JP2003226724A - Radical polymerizable resin composition for modeling, and three-dimensional molded article - Google Patents

Abstract

(57) [Summary] [Problems] (i) low viscosity when not cured;
(i) fast curing properties, (iii) good mechanical properties after curing, and (iv) low volumetric shrinkage during curing, and a three-dimensional structure by an optical three-dimensional molding method. The present invention provides a suitable molding resin composition for use in the production of SOLUTION: The radical polymerizable resin composition for molding of the present invention comprises at least one compound selected from the group consisting of at least polyester (meth) acrylate, urethane (meth) acrylate, and epoxy (meth) acrylate ( A), a water-soluble ethylenically unsaturated compound having at least one radically polymerizable ethylenically unsaturated bond in the molecule (B), and a polymerization initiator (C)
And a water (D) having a saturated moisture content of the mixture or less, and an E-type viscosity at 25 ° C. of 80
0 mPa · s or less.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a radically polymerizable resin composition suitable for use in producing a three-dimensional object by an optical three-dimensional object forming method, and a three-dimensional object produced by using the resin composition. It relates to a shaped object.

[0002]

2. Description of the Related Art In recent years, as a method for producing a three-dimensional object, a step of forming a thin film made of a resin composition for optical three-dimensional object and a step of irradiating the thin film with light energy and curing the same are repeated a plurality of times. Accordingly, an optical three-dimensional modeling method has been proposed in which a plurality of cured thin films are laminated to manufacture a three-dimensional model having a desired shape (Japanese Patent Laid-Open No. 56-144478).
JP, JP-A-60-247515, and JP-A-62.
-35,966, JP-A-1-204915,
JP-A-2-113925, JP-A-2-14561
No. 6, JP-A-2-153722, JP-A-3-
15520, JP-A-3-21432, JP-A-3-41126). According to such an optical three-dimensional modeling method, a desired three-dimensional molded article can be easily manufactured in a relatively short time even if the shape of the three-dimensional molded article to be manufactured is complicated, which is preferable.

[0003]

Conventionally, a cationically polymerizable resin composition has been proposed as a resin composition for optical three-dimensional modeling suitable for use in producing a three-dimensional molded article by an optical three-dimensional modeling method. There is. For example, JP-A 1-21330
No. 4 discloses an optical three-dimensional modeling resin composition containing an energy ray-curable cationically polymerizable organic compound and an energy ray-sensitive cationically polymerizable initiator. Further, JP-A-2-28261 discloses a resin composition for optical three-dimensional modeling containing an energy ray-curable cationically polymerizable organic compound and an energy ray-curable radically polymerizable organic compound.

A radically polymerizable resin composition has been proposed as another optical three-dimensional modeling resin composition.
For example, JP-A-1-204915 discloses a resin for optical stereolithography containing a monomer compound containing an ethylenically unsaturated compound having a crosslinked alicyclic hydrocarbon group and a polymer having an ethylenically unsaturated group. Compositions are disclosed.

Here, as the resin composition for optical three-dimensional molding, from the viewpoints of handleability, molding speed, molding accuracy, etc.
(I) low viscosity when uncured, (ii) rapid curing by irradiation with light energy, (iii) good mechanical properties (toughness, rigidity) after curing, (i)
v) It is necessary to have characteristics such as a small volume shrinkage ratio upon curing. Further, among these, in particular, it is possible to easily eliminate the bubbles mixed in when the resin composition for optical three-dimensional modeling is put into the tank in the three-dimensional modeling apparatus, and it is possible to shorten the time until the modeling work starts, and the lamination operation. Since it is easy to obtain a uniform laminated film in repeated steps,
(I) It is important to have a low viscosity when uncured.

[0006] However, the above-mentioned Japanese Patent Laid-Open No. 1-213.
The cationically polymerizable resin composition for optical three-dimensional modeling disclosed in Japanese Patent Application Laid-open No. 304-28261 and Japanese Patent Application Laid-Open No. 2-28261 has a relatively low viscosity when uncured, but has insufficient sensitivity to light energy. There was a problem that it was difficult to cure. Also, Japanese Patent Laid-Open No. 1-20491
The radically polymerizable resin composition for optical three-dimensional modeling disclosed in Japanese Patent Publication No. 5 needs to use a large amount of a photocurable diluent in order to reduce the viscosity of the radically polymerizable oligomer. As a photocurable diluent, it is necessary to have properties such as low viscosity, low skin irritation, fast curing speed, and excellent mechanical properties of the cured product. When a photo-curable diluent having is added, it is possible to reduce the viscosity when uncured, but the volumetric shrinkage rate at the time of curing tends to increase, and a three-dimensional object having a desired shape and size can be manufactured with high accuracy. There was a fear that it could not be manufactured well. In addition, there is a possibility that mechanical properties such as tensile strength and elongation of the obtained three-dimensionally shaped product may deteriorate.

Therefore, the present invention has been made in view of the above circumstances, and (i) has a low viscosity when uncured.
(Iii) fast curability, (iii) good mechanical properties after curing, and (iv) small volume shrinkage upon curing are all satisfied, and three-dimensional by an optical three-dimensional modeling method. It is an object of the present invention to provide a resin composition for modeling suitable for use in manufacturing a molded article, and a three-dimensional molded article obtained by using the resin composition.

