JP2525216B2 - Resin composition for optical three-dimensional modeling - Google Patents

Description

TECHNICAL FIELD The present invention relates to a resin composition for optical three-dimensional modeling, and particularly to a resin composition having a low viscosity, a small volume shrinkage ratio upon curing, and an excellent flexibility after curing. The present invention relates to a resin composition for optical three-dimensional modeling.

[Conventional technology]

In recent years, Japanese Patent Application Laid-Open No. Sho 60-247515 has proposed a method of forming a three-dimensional structure having a desired shape by selectively supplying light energy required for curing to a photocurable liquid material.
A similar method or an improved technique thereof is disclosed in US Pat.
No. 575,330 (JP-A-62-35966) and JP-A-62-1014.
It is also disclosed in the 08 gazette and the like. A typical example of this three-dimensional modeling method is to obtain a cured layer by selectively irradiating an ultraviolet laser, for example, on the liquid surface of the photocurable resin placed in a container so that a cured layer having a desired pattern can be obtained. Then, one layer of the photo-curable resin is supplied onto the cured layer, and then, similarly to the above, by selectively irradiating with light, a laminated operation of obtaining a cured layer continuous with the cured layer is repeated. The final method is to obtain a desired three-dimensional object.

This three-dimensional modeling method has attracted attention because it can easily obtain a desired modeled object in a short time even when the shape of the modeled object to be manufactured is complicated.

Conventionally, as a photocurable liquid substance used in this three-dimensional modeling method, modified polyurethane methacrylate, oligoester acrylate, urethane acrylate, epoxy acrylate, photosensitive polyimide, aminoalkyd, etc. have been mentioned. (JP-A-60-247515).

[Problems to be solved by the invention]

By the way, in the above-described three-dimensional modeling method, in order to form a three-dimensional molded article with high dimensional accuracy, the curable liquid substance used is required to have characteristics such as low viscosity and low volumetric shrinkage rate during curing. In addition, the flexibility after curing is further required depending on the application of the three-dimensional molded item.

Therefore, an object of the present invention is to provide a resin composition for optical three-dimensional modeling, which has a low viscosity, a small volume shrinkage ratio upon curing, and a cured product excellent in flexibility.

[Means for solving problems]

The present invention provides an optical system comprising (A) a monomer compound containing an ethylenically unsaturated compound having a cross-linked alicyclic hydrocarbon group, (B) a polymer having an ethylenically unsaturated group, and (C) a polymerization initiator. A three-dimensional modeling resin composition is provided.

In the present invention, the optical three-dimensional modeling method in which the above resin composition is used is to supply energy necessary for curing by selectively irradiating a curable liquid substance with light at a specific location, thereby producing a three-dimensional structure having a desired shape. A method of obtaining a modeled object. The curable liquid substance used here may be photocurable which is cured by ultraviolet rays, visible light or the like, or may be thermosetting which is cured by infrared rays. Therefore, as the light used for irradiation, as mentioned above, ultraviolet rays, visible light, and infrared rays can be mentioned. Further, the method of selectively irradiating light to a specific portion of the curable liquid substance is not limited, for example, laser light, a lens, a focused light obtained using a mirror or the like, a method of irradiating a specific portion, An example is a method of irradiating a curable liquid substance with unfocused light through a mask having a fixed pattern so that only a specific portion is irradiated. Further, the specific portion to be irradiated with light may be the liquid surface of the curable liquid substance contained in the container, the surface in contact with the side wall or the bottom wall of the container, or the liquid. To irradiate the liquid surface of the curable liquid substance or the contact surface with the vessel wall, light can be applied from the outside directly or through a transparent vessel wall. Can be illuminated by a light guide, such as an optical fiber.

In this optical three-dimensional molding method, usually, after a desired specific portion is cured, the irradiated position is continuously and stepwise moved from the cured portion to the uncured portion adjacent thereto, thereby curing the cured portion. Can be grown into a desired three-dimensional shape. There are various methods of moving the irradiated position, and examples thereof include a method of moving one or more of the light source, the container, and the cured portion, or a method of adding an uncured liquid curable substance to the container.

