stereolithography used in the present invention contains the above-mentioned cationically polymerizable organic compound and an energy ray-sensitive cationic polymerization initiator.

The use ratio of the energy ray-sensitive cationic polymerization initiator to the cationic polymerizable organic compound is not particularly limited, and may be used at a generally normal use ratio within a range not to impair the object of the present invention. For example, the energy-sensitive cationic polymerization initiator may be 0.05 to 10 parts by weight, preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the cationically polymerizable organic compound. If the amount is too small, curing tends to be insufficient, and if it is too large, the strength of the cured product may be adversely affected.

Basic ceramics used in the present invention
As the adsorbent, for example, SnO, MgO, MgO-A
l_TwoO_Three, ZnO-ZrO_Two, MgO-TiO_Two, SiO_Two
-CaO-MgO, SiO_Two-Al_TwoO_Three, SiO_Two-Mg
O, SiO_Two-SrO, SiO_Two-BaO, ZnO-Si
O_Two, TiO_Two-ZrO_Two, Al_TwoO_Three-TiO_Two, SiO_Two
-ZrO_Two, Al_TwoO_Three-ZrO_Two, SiO_Two-TiO_Two, M
oO_Three-SiO_Two, MoO_Three-Al_TwoO_Three, 1.25Mg
(OH)_Two・ Al (OH)_Three・ XCO_Three・ YH_TwoO, Mg₆
Al_Two(OH)₁₆CO_Three・ 4H_TwoO, 2MgO.6SiO_Two
・ XH_TwoO, Mg _4.5Al_Two(OH)₁₃CO_Three・ 3.5H_Two
O, Mg_0.7Al_0.3O_1.15And the like. Ma
As a commercial product, KYOWARD 10
0, kyoword 300, kyoword 300S, kyo
-Word 500, kyoword 500sh, kyowa
C 600, KYOWARD 600S, KYOWARD 100
0, KYOWARD 2000 (Kyowa Chemical Industry Co., Ltd.)
Manufactured).

These basic ceramic adsorbents can be used in the form of powder, granules, plates and the like.

The amount of the basic ceramics adsorbent used varies depending on the amount of unintended energy rays such as scattered light, transmitted light, heat, etc., which increase the viscosity of the resin composition for stereolithography. It may be about 0.01% by weight or more based on the sensitive cationic polymerization initiator.

In the present invention, these basic ceramics adsorbents are brought into contact with the above-mentioned resin composition for optical three-dimensional modeling, but the contact method is not particularly limited, and the resin composition for optical three-dimensional modeling is used. Any method may be used as long as it does not impair the workability and efficiency of the optical three-dimensional modeling that is the use of the object, and the contact may be performed before or during the optical three-dimensional modeling.

For example, as an example, there is a method in which a basic ceramics adsorbent is submerged in a resin tank containing a resin composition for optical three-dimensional modeling. In this case, the basic ceramics adsorbent is used. When uniformly dispersed in the optical three-dimensional modeling resin composition, it impairs the intended curing during the optical three-dimensional modeling. Is preferably located at

In the present invention, the basic ceramics adsorbent and the resin composition for optical three-dimensional modeling need not always be in constant contact. For example, each time a rise in viscosity is observed, the basic ceramics adsorbent is not adsorbed. A method of passing a resin composition for optical three-dimensional modeling through a filter filled with an agent to suppress a further increase in viscosity can also be exemplified.

Although not essential, the resin composition for stereolithography used in the present invention may optionally contain a photosensitizer and the like. For example, by using a photosensitizer such as anthracene derivative and pyrene derivative together,
As compared with the case where these are not blended, the curing speed when performing the optical three-dimensional molding is further improved, which is preferable as a resin composition.

Although not essential, the resin composition for stereolithography used in the present invention may optionally contain an organic compound having two or more hydroxyl groups in one molecule. For example, by blending an organic compound having two or more hydroxyl groups in one molecule such as a polyhydric alcohol, a hydroxyl group-containing polyether, a hydroxyl group-containing polyester, and a polyhydric phenol, the mechanical strength of the molded article can be increased.

Examples of polyhydric alcohols include ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane, glycerin, pentaerythritol, dipentaerythritol, 1,3-butanediol, 1,4-butanediol, 6-hexanediol and the like can be mentioned.