[0008]

Means for Solving the Problems The present inventor has found that a radical-polymerizable resin composition is used as a photo-curable diluent and is a water-soluble resin having at least one radically polymerizable ethylenically unsaturated bond in the molecule. Blending an ethylenically unsaturated compound,
Furthermore, it has been found that the above problems can be solved by adding water having a saturated water content or less, and the inventors have invented the following radical-polymerizable resin composition for modeling and a three-dimensional model.

The radically polymerizable resin composition for modeling of the present invention comprises at least a polyester (meth) acrylate,
Urethane (meth) acrylate and epoxy (meth)
At least one compound (A) selected from the group consisting of acrylates, water-soluble ethylenically unsaturated compound (B) having at least one radically polymerizable ethylenically unsaturated bond in the molecule, and polymerization initiation In a mixture of the agent (C), water (D) having a saturated water content of the mixture or less
Is blended.

The present inventor has blended a radically polymerizable resin composition with a water-soluble ethylenically unsaturated compound (B) and water (D) having a saturated water content or less to obtain a tensile strength and elongation after curing. It was found that the uncured viscosity can be reduced without lowering the mechanical properties (toughness, rigidity) such as.
Specifically, the E-type viscosity at 25 ° C is 800 mPa ·
It has been found that it can be set to s or less. It was also found that the radical-polymerizable resin composition for modeling of the present invention has fast curability and has a small volume shrinkage rate upon curing.

That is, the radical-polymerizable resin composition for modeling of the present invention has (i) a low viscosity when uncured,
(Ii) fast curing property, (iii) good mechanical properties after curing, and (iv) low volume shrinkage ratio upon curing are all satisfied. Therefore, the radically polymerizable resin composition for modeling of the present invention,
A resin composition suitable for use in producing a three-dimensional molded article by an optical three-dimensional molding method, and by using the radically polymerizable resin composition for molding of the present invention, a three-dimensional molded article having a desired shape or size Can be manufactured accurately, stably, and efficiently.

In the radically polymerizable resin composition for molding of the present invention, a photopolymerization initiator is suitable as the polymerization initiator (C). Moreover, in the radically polymerizable resin composition for modeling of the present invention, the mixture contains the compound (A) based on 100 parts by mass of the compound (A) and the compound (B).
To 5 to 90 parts by mass and the compound (B) to 95 to 10 parts by mass.

The three-dimensional molded article of the present invention is characterized by being produced using the above-described radically polymerizable resin composition for modeling of the present invention. Since the three-dimensional molded object of the present invention is manufactured by using the radically polymerizable resin composition for molding of the present invention, it can be manufactured accurately, stably and efficiently.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below. In the present specification, "(meth) acrylic acid" means "acrylic acid or methacrylic acid", "(meth) acryloyl group" means "acryloyl group or methacryloyl group", and "(meth) acrylate" means "acrylate or methacrylate". Respectively. The term "saturated water content" means the maximum amount that can be added at 25 ° C to 100 parts by mass of the mixture of components (A), (B), and (C) within a range that does not cause cloudiness. It means the amount of water.

[Radical Polymerizable Resin Composition for Modeling] The radical polymerizable resin composition for modeling of the present invention comprises at least:
Polyester (meth) acrylate, urethane (meth)
At least one compound (A) selected from the group consisting of acrylate and epoxy (meth) acrylate,
In a mixture of a water-soluble ethylenically unsaturated compound (B) having at least one radically polymerizable ethylenically unsaturated bond in the molecule, and a polymerization initiator (C),
It is characterized in that it comprises water (D) in an amount not more than the saturated water content of the mixture. The radically polymerizable resin composition for molding of the present invention is characterized by containing a water-soluble ethylenically unsaturated compound (B) and water (D) having a saturated water content or less. There is.

Hereinafter, each component will be described in detail. <Compound (A)> Polyester (meth) acrylate,
At least one compound (A) selected from the group consisting of urethane (meth) acrylate and epoxy (meth) acrylate is required to be a three-dimensional object manufactured using the radically polymerizable resin composition for modeling of the present invention. The compound can be appropriately selected depending on the characteristics and the like, and the following compounds can be exemplified.

Polyester (meth) acrylates include polybasic acids such as phthalic acid and adipic acid, and ethylene glycol, neopentyl glycol, caprolactane diol, 1,6-hexane diol, polyethylene glycol, polytetramethylene glycol. Examples thereof include polyester (meth) acrylates obtained by reacting a polyhydric alcohol such as the above with (meth) acrylic acid or a derivative thereof.