The above-mentioned optical three-dimensional modeling method includes, for example, JP-A-60-24.
7515, 62-101408, 62-35966, "mold technology"
In addition to the methods described in Volume 2, No. 9, pages 72 to 73, all methods included in the above definition are included.

The resin composition of the present invention is used as a curable liquid substance in the above-mentioned optical three-dimensional modeling method.

The monomer compound which is the component (A) used in the resin composition of the present invention includes an ethylenically unsaturated compound having a crosslinked alicyclic hydrocarbon group (hereinafter, abbreviated as "crosslinked ethylenically unsaturated compound"). Be done.

Specific examples of the crosslinked alicyclic hydrocarbon group include an isobornyl group, a dicyclopentenyl group and a bornyl group. Examples of the crosslinked ethylenically unsaturated compound having these crosslinked alicyclic hydrocarbon groups include acrylate, methacrylate, oxyethyl acrylate and oxyethyl methacrylate of these crosslinked alicyclic hydrocarbon groups. Examples of isobornyl acrylate, isobornyl methacrylate, dicyclopentenyl acrylate, dicyclopentenyl methacrylate, bornyl acrylate, bornyl methacrylate, isobornyloxyethyl acrylate, isobornyloxyethyl methacrylate, dicyclopentenyloxyethyl acrylate And dicyclopentenyloxyethyl methacrylate. Among these, preferable crosslinked ethylenically unsaturated compounds include isobornyl acrylate, isobornyl methacrylate, dicyclopentenyl acrylate, and dicyclopentenyl methacrylate.

The monomer compound as the component (A) may contain, in addition to the above-mentioned crosslinked ethylenically unsaturated compound, other monomer compounds, if necessary, for the curing rate of the resin composition of the present invention, mechanical properties after curing, and the like. It can be used in combination within a range where there is no harmful effect. Other monomer compounds that can be used in combination are compounds having good compatibility with the crosslinked ethylenically unsaturated compound and having an ethylenically unsaturated group, and the viscosity of the resin composition of the present invention and the mechanical properties of the cured product. Can be adjusted. As the other monomer compounds, both monofunctional compounds and polyfunctional compounds are used. When a cured product having a relatively low elastic modulus is desired, a monofunctional compound is mainly used, but the elastic modulus of the cured product can be adjusted by using a polyfunctional compound in an appropriate ratio. The monofunctional compound and the polyfunctional compound are not particularly limited, and the following compounds can be exemplified.

Monofunctional compounds: 2-hydroxyethyl acrylate, 2
-Hydroxypropyl acrylate, tetrahydrofurfuryl acrylate, butoxyethyl acrylate, ethyldiethylene glycol acrylate, 2-ethylhexyl acrylate, phenoxyethyl acrylate,
Dicyclopentadiene acrylate, polyethylene glycol acrylate, polypropylene glycol acrylate, methyltriethylene glycol acrylate,
Diethylaminoethyl acrylate, 7-amino-3,7
-Acrylic compounds such as dimethyloctyl acrylate, methacrylic compounds such as 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, polypropylene glycol methacrylate, diethylaminoethyl methacrylate, vinylpyrrolidone, vinylphenol, acrylamide, vinyl acetate, vinyl ether, styrene.

Polyfunctional compounds: trimethylolpropane triacrylate, ethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate. , Dicyclopentenyl diacrylate, polyester diacrylate, diallyl adipate, diallyl phthalate, triallyl isocyanurate, bisphenol A glycidyl ether adducts at both ends.

Among these, preferred are acrylates whose functional group is an acryloyl group from the viewpoint of curing speed and compatibility.

The proportion of the crosslinked ethylenically unsaturated compound in the monomer compound as the component (A) is preferably 2% by weight or more, and particularly preferably 10% by weight or more. If this proportion is less than 2% by weight, the viscosity of the composition, the curing rate, and the mechanical properties after curing, such as Young's modulus, will deteriorate.