The hydroxyl group-containing polyether is a compound obtained by adding one or more alkylene oxides to one or more polyhydric alcohols or phenols. Examples of the polyhydric alcohol used for this include ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane, glycerin, pentaerythritol, dipentaerythritol, 1,3-butanediol, 1,4-butanediol, , 6-hexanediol and the like. Examples of the polyhydric phenol include bisphenol A, bisphenol F, phenol novolak resin, cresol novolak resin, and the like. Also, as an example of the alkylene oxide. Butylene oxide, propylene oxide, ethylene oxide and the like can be mentioned.

The hydroxyl group-containing polyester is a hydroxyl group-containing polyester obtained by an esterification reaction of one or more polyhydric alcohols or phenols with one or more monobasic acids or polybasic acids. And a hydroxyl group-containing polyester obtained by an esterification reaction of one or more polyhydric alcohols or phenols with one or more lactones. Examples of the polyhydric alcohol and the polyhydric phenol include the same as those described above. Examples of the monobasic acid include formic acid, acetic acid, butyric acid, and benzoic acid.
Examples of the polybasic acid include adipic acid, terephthalic acid, trimellitic acid and the like. Examples of the lactones include β-propiolactone, γ-butyrolactone, ε-caprolactone, and the like.

The polyhydric phenol is a compound containing two or more hydroxyl groups directly bonded to an aromatic ring in one molecule.
The same as those described above can be used.

The resin composition for optical three-dimensional modeling used in the present invention may contain a thermoplastic polymer compound as required, though not essential. It is a polymer compound that is liquid or solid at room temperature and is uniformly mixed with the resin composition at room temperature.

Representative examples of the thermoplastic polymer compound include polyester, polyvinyl acetate, polyvinyl chloride, polybutadiene, polycarbonate, polystyrene, polyvinyl ether, polyvinyl butyral, polyacrylate, polymethyl methacrylate, polybutene, and styrene. Butadiene block coprimer hydrogenated product can be exemplified. Further, those obtained by introducing a functional group such as a hydroxyl group, a carboxyl group, a vinyl group, or an epoxy group into these thermoplastic polymer compounds can also be used.
For such a thermoplastic polymer compound, a desirable number average molecular weight for the present invention is 10,000 to 500,000, and a more preferred number average molecular weight is 5,000 to 1,000.
00. Although it is not impossible to use even if it is outside this range, if the molecular weight is too low, the effect of improving the strength is not sufficiently obtained, and if the molecular weight is too high, the viscosity of the resin composition becomes high, and the optical It cannot be said that it is preferable as a resin composition for three-dimensional modeling.

The resin composition for optical three-dimensional modeling used in the present invention, which contains a thermoplastic polymer compound, has a higher mechanical strength than the one containing no such compound. The physical properties further increase, and this is preferable as a resin composition for optical three-dimensional modeling.

Although not essential, the resin composition for stereolithography used in the present invention may optionally contain a radically polymerizable organic substance and an energy-ray-sensitive radical polymerization initiator.

The radically polymerizable organic substance is a radically polymerizable organic compound which is polymerized or cross-linked by irradiation with an energy ray in the presence of an energy-sensitive radical polymerization initiator, and preferably at least one or more per molecule. Is a compound having an unsaturated double bond.

Examples of such compounds include acrylate compounds, methacrylate compounds, allyl urethane compounds, unsaturated polyester compounds, styrene compounds and the like.

Among such radically polymerizable organic compounds, compounds having a (meth) acryl group are preferable because they are easy to synthesize and obtain and easy to handle. For example, epoxy (meth) acrylate, urethane (meth) acrylate, polyester (meth) acrylate, polyether (meth) acrylate, (meth) acrylate of alcohols, and the like can be given.

Here, the epoxy (meth) acrylate is, for example, an epoxy obtained by reacting a conventionally known aromatic epoxy resin, alicyclic epoxy resin, aliphatic epoxy resin or the like with (meth) acrylic acid. (Meth) acrylate.

Of these epoxy (meth) acrylates, particularly preferred is a (meth) acrylate of an aromatic epoxy resin, and a polyglycidyl of a polyhydric phenol having at least one aromatic nucleus or an alkylene oxide adduct thereof. Epoxy (meth) acrylate obtained by reacting ether with (meth) acrylic acid.