Examples of urethane (meth) acrylates include isocyanates such as hexamethylene diisocyanate, isophorone diisocyanate, tolylene diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, naphthalene diisocyanate and norbornane diisocyanate. Compounds and polyethylene glycol, polypropylene glycol, polytetramethylene glycol, ethylene oxide adduct of bisphenol A, propylene oxide adduct of bisphenol A, polyester polyol, polycarbonate diol, γ-butyrolactone, γ-valerolactone, δ-valerolactone , Ε-caprolactone, etc. And Rokishikarubon ester, ammonia, or ethanolamine, diethanolamine, N- methylethanolamine, N- ethyl ethanolamine, N- phenylethanolamine, 2-amino-1-butanol, 2-amino-2-ethyl-1,
Compounds containing one primary or secondary amino nitrogen such as 3-propanediol, 6-amino-1-hexanol, 1,4-diaminobutane, 1,2-diaminocyclohexane, 1,10-diaminodecane A polyol compound such as an aminohydroxy compound which is a reaction product of
-(Meth) acrylate having a hydroxyl group such as hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate Urethane di (meth) obtained by reacting with other compounds
Acrylates; isocyanate compounds such as hexamethylene diisocyanate, isophorone diisocyanate, tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, naphthalene diisocyanate, norbornane diisocyanate, and their multimers, and 2-hydroxyethyl (meth) acrylate. Two
-Hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate and urethane poly (meth) acrylates to which a (meth) acrylate having a hydroxyl group such as a caprolactone adduct thereof is added can be exemplified.

As the epoxy (meth) acrylate, a glycidyl ether compound such as a phenol novolac type epoxy resin, a cresol novolac type epoxy resin, a bisphenol A type epoxy resin, a bisphenol F type epoxy resin or the like is added to (meth) acrylic acid or its Examples thereof include epoxy poly (meth) acrylates obtained by reacting a derivative.

Among these, urethane acrylate is particularly preferable because of its excellent mechanical properties such as tensile strength and elongation of the obtained three-dimensional model, and among them, isophorone diisocyanate, amide diol, polybutylene glycol, Urethane acrylates obtained by reacting 2-hydroxypropyl acrylate are preferred.

In the radically polymerizable resin composition for molding of the present invention, the content of the compound (A) is 5 to 90 parts by mass based on 100 parts by mass of the total of the compound (A) and the compound (B). It is preferable that the amount is 10 to 50 parts by mass. When the content of the compound (A) exceeds 90 parts by mass, the viscosity of the obtained radically polymerizable resin composition for modeling becomes high, and workability at the time of producing a three-dimensional modeled object may be lowered, which is preferable. Absent. Further, when the content of the compound (A) is less than 5 parts by mass, it cannot be completely cured when producing a three-dimensional object, and mechanical properties of the obtained three-dimensional object may be deteriorated. Not preferable.

<Compound (B)> The water-soluble ethylenically unsaturated compound (B) having at least one radically polymerizable ethylenically unsaturated bond in the molecule is the radically polymerizable resin for modeling of the present invention. It can be appropriately selected according to the required properties of the three-dimensional model produced using the composition, but (meth) acrylic acid, N-isopropylacrylamide, N-vinylpyrrolidone, N-vinylcaprolactam, (meth) Allylsulfonic acid, N, N-dimethyl (meth) acrylamide, (meth) acrylic acid N, N-
Dimethylaminoethyl, N, N-diethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylamide, (meth) acryloylmorpholine, 2-hydroxyethyl (meth) acrylate, (
(Meth) 2-hydroxypropyl acrylate, 2-hydroxybutyl (meth) acrylate, polyoxyalkylene-modified polyethylene glycol di (meth) acrylates, polyoxyalkylene-modified bisphenol A di (meth) acrylates, polyoxyalkylene-modified nonylphenol Examples thereof include (meth) acrylates.

Of these, ethylenically unsaturated compounds having an amide group and / or an alkylamino group in the molecule are particularly preferred because of their high solubility in water and the improved mechanical properties of the resulting three-dimensional model. Compounds are preferred. Among them, N, N-dimethyl (meth) acrylamide or (meth) acryloylmorpholine is particularly preferable. One of these may be used alone, or two or more of them may be used in combination.

In the radically polymerizable resin composition for molding of the present invention, the content of the compound (B) is 10 to 95 parts by mass based on 100 parts by mass of the total amount of the compound (A) and the compound (B). It is preferable that the amount is 10 to 50 parts by mass. When the content of the compound (B) exceeds 90 parts by mass, the resulting radical-polymerizable resin composition for modeling and the three-dimensional molded article have remarkably high hygroscopicity, and the three-dimensional molded article tends to soften, which is preferable. Absent. Moreover, when the content of the compound (B) is less than 10 parts by mass, the saturated water content of the obtained radically polymerizable resin composition for molding decreases. Therefore, the amount of soluble water decreases, and the viscosity of the obtained radical-polymerizable resin composition for modeling when uncured may increase, which is not preferable.

<Other ethylenically unsaturated compounds (E)
In the radical-polymerizable resin composition for molding of the present invention, in addition to the compound (A) and the compound (B), an ethylenic unsaturated compound having at least one radical-polymerizable ethylenically unsaturated bond in the molecule. You may add a saturated compound (E) as needed. Specific examples thereof include vinyl ester monomers such as divinyl adipate; vinyl ethers such as ethyl vinyl ether and phenyl vinyl ether;
Methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, (meth)
T-butyl acrylate, hexyl (meth) acrylate,
2-Ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, glycidyl (meth) acrylate, benzyl (meth) acrylate, (meth) acrylic Acid cyclohexyl, phenoxyethyl (meth) acrylate, tricyclodecane (meth) acrylate, allyl (meth) acrylate, (meth) acrylic acid 2
-Ethoxyethyl, isobornyl (meth) acrylate,
Phenyl (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate,
Polyethylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylic acid, di ( (Meth) acrylic acid 1,9-nonanediol, di (meth) acrylic acid neopentyl glycol, hydroxypivalic acid neopentyl glycol di (meth) acrylic acid ester, propylene glycol di (meth) acrylic acid, di (meth) acrylic acid Examples include dipropylene glycol, tripropylene glycol di (meth) acrylate, tetrapropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, and polytetramethylene glycol di (meth) acrylate. These can be used alone or in combination of two or more.