Further, the total amount of the monomer compound as the component (A) used is preferably 5 to 80% by weight, and particularly preferably 10 to 60% by weight, based on the resin composition of the present invention.

The type of the polymer having an ethylenically unsaturated group which is the component (B) used in the resin composition of the present invention is not particularly limited, and a polymer having an ethylenically unsaturated group such as an acryloyl group or a methacryloyl group is used. You can

Examples of the polymer as the component (B) that can be used in the present invention include polymers having an ester skeleton, an ether skeleton, a urethane skeleton, an epoxy skeleton and the like and having an ethylenically unsaturated group.

Specific examples include polymers obtained by reacting diol compounds such as polyether diols, polyester diols, polycaprolactone diols, polycarbonate diols, and polyepoxy diols with diisocyanate compounds and compounds having an ethylenically unsaturated group. You can

Here, examples of the polyether diol include polyoxyethylene diol, polyoxypropylene diol, and polyoxytetramethylene diol.

Examples of the polyester diol include polyhydric alcohols such as ethylene glycol, propylene glycol, tetramethylene glycol, 1,6-hexanediol, neopentyl glycol, 1,4-cyclohexanedimethanol and phthalic acid, isophthalic acid, terephthalic acid, maleic acid. Examples thereof include polyester diols obtained by reacting an acid, a polybasic acid such as fumaric acid, adipic acid, and sebacic acid.

The polycaprolactone diol can be obtained by reacting ε-caprolactone with a divalent diol such as ethylene glycol, tetramethylene glycol, 1,6-hexanediol, neopentyl glycol or 1,4-butanediol. Polycaprolactone diol may be mentioned, and as the polycarbonate diol, DN-
980 (Nippon Polyurethane Co., Ltd.), DN-981 (same), DN
-982 (same), DN-983 (same), PC-8000 (manufactured by PPG, USA) and the like.

Further, examples of the polyepoxy diol include diols obtained by reacting bisphenol A or an alkylene oxide adduct of bisphenol A with epichlorohydrin to form diglycidyl ether, and reacting this diglycidyl ether with (meth) acrylic acid.

Further, as the diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 1,3-xylene diisocyanate, 1,4-xylene diisocyanate, 1,5-naphthalene diisocyanate,
p-Phenylene diisocyanate, 3,3'-dimethyl-
4,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, 3,3'-dimethylphenylene diisocyanate, 4,4'-biphenylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, methylenebis (4-cyclohexyl Isocyanate), hydrogenated diphenylmethane diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, bis (2-isocyanatoethyl) fumarate, 6-
Isopropyl-1,3-phenyl diisocyanate, 4
Examples thereof include diphenylpropane diisocyanate and lysine diisocyanate.

Further, examples of the compound having an ethylenically unsaturated group include an acrylic or methacrylic compound having a hydroxyl group, an acid halide group or an epoxy group.

Examples of the acrylic or methacrylic compound having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxyoctyl (meth) acrylate, pentaerythritol tri (meth) acrylate, and glycerin diester. (Meth) acrylate, dipentaerythritol monohydroxypenta (meth) acrylate, 1,4-butanediol mono (meth) acrylate, 4-hydroxycyclohexyl (meth) acrylate, 1,6-hexanediol mono (meth) acrylate, neo Pentyl glycol mono (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolethanedi (meth) arylate, the following structural formula: (In the formula, R ⁴ is H or CH ₃ and n is 1 to 5), and further contains a glycidyl group such as alkyl glycidyl ether, aryl glycidyl ether, glycidyl (meth) acrylate and the like. The compound obtained by the addition reaction of a compound and (meth) acrylic acid can also be mentioned.

Examples of the acrylic or methacrylic compound having an acid halide group include acrylic acid halides such as acrylic acid chloride, methacrylic acid chloride, acrylic acid bromide, and methacrylic acid bromide, and methacrylic acid halides.

Examples of the acrylic or methacrylic compound having an epoxy group include glycidyl ester of acrylic acid or methacrylic acid.

Furthermore, polymers obtained by introducing an ethylenically unsaturated group into a polyether, polyester, or polyepoxy resin other than the above can also be used.