For example, an epoxy (meth) acrylate or epoxy novolak resin obtained by reacting glycidyl ether obtained by reacting bisphenol A or an alkylene oxide adduct thereof with epichlorohydrin with (meth) acrylic acid is used. Epoxy (meth) acrylate obtained by reacting (meth) acrylic acid can be exemplified.

Preferred urethane (meth) acrylates include urethane (meth) acrylates obtained by reacting one or more hydroxyl group-containing polyesters or hydroxyl group-containing polyethers with hydroxyl group-containing (meth) acrylates and isocyanates. And acrylates and urethane (meth) acrylates obtained by reacting hydroxyl group-containing (meth) acrylic acid with isocyanates.

Preferred as the hydroxyl group-containing polyester used here is a hydroxyl group-containing polyester obtained by reacting one or more polyhydric alcohols with one or more polybasic acids, Examples of the polyhydric alcohol include 1,3-butanediol,
4-butanediol, 1,6-hexanediol, diethylene glycol, triethylene glycol, neopentyl glycol, polyethylene glycol, polypropylene glycol, polybutylene glycol, trimethylolpropane, glycerin, pentaerythritol, dipentaerythritol, and the like. it can. Examples of the polybasic acid include adipic acid, terephthalic acid, phthalic anhydride, trimellitic acid and the like.

The hydroxyl group-containing polyether is preferably a hydroxyl group-containing polyether obtained by adding one or more alkylene oxides to a polyhydric alcohol. The same thing can be illustrated. Examples of the alkylene oxide include ethylene oxide, propylene oxide, butylene oxide and the like.

Preferred as the hydroxyl group-containing (meth) acrylic acid ester are hydroxyl group-containing (meth) acrylic acid esters obtained by an esterification reaction between a polyhydric alcohol and (meth) acrylic acid. The same compounds as those described above can be exemplified.

Among the hydroxyl group-containing (meth) acrylic acids, a hydroxyl group-containing (meth) acrylate obtained by an esterification reaction between a dihydric alcohol and (meth) acrylic acid is particularly preferred. A) acrylates.

As the isocyanates, compounds having at least one isocyanate group in the molecule are preferable, and divalent isocyanate compounds such as tolylene diisocyanate, hexamethylene diisocyanate and isophorone diisocyanate are particularly preferable.

Preferred as the polyester (meth) acrylate is a polyester (meth) acrylate obtained by reacting a hydroxyl group-containing polyester with (meth) acrylic acid. Preferred as the hydroxyl group-containing polyester used here is a hydroxyl group-containing polyester obtained by an esterification reaction of one or more polyhydric alcohols with one or more monobasic acids or polybasic acids. As the polyhydric alcohol, those similar to the aforementioned compounds can be exemplified. As a monobasic acid,
For example, formic acid, acetic acid, butyric acid, benzoic acid and the like can be mentioned. Examples of the polybasic acid include adipic acid, terephthalic acid, phthalic anhydride, trimellitic acid and the like.

Preferred examples of the polyether (meth) acrylate include a hydroxyl group-containing polyether and (meth)
It is a polyether (meth) acrylate obtained by reacting with acrylic acid. Preferred as the hydroxyl group-containing polyether to be used here is one of polyhydric alcohols.
A hydroxyl-containing polyether obtained by adding one or more alkylene oxides,
Examples of the polyhydric alcohol include the same compounds as those described above. Examples of the alkylene oxide include ethylene oxide, propylene oxide, butylene oxide and the like.

Preferred as (meth) acrylic acid esters of alcohols are aromatic or aliphatic alcohols having at least one hydroxyl group in the molecule, and an alkylene oxide adduct thereof reacted with (meth) acrylic acid. (Meth) acrylate obtained by, for example, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, isoamyl (meth) acrylate, lauryl (meth) acrylate, Stearyl (meth) acrylate, isooctyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isobonyl (meth) acrylate, benzyl (meth) acrylate, 1,3-butanediol di (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) acrylate, trimethylolpropane tri (meth) acrylate, ethylene oxide-modified trimethylolpropane tri (meth) acrylate, propylene oxide-modified tri Examples include methylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and ε-caprolactone-modified dipentaerythritol hexa (meth) acrylate.

It is preferable that at least 50 parts by weight of the radical polymerizable organic compound is a compound having a (meth) acryl group in the molecule.