Among these, in particular, since it has a low viscosity and has a diluting action, 2-ethylhexyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, benzyl (meth) acrylate, and (meth) acrylic. Cyclohexyl acid, phenoxyethyl (meth) acrylate, tricyclodecane (meth) acrylate, isobornyl (meth) acrylate, phenyl (meth) acrylate,
Di (meth) acrylic acid 1,6-hexanediol, di (meth) acrylic acid 1,9-nonanediol, di (meth) acrylic acid neopentyl glycol, hydroxypivalic acid neopentyl glycol di (meth) acrylic acid ester, etc. Is preferred.

<Polymerization Initiator (C)> The polymerization initiator (C) is not particularly limited, but a photopolymerization initiator is preferred. As the photopolymerization initiator, benzophenone,
4,4-bis (diethylamino) benzophenone, 2,
4,6-trimethylbenzophenone, methylorthobenzoylbenzoate, 4-phenylbenzophenone, t
-Butylanthraquinone, 2-ethylanthraquinone, thioxanthones such as 2,4-diethylthioxanthone, isopropylthioxanthone, and 2,4-dichlorothioxanthone; diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropane-1- On, benzyl dimethyl ketal, 1-hydroxycyclohexyl-phenyl ketone, 2-methyl-2-morpholino (4-thiomethylphenyl) propan-1-one, 2
-Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone and other acetophenones; benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether and other benzoin ethers; 2,4,6- Trimethylbenzoyldiphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, bis (2,4,4)
Examples include acylphosphine oxides such as 6-trimethylbenzoyl) -phenylphosphine oxide; methylbenzoyl formate, 1,7-bisacridinyl heptane, 9-phenylacridine, and the like. These can be used alone or in combination of two or more.

In the radically polymerizable resin composition for molding of the present invention, the content of the polymerization initiator (C) is the same as that of the compound (A).
0.01 with respect to 100 parts by mass of the total amount of the compound (B) and
It is preferably ˜15 parts by mass, more preferably 0.1 to 10 parts by mass. When the content of the polymerization initiator (C) is less than 0.01 parts by mass, the curability of the obtained radically polymerizable resin composition for molding is significantly reduced, and the productivity in producing a three-dimensional molded article is significantly reduced. There is a fear that it is not preferable. Further, when the content of the polymerization initiator (C) exceeds 15 parts by mass, if the irradiation light energy is small during the production of the three-dimensional object, odor may remain in the obtained three-dimensional object, which is not preferable. .

<Water (D)> The radical-polymerizable resin composition for modeling of the present invention is prepared by adding at least a mixture of the above-mentioned compound (A), compound (B) and polymerization initiator (C) to the mixture. It is constituted by dissolving water (D) having a saturated water content equal to or less than. Distilled water is suitable as the water (D). The term "saturated water content" used here means the components (A), (B),
It means the maximum amount of water that can be added at 25 ° C. with respect to 100 parts by mass of the mixture composed of (C) within a range in which the resulting composition does not become cloudy. At least compound (A),
Mechanical properties such as tensile strength and elongation (toughness) of a three-dimensional model obtained by dissolving water (D) having a saturated water content or less in a mixture composed of a compound (B) and a polymerization initiator (C) , Rigidity) can be reduced without lowering the uncured viscosity. Specifically, the E-type viscosity at 25 ° C. can be set to 800 mPa · s or less. Thus, the E-type viscosity at 25 ° C is 800 mP
Since the viscosity can be as low as a · s or less, by using the radical-polymerizable resin composition for molding of the present invention,
It is possible to remarkably improve workability when manufacturing a three-dimensional molded item.

The amount of water (D) added is at least
When the saturated water content of the mixture of the components (A), (B), and (C) is exceeded, the resulting radical-polymerizable resin composition for modeling and the three-dimensional molded article become turbid, and the transparency is deteriorated.
Aesthetically unpleasant. In addition, mechanical properties such as tensile strength and elongation of the obtained three-dimensional model may be deteriorated, which is not preferable.

<Other Components> In the radical-polymerizable resin composition for modeling of the present invention, if necessary, ethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine, methyl 4-dimethylaminobenzoate, Known photosensitizers such as ethyl 4-dimethylaminobenzoate, amyl 4-dimethylaminobenzoate, and 4-dimethylaminoacetophenone can also be added. Further, the radical-polymerizable resin composition for modeling of the present invention, within the scope not departing from the gist of the present invention, a release agent, a lubricant, a plasticizer, an antioxidant, an antistatic agent,
Light stabilizers, ultraviolet absorbers, flame retardants, flame retardant aids, polymerization inhibitors, fillers, pigments, dyes, silane coupling agents, etc.,
Various additives can be appropriately added depending on the application.
Further, the modeling radical-polymerizable resin composition of the present invention,
If necessary, an organic solvent may be added as long as the performance of the obtained three-dimensional molded item is not impaired.