Further, the polymer having an ethylenically unsaturated group as the component (B) preferably has a number average molecular weight of 300 to 7,000, particularly preferably 500 to 5,000.

It is preferable that the polymer as the component (B) is added to the resin composition of the present invention in an amount of 5 to 90% by weight, particularly 20 to 80% by weight. When the proportion of the polymer is less than 5% by weight, the volumetric shrinkage of the composition at the time of curing, the mechanical properties of the cured product, and the like tend to be deteriorated. Further, when the proportion of the polymer exceeds 90% by weight, the viscosity of the obtained resin composition increases, and it becomes difficult to produce an optical three-dimensional model.

The type of the weight initiator which is the component (C) used in the composition of the present invention is not particularly limited, and various photopolymerization initiators and thermal polymerization initiators can be used. Specifically, the following compounds are used. Can be illustrated.

Photoinitiator: 2,2-dimethoxy-2-phenylacetophenone, acetophenone, benzophenone, xanthone, fluorenone, benzaldehyde, fluorene, anthraquinone, triphenylamine, carbazole, 3
-Methylacetophenone, 4-chlorobenzophenone,
4,4'-dimethoxybenzophenone, 4,4'-diaminobenzophenone, Michler's ketone, benzoin propyl ether, acetophenone diethyl ketal, benzoin ethyl ether, benzyl dimethyl ketal, 1- (4
-Isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 2-hydroxy-2-methyl-
1-phenylpropan-1-one, thioxanthone compounds and the like.

These photopolymerization initiators are used alone or in combination of two or more, and if necessary, a sensitizer (radiation polymerization accelerator) such as an amine compound is used in combination.

Thermal polymerization initiator: benzoin peroxide, t-butylperoxybenzoate, dicumyl peroxide,
2,4-dichlorohenzoyl peroxide, t-butyl peroxide, azobisisobutyronitrile and the like.

The amount of the polymerization initiator which is the component (C) is usually
0.1 to 5% by weight, preferably 1 to 5 in the resin composition of the present invention
It is 3% by weight.

The resin composition of the present invention may contain a leveling agent, a surfactant, an organic silicon compound, an inorganic filler, etc., if necessary.

The resin composition of the present invention is prepared by mixing the above-mentioned (A), (B) and (C), or adding other components as necessary. Not limited.

The light used when obtaining a molded article by an optical three-dimensional molding method using the resin composition of the present invention is selected depending on whether the composition is photocurable or thermosetting. Ultraviolet rays, visible light, infrared rays, etc. are used.

The optical three-dimensional modeling method in which the resin composition of the present invention is used is as described above, and as a typical method thereof,
This composition which is liquid is selectively irradiated with light so as to obtain a cured layer having a desired pattern to form a cured layer, and then the uncured composition layer adjacent to the cured layer is similarly formed. This is a method of irradiating light to newly form a cured layer continuous with the above-mentioned cured layer, and repeating the lamination operation to finally obtain a three-dimensional shaped object to be aimed at.

More specific embodiments of the above method include the following examples.

After the first cured layer is formed, an uncured composition for the next cured layer is additionally supplied onto the obtained first cured layer,
A method of repeating the operation of irradiating light and forming the next cured layer.

Immersing the bottom plate in the composition by the depth of the first hardened layer,
After the first hardened layer is formed, the bottom plate is further sunk by a depth of one layer to allow one layer of the uncured composition to flow into the first hardened layer and further irradiate with light. A method of repeating the operation of forming the next cured layer.

A box having a transparent bottom plate is submerged in the composition contained in the container, and the composition layer formed in the gap between the bottom plate and the bottom surface of the container is made to have the same thickness as the first cured layer. And irradiating the composition layer with light through the transparent bottom plate of the box,
After forming the cured layer of, the box is lifted to allow the composition to flow into the gap between the first cured layer and the transparent bottom plate of the box,
A method of repeating the operation of irradiating light similarly and forming the next cured layer.