An energy ray-sensitive radical polymerization initiator is a compound capable of initiating radical polymerization by irradiation with energy rays, and a ketone compound such as an acetophenone compound, a benzyl compound, a benzophenone compound or a thioxanthone compound. Is preferred.

Examples of the acetophenone-based compound include, for example, diethoxyacetophenone, 2-hydroxy-2-
Methyl-1-phenylpropan-1-one, 4'-isopropyl-2-hydroxy-2-methylpropiophenone, 2-hydroxymethyl-2-methylpropiophenone, 2,2-dimethoxy-1,2-diphenyl Ethane
1-one, p-dimethylaminoacetophenone, p-tert-butyldichloroacetophenone, p-tert-butyltrichloroacetophenone, p-azidobenzalacetophenone, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1- [4- ( Methylthio) phenyl] -2-morpholinopropanone-1, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, Benzoin-n-butyl ether, benzoin isobutyl ether and the like can be mentioned.

Examples of the benzyl compound include benzyl, anisyl and the like.

Examples of the benzophenone compound include, for example, benzophenone, methyl o-benzoylbenzoate,
Michler's ketone, 4,4'-bisdiethylaminobenzophenone, 4,4'-dichlorobenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide and the like can be mentioned.

Examples of the thioxanthone compound include thioxanthone, 2-methylthioxanthone,
Ethylthioxanthone, 2-chlorothioxanthone, 2
-Isopropylthioxanthone, 2,4-diethylthiooxanthone and the like.

One or more of these energy ray-sensitive radical polymerization initiators can be used in combination according to the desired performance.

[0073]

Examples of the present invention will be described below.

As the resin, an epoxy-based resin for stereolithography, AdecalaScure HS-673S, was used. The resin is irradiated with light from a chemical lamp while stirring to reduce the viscosity to 45.
The viscosity was increased to 0 cps / 25 ° C. This resin is 5
0 g, and as a stabilizer, Kyoward 500 (Mg ₆ Al ₂ (OH)
₁₆ CO ₃ .4H ₂ O), Kyoward 600S (2MgO)
· 6SiO ₂ · xH ₂ O) was placed 1g respectively, it was 24 hours warmed sufficiently 80 ° C. After stirring. In addition, the system which does not add a stabilizer as a blank was tested similarly. The results were as shown in Table 1.

[0075]

[Table 1]

As is apparent from the results, by bringing the optical three-dimensional modeling resin composition into contact with the basic ceramics adsorbent, it is possible to effectively suppress the increase in the viscosity of the optical three-dimensional modeling resin composition. it can.

The following test was conducted to confirm that the stabilizer did not adversely affect the curability of the resin.

Resin AdecalaScure HS-67 for Stereolithography
1% by weight of a stabilizer was added to 3S, heated at 80 ° C. for 24 hours, and allowed to stand to settle the stabilizer. For the supernatant resin, see Paul F. The sensitivity of the resin was measured according to the window pane method described by Jacobs in the basics of high-speed three-dimensional molding (Nikkei BP Publishing Center). The results were as shown in Table 2.

[0079]

[Table 2]

As is apparent from the results, it is found that the optical three-dimensional modeling resin composition brought into contact with the basic ceramics adsorbent is not adversely affected at all.

[0081]

The effects of the present invention are as follows. In an optical stereolithography method using an optical stereolithography resin composition based on a cationically polymerizable organic material and an energy ray-sensitive cationic polymerization initiator, An object of the present invention is to provide a method for stabilizing a resin composition for optical three-dimensional modeling, which does not inhibit curing, has no adverse effect on workability and efficiency, and suppresses an increase in viscosity of the resin composition during long-term use.

Continuation of the front page F term (reference) 4F213 AA44 AD04 WA25 WL02 WL12 WL23 WL25 WL96 4J002 CD011 CD021 CD051 CD091 CD101 DD047 DD077 DE197 EE038 EL056 EN068 EV187 EV237 EV308 EW047 EW177 EY017 EY027 GP00

Claims (1)

[Claims] 1. A resin for optical stereolithography, comprising: contacting a resin composition for optical stereolithography containing a cationically polymerizable organic compound and an energy ray-sensitive cationic polymerization initiator with a basic ceramic adsorbent. A method for stabilizing a composition.