The radical-polymerizable resin composition for modeling of the present invention is constituted as described above. In the radical-polymerizable resin composition for modeling of the present invention, the water-soluble ethylenically unsaturated compound (B) and saturated water content are contained. The greatest feature is that the following water (D) is added. By adopting such a configuration, the E-type viscosity at 25 ° C. is set to 800 mPa · s or less without lowering the mechanical properties (toughness, rigidity) such as tensile strength and elongation of the obtained three-dimensional molded item. It is possible to achieve low viscosity when uncured.

Further, since a low viscosity at the time of uncuring can be realized in this way, the workability of three-dimensional modeling is remarkably improved by producing a three-dimensional molded article using the radical-polymerizable resin composition for modeling of the present invention. Can be improved. In particular,
Bubbles mixed in when the radically polymerizable resin composition for molding of the present invention is put into the tank in the three-dimensional modeling device are easily lost, and the time until the start of modeling work can be shortened, and the production efficiency of three-dimensional modeling is improved. can do. In addition, since a uniform laminated film can be stably obtained in the repeating step of the laminating operation, a uniform three-dimensional object can be stably manufactured.

Further, the radical-polymerizable resin composition for molding of the present invention has the property that it is rapidly cured by irradiation with light energy and has a small volume shrinkage ratio upon curing.
Further, the radical-polymerizable resin composition for modeling of the present invention has no turbidity, is excellent in transparency, and is excellent in aesthetics. Therefore, by using the radically polymerizable resin composition for modeling of the present invention, a three-dimensional model having a desired shape and dimensions can be obtained.
It can be manufactured accurately, stably, and efficiently.

The radical-polymerizable resin composition for modeling of the present invention is suitable for optical three-dimensional modeling, but is not limited to this application. The modeling radical-polymerizable resin composition of the present invention has a small volume shrinkage ratio upon curing, is excellent in dimensional accuracy after curing, is excellent in mechanical properties such as tensile strength and elongation after curing, and is transparent. Since it has characteristics such as excellentness, it is suitable as a resin for vacuum casting and a resin for 2P other than optical three-dimensional modeling.

[Three-dimensional object] The three-dimensional object of the present invention can be produced by using the above-described radically polymerizable resin composition for modeling of the present invention. The structure, shape, size, etc. of the three-dimensional model to be manufactured are not particularly limited and can be appropriately designed according to the application. As a method for producing a three-dimensional molded article, a known optical three-dimensional modeling method can be adopted. For example, a step of forming a thin film composed of the radically polymerizable resin composition for molding of the present invention, and the thin film An optical three-dimensional modeling method in which a plurality of cured thin films are laminated to produce a three-dimensional model having a desired shape by repeating a step of selectively irradiating and curing light energy by a plurality of times is suitable. It should be noted that the three-dimensional object manufactured by the optical three-dimensional molding method may be used as it is as a product, and further, it may be post-cured by light irradiation or heating to improve its mechanical characteristics or shape stability. Good as a product.

As a light beam for irradiating to cure the thin film, Ar laser, He-Cd laser, He-Ne laser, ArF excimer laser, CO ₂ laser, N
A laser beam emitted from a d: YAG laser, a semiconductor laser, a Dye laser, or the like, or an active energy ray such as an ultraviolet ray emitted from a xenon lamp, a metal halide lamp, a mercury lamp, a fluorescent lamp, or the like is preferable. Of these, a laser beam is particularly preferable. With the laser beam, the irradiation energy can be increased, the curing time can be shortened, and the beam shape can be reduced, so that the light irradiation area for one time can be reduced and the molding accuracy can be improved. A high three-dimensional model can be obtained.

Since the three-dimensional molded article of the present invention is manufactured using the radically polymerizable resin composition for molding of the present invention, it can be manufactured accurately, stably and efficiently. Become.

The technique of the present invention is incorporated into a machine product or the like as a model for verifying the appearance design in the middle of design, a model for checking the functionality of parts, and an actual part.
It can be applied to applications such as making models for checking performance, resin molds, base models for making molds, and direct molds for prototype molds. More specifically, applications such as production of models for precision parts, electric / electronic parts, furniture, building structures, automobile parts, various containers, castings, dies, mother dies, etc. and processing models. Can be applied to. In particular, taking advantage of its good mechanical properties (toughness, rigidity) and transparency, it is possible to fabricate parts for repeated fatigue testing, such as the design of fitting parts of home appliances, and parts for mechanical strength analysis of complex structures. Very useful for manufacturing.