The plate is submerged in a composition contained in a container having a transparent bottom, and the composition layer formed in the gap between the plate and the bottom surface of the container is made to have the same thickness as the first cured layer. Then, the composition layer is irradiated with light through the transparent bottom of the container to form a first cured layer, and then the plate is raised by a thickness of one layer to form a uncured composition for one layer. Is introduced into the gap between the first hardened layer and the plate, and then light is irradiated in the same manner as above to form the next hardened layer.

〔Example〕

Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited thereto.

Example 1 In a reaction vessel equipped with a stirrer, 38.4 g of isobonyl acrylate, 57.6 g of diepoxy acrylate polymer (Kyoeisha Oil and Fat Chemical Co., Ltd. epoxy ester 3002A, number average molecular weight 580), photopolymerization initiator ( Ciba Geigy Co., Ltd.
3.99 g of Irgacure 184) and 0.01 g of a polymerization inhibitor hydroquinone monomethyl ether were added and mixed to obtain a resin composition.

The viscosity of this resin composition was measured, and the shrinkage of the cured product, the gel content of the cured product, and the Young's modulus of the cured product were further measured according to the following methods. The results are shown in Table 1.

Shrinkage and gel content of cured product Focused He-Cd laser light (output 20mW, wavelength 3250Å)
, Perpendicular to the surface of the resin composition, 60 mm × 70 mm × 0.
It was irradiated so that a 5 mm rectangle could be obtained. The density (D ₁ ) of the cured resin composition and the density (D ₂ ) of the resin composition before curing were measured, and the shrinkage rate of the cured product was calculated from the following formula.

Shrinkage (%) = 100 × [(1 / D ₂ ) − (1 / D ₁ )] / (1 / D ₂ ) The gel content of the cured product at this time was measured according to the following method. .

The resin composition was cured under the same conditions as those used to measure the shrinkage rate of the cured product, and 60 mm x 10 mm was obtained from the resulting cured product.
Seven rectangles of × 0.5 mm were cut out. After measuring their weight at 23 ° C., they were filled in a cylindrical filter paper and extracted with methyl ethyl ketone for 10 hours using a Soxhlet extractor. After the extraction was completed, it was dried at 50 ° C. under reduced pressure for 5 hours.
After the completion of drying, the weight of the residual cured product was measured again at 23 ° C. to calculate the gel content.

Young's modulus of cured product Focused He-Cd laser light (output 20mW, wavelength 3250Å)
, Perpendicular to the surface of the resin composition, 100 mm × 6 mm × 0.
Irradiation was performed to obtain a 5 mm rectangle. The cured resin composition was conditioned at 23 ° C. and 50% relative humidity for 24 hours to prepare a test piece. Using a tensile tester, the Young's modulus of this test piece was measured at a humidity of 23 ° C and a relative humidity of 50% at a tensile speed of 25 mm / mi.
n, the distance between the marked lines was 50 mm.

Comparative Example 1 A composition was obtained in the same manner as in Example 1 except that vinylpyrrolidone was used instead of isobornyl acrylate in an amount of 38.4 g. The gel content of the cured product and the Young's modulus of the cured product were measured. The results are shown in Table 1.

(Effect of the Invention) The optical three-dimensional modeling resin composition of the present invention has a low viscosity,
Moreover, since the volumetric shrinkage rate at the time of curing is small, it is possible to obtain a modeled article with good dimensional accuracy by the optical three-dimensional modeling method. Further, since the flexibility after curing is also excellent, a molded article having good mechanical properties can be obtained.

 ─────────────────────────────────────────────────── ─── Continued Front Page (72) Inventor Edward Murphy, Illinois, USA 60058, Mount Prospect, S. High Lucy 18 (72) Inventor Robert E. Ansel United States, Illinois 60194, Hoffman Estates, Coldwell Lane 1440 (56) References JP 62-129306 (JP, A)

Claims (1)

(57) [Claims] 1. An optical system comprising (A) a monomer compound containing an ethylenically unsaturated compound having a cross-linked alicyclic hydrocarbon group, (B) a polymer having an ethylenically unsaturated group, and (C) a polymerization initiator. Resin composition for stereoscopic modeling.