[0040]

EXAMPLES Next, examples and comparative examples according to the present invention will be described. (Synthesis Example 1) Production of Urethane Acrylate (UA1: Compound (A)) (1) 1853 g of dicyclohexylmethane diisocyanate in a three-necked flask having an internal volume of 5 liter equipped with a stirrer, a temperature controller, a thermometer and a condenser ( 14 mol equivalents) and 0.7 g of dibutyltin dilaurate were charged and heated in a water bath so that the internal temperature was 70 ° C. (2) On the other hand, 175 g (2.8 g of N-methyl-N- (2-hydroxyethyl) -3-hydroxypropylamide)
(Mole equivalent weight) and 1528 g (3.5 mole equivalent weight) of polybutylene glycol (n = 12, average molecular weight: 850) were uniformly mixed and dissolved into a dropping funnel equipped with a side tube.
The liquid in the dropping funnel was added dropwise to the contents in the flask in (1) above. In addition, while stirring the content in the flask of (1) above, while maintaining the flask internal temperature at 65 to 75 ° C., the mixture was added dropwise at a constant rate over 4 hours. Further, after completion of dropping, the mixture was stirred at the same temperature for 2 hours for reaction. (3) Then, after cooling the contents of the flask to 60 ° C., 886 g (7.6 mol equivalent) of 2-hydroxyethyl acrylate charged in another dropping funnel and 2.5 g of hydroquinone monomethyl ether were uniformly mixed and dissolved. The resulting solution was added dropwise at a constant rate over 2 hours while maintaining the flask internal temperature at 55 to 65 ° C., and then reacted for 4 hours while maintaining the flask content temperature at 75 to 85 ° C. Urethane acrylate (UA1) which is (A) was manufactured. The obtained reaction product was colorless and transparent. Incidentally, the residual isocyanate equivalent is measured,
The time point when the residual isocyanate equivalent was less than 1% was taken as the end point of the reaction.

(Synthesis Example 2) Urethane acrylate (U
A2: Production of Compound (A) (1) In a three-necked flask having an internal volume of 5 liters equipped with a stirrer, a temperature controller, a thermometer and a condenser, 600 g (5.2 molar equivalents) of isophorone diisocyanate and dibutyl. 0.2 g of tin dilaurate was charged and heated in a water bath so that the internal temperature became 70 ° C. (2) On the other hand, N-methyl-N- (2-hydroxyethyl) -3-hydroxypropylamide 63 g (0.7 molar equivalent) and polybutylene glycol (n = 12, average molecular weight: 850) 393 g (0.9) A liquid in which (molar equivalents) were uniformly mixed and dissolved was charged into a dropping funnel with a side tube, and the liquid in the dropping funnel was added dropwise to the contents in the flask of (1) above. In addition, while stirring the content in the flask of (1) above, while maintaining the flask internal temperature at 65 to 75 ° C., the mixture was added dropwise at a constant rate over 4 hours. Further, after completion of dropping, the mixture was stirred at the same temperature for 2 hours for reaction. (3) Next, after lowering the temperature of the flask contents to 60 ° C., 436 g (3.8 mol equivalent) of 2-hydroxyethyl acrylate charged in another dropping funnel and 0.8 g of hydroquinone monomethyl ether were uniformly mixed. After the dissolved liquid was added dropwise at a constant rate over 2 hours while maintaining the flask internal temperature at 55 to 65 ° C, the reaction was carried out for 4 hours while maintaining the temperature of the flask contents at 75 to 85 ° C. , Urethane acrylate (UA2) which is the compound (A) was produced. The obtained reaction product was colorless and transparent. The end point of the reaction was determined in the same manner as in Synthesis Example 1.

Example 1 <Preparation of Radical Polymerizable Resin Composition for Modeling> As the compound (A), 35 parts by mass of the urethane acrylate (UA1) synthesized in Synthesis Example 1, a water-soluble ethylenically unsaturated compound ( As B), 40 parts by mass of acrylic morpholine (ACMO manufactured by Kojin Co., Ltd.), and 5 parts by mass of N, N-dimethylacrylamide (DMAA manufactured by Kojin Co., Ltd.) other than compound (A) and compound (B) As the ethylenically unsaturated compound (E), a diacrylic acid ester (Kayarad HX220, manufactured by Nippon Kayaku Co., Ltd.) of a caprolactone 2 mol adduct of neopentyl glycol hydroxypivalate 10
Parts by mass, and triisocyanuric acid EO-modified triacrylate (Aronix M-315 manufactured by Toagosei Co., Ltd.) 10
Parts by mass, 3 parts by mass of 1-hydroxycyclohexyl phenyl ketone as a polymerization initiator (C), and distilled water (D)
2 parts by mass was mixed to obtain a radical-polymerizable resin composition for modeling. The maximum amount of water that can be added within a range where the composition does not become cloudy at 25 ° C., that is, the saturated amount of water is 8 parts by mass with respect to 100 parts by mass of the mixture of components (A), (B), and (C). there were. Table 1 shows the composition of the radically polymerizable resin composition for modeling prepared in Example 1. <Manufacture of a three-dimensional object by optical three-dimensional molding method> Using the obtained radically polymerizable resin composition for modeling, an ultra-high-speed stereolithography system (“SOLIFORM 25 manufactured by Teijin Seiki Co., Ltd.”
0 "), solid-state laser light (power 100 mW,
(Wavelength 365 nm) is irradiated perpendicularly to the surface, the slice pitch (lamination thickness) is 0.127 mm, and the average molding time per layer is 2 minutes to perform optical molding.
A dumbbell test piece-shaped three-dimensional object conforming to 113 was obtained. Further, the obtained three-dimensional model is washed with isopropyl alcohol to remove the uncured composition adhering thereto, and then post-cured by irradiating with 3 kW of ultraviolet rays for 10 minutes.
I got a three-dimensional object.

(Examples 2 to 7) Radical-polymerizable resin compositions for molding were obtained in the same manner as in Example 1 except that the compositions shown in Table 1 were used. Further, using the obtained radically polymerizable resin composition for modeling, a three-dimensional modeled object was obtained in the same manner as in Example 1. (Comparative Examples 1 to 7) Radical polymerizable resin compositions for modeling were obtained in the same manner as in Example 1 except that the compositions shown in Table 2 were used. Further, using the obtained radically polymerizable resin composition for modeling, a three-dimensional modeled object was obtained in the same manner as in Example 1.

In Tables 1 and 2, the unit of the blending amount of each component is "part by mass", and the "saturated water content" is the mixture 100 consisting of the components (A), (B) and (C). With respect to parts by mass, the maximum amount of water that can be added within the range where the composition does not become cloudy at 25 ° C is shown. Further, each abbreviation in Tables 1 and 2 represents the following compound. UA1: urethane acrylate UA2: urethane acrylate UK-4203: polyester acrylate (manufactured by Mitsubishi Rayon Co., Ltd.) UK-6105: epoxy acrylate (manufactured by Mitsubishi Rayon Co., Ltd.) ACMO: acrylic morpholine (manufactured by Kojin Co., Ltd.) DMAA: N, N-dimethylacrylamide (manufactured by Kojin Co., Ltd.) HX-220: diacrylic acid ester of caprolactone adduct of neopentyl glycol hydroxypivalate (n + m = 2) (manufactured by Nippon Kayaku Co., Ltd.) BPE-4: EO-modified bisphenol A diacrylate (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) M-315: triisocinuric acid EO-modified triacrylate (manufactured by Toagosei Co., Ltd.) Irg184: 1-hydroxycyclohexyl phenyl ketone

(Evaluation Items and Evaluation Methods) The radical-polymerizable resin composition for modeling and the three-dimensional molded objects obtained in each of the examples and comparative examples were evaluated as follows. 1. Transparency of the radical-polymerizable resin composition for modeling (solubility in water) The obtained radical-polymerizable resin composition for modeling is placed in a glass container, visually observed, and its transparency is evaluated based on the following criteria. did. When the composition is uniform and transparent, the added water is completely dissolved, and when the composition is cloudy or separated, it means that the added water is not completely dissolved. . Criteria o: The composition was uniform and excellent in transparency. (The added water was completely dissolved.) X: The composition was cloudy or separated. (The added water was not completely dissolved.)

2. Viscosity of radical-polymerizable resin composition for modeling The E-type viscosity of the obtained radical-polymerizable resin composition for modeling at 25 ° C was measured and evaluated based on the following criteria. Judgment Criteria: E-type viscosity at 25 ° C. is 300 to 800 mPa.
It was s. X: E type viscosity at 25 ° C. was more than 800 mPa · s.

3. Mechanical properties of three-dimensional model The tensile properties of the three-dimensional model obtained are measured according to JIS K 7113.
It was measured according to. Since it is considered to have sufficient mechanical properties, the maximum point stress (tensile strength) was evaluated as ◯ when it was 30 MPa or more, and as x when it was less than that. The elongation at break (tensile elongation) was evaluated as ◯ when it was 10% or more and as x when it was less than that. The Young's modulus (elastic modulus) was evaluated as ◯ when it was 1200 MPa or more and as x when it was less than 1200 MPa.

(Results) Tables 1 and 2 show the results obtained in each Example and Comparative Example. As shown in Table 1, the compound (A), the compound (B), the polymerization initiator (C), and water (D) are blended, and the compound (A) is blended in an amount of 35 to 50 parts by mass and the compound (B). A radically polymerizable resin composition for modeling is prepared by using 35 to 50 parts by mass of), 3 parts by mass of a polymerization initiator (C), and 1 to 5 parts by mass of water (D). In Examples 1 to 7, which are excellent in transparency,
A low-viscosity resin composition having an E-type viscosity at 25 ° C. of 540 to 750 mPa · s was obtained. Further, by using the obtained resin composition, a three-dimensional modeled article excellent in tensile strength, tensile elongation, elastic modulus and mechanical properties was obtained.

On the other hand, in Comparative Examples 1 to 3 in which the radical-polymerizable resin composition for modeling was prepared without blending water (D), resin compositions having excellent transparency were obtained and obtained. By using the resin composition, a three-dimensional molded article having excellent tensile strength, tensile elongation, elastic modulus, and mechanical properties was obtained.
However, the E of the obtained resin composition at 25 ° C.
The mold viscosity was 900 to 1300 mPa · s, and reduction in viscosity could not be realized.

Further, the compounding amount of the compound (A) is 35 parts by mass, the compounding amount of the compound (B) is 45 parts by mass, the compounding amount of the polymerization initiator (C) is 3 parts by mass, and the compounding amount of water (D). In Comparative Example 4 in which the radical-polymerizable resin composition for modeling was prepared with 10 parts by mass as E.C.
A low-viscosity resin composition of a · s was obtained. However, the obtained resin composition was cloudy and was not preferable in terms of appearance. This is because water (D) having a saturated water content or more was added. In addition, the tensile strength of the three-dimensional model obtained by using this resin composition was low, and the mechanical properties of the obtained three-dimensional model were not sufficient.

Further, the compound (A) was prepared without adding water (D).
In Comparative Example 5 in which 97 parts by mass of the compound (B) was blended with 100 parts by mass of the compound and the compound (B), the transparency was excellent and the E-type viscosity at 25 ° C. was 10 mPa · s.
A resin composition having an extremely low viscosity was obtained. However, since the amount of the compound (A) added was too small, curing failure occurred during the production of a three-dimensional structure, and curing could not be completed completely. Therefore, the mechanical properties of the three-dimensional model could not be measured. That is, the three-dimensional molded item obtained in Example 5 was a soft one having completely insufficient mechanical properties.

Further, the compound (A) was prepared without adding water (D).
In Comparative Example 6 in which 97 parts by mass of the compound (A) was mixed with 100 parts by mass of the compound (B) in total, a resin composition having excellent transparency was obtained. However, since the amount of the compound (A) added was too large, the obtained resin composition had an E-type viscosity at 25 ° C. of 10000 mPa · s.
It had a very high viscosity. Therefore, the air bubbles present in the composition could not be completely eliminated, and the three-dimensional model could not be manufactured.

Further, in Comparative Example 7 in which 97 parts by mass of the compound (A) and 1 part by mass of water (D) were mixed with 100 parts by mass of the total amount of the compound (A) and the compound (B), it was obtained. The resin composition was cloudy and was not aesthetically pleasing. This is because the compounded amount of the compound (B) was small, the saturated water content was lowered, and even a small amount of water (D) exceeded the saturated water content. Further, since the amount of the compound (A) added was too large, the obtained resin composition had an E-type viscosity at 25 ° C. of more than 10,000 mPa · s, which was a very high viscosity. Therefore, the air bubbles present in the composition could not be completely eliminated, and the three-dimensional model could not be manufactured.

[0054]

[Table 1]

[0055]

[Table 2]

From the above results, the compound (A), the compound (B) and the polymerization initiator (C) were blended, and at least in the mixture of the components (A), (B) and (C),
By blending water (D) in an amount not more than the saturated water content of the mixture, it is possible to provide a radical-polymerizable resin composition for molding which has a low viscosity when uncured and has good mechanical properties after curing. There was found.

[0057]

According to the present invention, (i) it has a low viscosity when uncured, (ii) it has fast curing property, and (i
ii) good mechanical properties after curing, and (i
v) Satisfactory that the volumetric shrinkage rate upon curing is small,
A radically polymerizable resin composition suitable for use in producing a three-dimensional object by an optical three-dimensional object can be provided. Moreover, by using this radically polymerizable resin composition for modeling of the present invention, a three-dimensional molded article having a desired shape and size can be manufactured accurately, stably, and efficiently.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Taro Ishii             4-1-1 Sunadabashi, Higashi-ku, Nagoya-shi, Aichi               Mitsubishi Rayon Co., Ltd. Product Development Laboratory F-term (reference) 4F213 AA21 AA43 AA44 AA46 WL02                       WL12 WL23 WL24 WL25 WL43                       WL92 WL96                 4J027 AB03 AB10 AB15 AB18 AB23                       AB24 AC02 AC04 AC07 AE03                       AE04 AG03 AG04 AG08 AG12                       AG23 AG24 AG27 AG32 AG33                       BA04 BA07 BA09 BA10 BA11                       BA12 BA17 BA19 BA20 BA21                       CB10 CC05 CC07 CD01

Claims (6)

[Claims] 1. At least one compound (A) selected from the group consisting of polyester (meth) acrylate, urethane (meth) acrylate, and epoxy (meth) acrylate, and at least one radical polymerization in the molecule. A mixture of a water-soluble ethylenically unsaturated compound (B) having a possible ethylenically unsaturated bond and a polymerization initiator (C) is mixed with water (D) having a saturated water content of not more than the mixture. A radically polymerizable resin composition for modeling, which is 2. The E-type viscosity at 25 ° C. is 800 mPas.
The radical-polymerizable resin composition for molding according to claim 1, which is s or less. 3. The radically polymerizable resin composition for molding according to claim 1, wherein the polymerization initiator (C) is a photopolymerization initiator. 4. The mixture contains 5 parts of the compound (A) with respect to 100 parts by mass of the total of the compound (A) and the compound (B).
To 90 parts by mass and 95 to 10 parts by mass of the compound (B), the radically polymerizable resin composition for modeling according to any one of claims 1 to 3. 5. The radically polymerizable resin composition for modeling according to any one of claims 1 to 4, which is for optical three-dimensional modeling. 6. Any one of claims 1 to 5
A three-dimensional molded article manufactured using the radically polymerizable resin composition for molding according to the item.